Beruflich Dokumente
Kultur Dokumente
Polymeric
Nanocomposites
Volume 1
L.A. Utracki
Clay-Containing
Polymeric
Nanocomposites
Volume 1
L.A. Utracki
C. Vasile
A catalogue record for this book is available from the British Library.
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reproduced within the text and the authors and publishers apologise if any
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ISBN: 1-85957-437-8
Preamble
L.A. Utracki
During the last few years terms like nanomaterials, nanocomposites and
nanosystems have become fashionable. It seems that anything with ‘nano’ attached
to it has nearly a magical effect – not so much on performance as on expectations.
There is an extensive worldwide effort to introduce nanotechnology for the
production of materials with specific functional characteristics, e.g.,
semiconducting, electromagnetic, optical, etc. New magneto-resistance materials
with nanometre-scale spin-flip mean free path of electrons have been
commercialised. The National Science Foundation (NSF) has solicited
collaborative research proposals in the area of nanoscale science and engineering,
including: nanoscale biosystems; nanoscale structures; novel phenomena and
control; nanoscale devices and system architecture; nanosystems-specific software;
nanoscale processes; multi-phenomena modelling and simulation at the nanoscale
level; studies on societal implications of nanoscale science and engineering, etc.
Nanostructures are of interest to many technologies. The potential of precise
control of impurities and defects in a crystal and the ability to integrate perfect
inorganic and organic nanostructures may lead to a new generation of advanced
materials. To electronics, they offer quantum devices (resonant tunnelling
transistors; single electron transistors; cellular automata based on quantum dots)
and new processor architectures. To catalysis, they form the templates for catalytic
activity, zeolite pores, etc. In biology, nanostructures are components of the
mitochondrion, the chloroplast, and the ribosome.
The advances in the synthesis and fabrication of isolated nanostructures range
from colloidal synthesis of nanocrystals to the growth of epitaxial quantum dots.
The techniques of molecular biology have made a wide range of biological
nanostructures readily available through cloning and overexpression in bacterial
production systems. Furthermore, work has begun on the use of self-assembly
techniques to prepare complex and designed spatial arrangements of
nanostructures. Techniques derived from microlithography in microelectronics
(viz. photo, X-ray, and e-beam lithography) offer the potential to economically
generate new types of 3D-structures. In short, there is a great potential for the
wide use of nanotechnology for functional materials and devices.
The central theme of this book is the use of nanotechnology for the
development of new structural polymeric systems, the polymeric nanocomposites
(PNCs), and particularly the clay-containing polymeric nanocomposites (CPNCs).
These mass produced materials are dispersions of inorganic, nanoscale platelets
in a polymeric matrix. Economics preclude the use of most of the manufacturing
methods developed for ceramic and metallic nanocomposites. The key to the
success of the CPNC industry is to provide new materials significantly
outperforming the old ones at a marginal incremental cost increase per unit
volume. Considering that at present the nanoclay is a natural mineral with well-
i
Clay-Containing Polymeric Nanocomposites
ii
Preamble
iii
Clay-Containing Polymeric Nanocomposites
iv
Contents
Contents Volume 1
Preamble .................................................................................................... i
Part 1 Introduction
1.1 General ............................................................................................... 1
1.2 NCs with Ceramic or Metallic Matrix .............................................. 2
1.2.1 Metallic Nanoparticles in Amorphous Matrix ................................ 2
1.2.2 Magnetic Oxides in Silica Nanocomposites .................................... 2
1.2.3 Optoelectronics ............................................................................... 3
1.2.4 Summary on Non-Polymeric NC .................................................... 3
1.3 NCs with Polymeric Matrix .............................................................. 3
1.3.1 PNC Definitions .............................................................................. 6
1.3.2 Methods of Characterisation of CPNCs .......................................... 8
1.3.2.1 X-Ray Diffraction (XRD) .................................................. 8
1.3.2.2 Small Angle Neutron Scattering (SANS) .......................... 11
1.3.2.3 Transmission and Atomic Force Electron Microscopy
(TEM and AFM) ............................................................. 14
1.3.2.4 Fourier Transform Infrared Spectroscopy (FTIR) ............ 15
1.3.2.5 Nuclear Magnetic Resonance Spectroscopy (NMR) ........ 16
1.3.2.6 Other Methods ................................................................ 17
1.3.3 Determination of PNC Properties ................................................. 18
1.3.4 PNC Types and Methods of their Preparation .............................. 18
1.3.5 PNCs of Commercial Interest ........................................................ 18
1.3.6 Journals and Research Groups ...................................................... 29
1.3.7 Historical Perspective .................................................................... 30
v
Clay-Containing Polymeric Nanocomposites
2.1.3.1.7 PNC with CNTs – Thermoset Matrix ................. 48
2.1.3.1.8 PNC with CNTs – Thermoplastic Matrix ............ 50
2.1.3.2 Rod-Like CdSe Nanocrystals ........................................... 54
2.1.3.3 Imogolite ......................................................................... 54
2.1.3.4 Vanadium Pentoxide, V2O5 ............................................. 54
2.1.3.5 Inorganic Nanotubes ....................................................... 55
2.1.4 Other Nanoparticles ...................................................................... 56
2.1.4.1 Spherical or Nearly-Spherical Particles ............................ 56
2.1.4.2 Sol-Gel Hybrids ............................................................... 56
2.1.4.3 Polyhedral Oligomeric Silsesquioxanes (POSS) ............... 58
2.1.4.3.1 Origin and Structure ............................................ 58
2.1.4.3.2 Properties ............................................................. 60
2.1.4.3.3 Sources ................................................................. 66
2.1.4.3.4 Applications ......................................................... 67
2.2 Clays ............................................................................................... 73
2.2.1 General Characteristics ................................................................. 73
2.2.2 Crystalline Clays ........................................................................... 74
2.2.2.1 Kaolins ............................................................................ 74
2.2.2.2 Serpentines ...................................................................... 74
2.2.2.3 Illite Group (Micas) ......................................................... 74
2.2.2.4 Chlorites and Vermiculites .............................................. 76
2.2.2.5 Other Clays ..................................................................... 76
2.2.2.5.1 Glauconite ........................................................... 76
2.2.2.5.2 Sepiolite, Palygorskite and Attapulgite ................ 76
2.2.2.5.3 Mixed-Layer Clay Minerals ................................. 76
2.2.2.6 Smectites or Phyllosilicates .............................................. 76
2.2.2.6.1 Bentonite ............................................................. 79
2.2.2.6.2 Montmorillonite (MMT) ..................................... 80
2.2.3 Purification of Clay ....................................................................... 84
2.2.4 Reactions of Clays with Organic Substances ................................. 85
2.2.4.1 Clay in Aqueous Medium ................................................ 90
2.2.4.1.1 General ................................................................ 90
2.2.4.1.2 Reactions with Edge Cations ............................... 91
2.2.4.1.3 Reactions with –OH Groups ............................... 91
2.2.4.1.4 Reaction with the Silicilic Surface Anions ........... 91
2.2.4.1.5 Stabilisation by Polyelectrolytes .......................... 92
2.2.4.2 Clay Dispersion in Polar Organic Liquids ....................... 93
2.2.4.3 Absorption of Organic Molecules by Organoclay ........... 93
2.3 Intercalation of Clay ....................................................................... 97
2.3.1 Introduction .................................................................................. 97
2.3.2 Intercalation by Solvents and Solutions ....................................... 100
2.3.3 Intercalation by Organic Cations ................................................ 102
2.3.4 Intercalation by Organic Liquids ................................................. 124
2.3.5 Intercalation by Monomers, Oligomers or Polymers ................... 126
vi
Contents
2.3.5.1 Intercalation of Purified Clay by Hydrophobic
Compounds ................................................................... 126
2.3.5.2 Intercalation of Purified Clay by Hydrophilic
Compounds ................................................................... 127
2.3.6 Two-Step Intercalation ................................................................ 135
2.3.6.1 Intercalation by Silylation ............................................. 136
2.3.6.2 Intercalation Utilising Epoxy Compounds .................... 138
2.3.6.3 Intercalation Utilising Organic Anions .......................... 139
2.3.6.4 Intercalation Utilising Macrocyclic Oligomers
(Cyclomers) ................................................................... 139
2.3.7 Intercalation by Inorganic Intercalants ........................................ 140
2.3.8 Melt Intercalation ....................................................................... 142
2.3.8.1 Quiescent (or Static) Melt Intercalation ........................ 143
2.3.8.2 Dynamic Melt Intercalation .......................................... 149
2.3.8.2.1 Melt Mixing ...................................................... 149
2.3.8.2.2 Mixing Equipment ............................................. 150
2.3.8.2.3 Mixing in an Extensional Flow Field ................. 158
2.3.8.2.4 Melt Intercalation in a PA Matrix ..................... 160
2.3.8.2.5 Melt Intercalation in PEG Matrix ..................... 165
2.3.8.2.6 Melt Intercalation in PO Matrix ....................... 165
2.3.9 Temperature and Pressure Effects on Interlamellar Spacing ........ 183
2.3.10 Layered Nanofillers, other than Montmorillonite ....................... 185
2.3.10.1 Kaolinite ........................................................................ 186
2.3.10.2 Micas and Synthetic Micas ............................................ 189
2.3.11 Summary of the Intercalation Methods ....................................... 198
2.4 Exfoliation of Clays ...................................................................... 201
2.4.1 Principles ..................................................................................... 202
2.4.2 Polymerisation in the Presence of Organoclay ............................. 204
2.4.2.1 Monomer Intercalation – PA-6 Nanocomposites .......... 204
2.4.2.2 Monomer Modification – Acrylic-Based
Nanocomposites ............................................................ 206
2.4.2.3 Non-Reactive Intercalated Clays ................................... 209
2.4.2.4 Co-Vulcanisation ........................................................... 210
2.4.2.5 Common Solvent Method – Polyimide Based
Nanocomposites ............................................................ 210
2.4.2.6 Other Methods – Epoxy-Based Nanocomposites .......... 218
2.4.2.7 Other Methods – PU-Based Nanocomposites ................ 224
2.4.2.7.1 Metal Particles ................................................... 224
2.4.2.7.2 Silica .................................................................. 225
2.4.2.7.3 Cadmium Sulfide Particles (CdS) ....................... 225
2.4.2.7.4 Organoclays ....................................................... 225
2.4.3 Melt Exfoliation .......................................................................... 232
2.4.3.1 PA-Based CPNCs ........................................................... 233
2.4.3.2 PO-Based CPNCs .......................................................... 237
vii
Clay-Containing Polymeric Nanocomposites
2.4.3.3 PCL-Based CPNCs ........................................................ 242
2.4.3.4 Other Systems ............................................................... 245
2.4.4 Functional CPNC ........................................................................ 245
2.4.4.1 Liquid Crystal/Clay Composite (LCC) .......................... 245
2.4.4.2 Biodegradable CPNC with Polylactic Acid (PLA) ......... 246
2.4.4.3 Poly(N-Vinyl Carbazole)/MMT .................................... 252
2.4.4.4 Polydiacetylene .............................................................. 254
2.4.4.5 Clay-Functional Organic Molecules .............................. 254
2.4.4.6 Super-Absorbent CPNC ................................................ 255
2.4.4.7 Emulsion Polymerisation of CPNC ............................... 255
viii
Contents
3.1.9.2 Simha-Somcynsky (S-S) Equation of State ..................... 310
3.1.9.3 Extension of S-S eos to Binary Miscible Systems ........... 315
3.1.9.4 Extension of S-S eos to Suspensions .............................. 317
3.1.9.5 Extension of S-S eos to Nanocomposites ....................... 318
3.1.9.5.1 Diluted, Exfoliated CPNC
– Simplified Approach ....................................... 319
3.1.9.5.2 Dilute, Exfoliated CPNC
– Gradient Mobility Approach .......................... 324
3.1.9.5.3 Intercalated CPNC – Concentration Gradient ... 327
3.1.9.5.4 PVT – Concluding Notes ................................... 331
3.2 Thermal Stability ........................................................................... 333
3.2.1 Thermal Stability During Processing ........................................... 333
3.2.2 Flame Retardancy and High Temperature Stability ..................... 339
3.2.3 Photo-Oxidative Stability ............................................................ 340
3.3 Rheology ....................................................................................... 341
3.3.1 Introduction ................................................................................ 341
3.3.2 Multi-Phase Flow Behaviour – An Overview .............................. 342
3.3.3 Rheology and Microrheology of Disc Suspensions ...................... 344
3.3.4 Similarity Between CPNC and Liquid Crystal Flow .................... 347
3.3.5 End-Tethered versus Non-Tethered CPNC .................................. 350
3.3.6 Fourier-Transform Rheology of CPNC ....................................... 356
3.3.7 Rheology of CPNC with PA Matrix ............................................ 356
3.3.7.1 Effects of Moisture ........................................................ 360
3.3.7.2 Strain Effects ................................................................. 363
3.3.7.3 Dynamic Flow Curves ................................................... 363
3.3.7.4 Apparent Yield Stress .................................................... 368
3.3.7.5 Zero-Shear Viscosity and the Clay Aspect Ratio ........... 369
3.3.7.6 Flow-Induced Orientation ............................................. 370
3.3.7.7 Steady-State Flow Curves – Shear History Effects ......... 372
3.3.7.8 Fourier Transform Analysis of CPNC ........................... 376
3.3.8 Rheology of CPNC with PO Matrix ........................................... 376
3.3.9 Foaming of CPNC ....................................................................... 384
3.3.10 Rheology of CPNC with PS and Styrenics Matrix ...................... 387
3.3.11 Rheology of CPNC with Other Polymer Matrix Types ............... 390
3.3.12 Rheology of CPNC – A Summary ............................................... 392
3.4 Nucleation and Crystallisation ...................................................... 395
3.4.1 Introduction ................................................................................ 395
3.4.2 Fundamentals of Crystallisation .................................................. 396
3.4.3 Effects of Clay on Crystallisation of PA-6 Matrix ....................... 399
3.4.4 Clay Effect on Crystallisation of Other Polyamides .................... 408
3.4.5 Crystallisation of PO Matrix ....................................................... 409
ix
Clay-Containing Polymeric Nanocomposites
3.4.6 Crystallisation of PEST Matrix ................................................... 414
3.4.7 Crystallisation of Syndiotactic PS Matrix .................................... 416
3.5 Mechanical Behaviour ................................................................... 417
3.5.1 Micromechanics of CPNC ........................................................... 417
3.5.2 Prediction of Tensile Strength ...................................................... 426
3.5.3 Fatigue Resistance of CPNC ........................................................ 428
Contents Volume 2
x
Contents
4.1.4.3 Vinyl-Type CPNC Prepared by Melt Compounding ...... 533
4.1.4.4 Vinyl Polymer Matrix – A Summary ............................. 542
4.1.5 CPNC in Water-Soluble Polymeric Matrix .................................. 543
4.1.6 Thermoplastic Polyesters (PEST) ................................................. 553
4.1.7 Polycarbonate (PC) ..................................................................... 565
4.1.8 Liquid Crystal Polymers (LCP) .................................................... 567
4.1.9 Fluoropolymers ........................................................................... 569
4.1.10 CPNC with High Temperature Polymers .................................... 573
4.1.11 Electroconductive CPNC ............................................................. 576
4.2 Thermoset CPNC .......................................................................... 579
4.2.1 Epoxy Resins ............................................................................... 579
4.2.2 Unsaturated Polyester Resin ........................................................ 588
4.2.3 Polyurethanes .............................................................................. 590
4.2.4 Other CPNC with Thermoset Matrix ......................................... 599
4.3 Elastomeric CPNC ........................................................................ 601
Part 5 Performance
5.1 Mechanical Properties ................................................................... 611
5.2 Flame Retardancy of CPNC .......................................................... 611
5.3 Permeability Control ..................................................................... 618
Part 7 Appendices
7.1 General and Chemical Abbreviations ............................................ 631
7.2 International Abbreviations for Polymers ...................................... 640
7.3 Abbreviations for Organic Cations Used as Clay Intercalants ....... 646
7.4 Notations ...................................................................................... 649
7.4.1 Notation Roman Letters ............................................................. 649
7.4.2 Notation – Greek Letters ............................................................. 652
7.4.3 Subscripts .................................................................................... 655
7.4.4 Superscripts ................................................................................. 655
7.4.5 Mathematical Symbols ................................................................ 655
xi
Clay-Containing Polymeric Nanocomposites
7.5 Dictionary ..................................................................................... 656
Dictionary References .......................................................................... 692
7.6 Companies Active in Organoclay, and/or CPNC Technology ....... 694
Part 8 References
References ..................................................................................... 697
Part 9 Index
Index .................................................................................................... 765
xii
Introduction
Part 1
Introduction
Clay-Containing Polymeric Nanocomposites
Introduction
1
Introduction
1.1 General
Nanocomposites (NCs) are materials that comprise a dispersion of nanometre-
size particles in a matrix. The matrix may be single or multicomponent. It may
contain additional materials that add other functionalities to the system (e.g.,
reinforcement, conductivity, toughness, etc.). The matrix may be either metallic,
ceramic or polymeric - only the latter type is of interest at present.
Depending on the matrix nature, NCs may be assigned into one of the three
categories:
• Polymeric (PNC),
• Ceramic (CNC),
• Metallic (MNC).
The nanoparticles are classified as:
1. Lamellar,
2. Fibrillar,
3. Tubular,
4. Spherical, and
5. Others.
For the enhancement of mechanical and barrier properties anisometric particles,
especially lamellae are preferred. However, for rigidity and strength fibrillar are
preferred, while for functional NCs (e.g., optical, electrical conductivity) spherical
or other particles have also been used.
Since the aspect ratio of exfoliated, mineral MMT is p = 50 to 2000, the specific
surface is in the order of 750 to 800 m2/g. The reinforcing effect of nanoparticles is
related to the aspect ratio (p) (ratio of the length or thickness to that of the diameter)
and to the particle-matrix interactions. Independent of the actual dimensions, for
p > 500 the reinforcing effects are the same as those of an infinitely large particle.
Furthermore, the anisometric particles start overlapping when the volume fraction
exceeds the ‘maximum packing volume fraction (φm)’ [Utracki, 1995]:
for discs: 1/φm = 1.55 + 0.0598p
for rods: 1/φm = 1.38 + 0.0376p1.4 (1)
For example, Equation 1 predicts that for discs with an aspect ratio of
p = 500 the overlapping volume fraction is φm = 0.00032 (for rods φm = 0.00004).
The overlapping generates a 3D network that in melts is responsible for the yield
stress and in solid state for significant reinforcing effects. Hence a small amount
of anisometric particles leads to large effects.
1
Clay-Containing Polymeric Nanocomposites
Because of the small size, the nanoparticles are invisible to the naked eye;
hence, they may be used to engender reinforced, but transparent composites
(polymeric or ceramic). On a molecular level, the surface energy of clay particles
is high. As a result, adsorbed molecules have a tendency to be strongly bonded in
the layer adjacent to the clay surface [Horn and Israelachvili, 1998]. This results
in a solid-like behaviour of the 5 to 6 nm thick surface layer and progressive
reduction of viscosity with distance to bulk liquid viscosity at about 100 to
120 nm.
In the absence of antagonistic interactions (such as hydrophilic nanoparticles
in a hydrophobic matrix) the clay/organic liquid system may not require interface
modification. PNCs can be used as a matrix for traditional multiphase systems
(viz. blends, composites or foams), replacing neat polymers.
2
Introduction
1.2.3 Optoelectronics
Semiconductors with carrier lifetime of the order of one picosecond (ps) are necessary
for ultrafast optoelectronic applications. NC semiconductors of GaAs grown by
molecular-beam-epitaxy at low temperatures (LT-GaAs) show a unique combination
of electronic and optoelectronic properties. Implantation of GaAs can result in
properties that are similar to those of LT-GaAs: sub-ps carrier lifetime, high resistivity,
and high electron mobility. Carrier lifetimes as short as 30 fs were determined for the
samples annealed at 500 °C. The short carrier lifetime in high energy ion implanted
GaAs seems to be controlled by the nanoscale morphology, i.e., by the carrier capture/
recombination at the intrinsic point and/or by extended defects.
Another nanocomposite optoelectronic material system comprises Cu-diffused
InP crystals. These contain nanometre-size metallic precipitates that radically
modify the dynamics of photoconductivity and photoluminescence decay.
Furthermore, they significantly reduce the electron and hole trapping time. Spectral
photoresponse measurements evidenced the presence of a well-exposed Urbach-
tail in the sub-band gap radiation absorption, whereas a Z-scan type experiment
has shown an enhancement in both the intensity dependent IR absorption and
the nonlinear refractive index.
3
Clay-Containing Polymeric Nanocomposites
4
Introduction
Table 1 Continued...
Matrix Nano-particles Properties
Al2O3 Ni or Ni-Co Pressureless sintering, processing,
properties
CoPt Ag For high density recording media
Metal matrix Nanosize Structure-related mechanical
C-fibres performance
Al Cu Jet vapour deposition
Al2O3ZrO2 BaTiO3 Bio-applications for bone grafting
The materials are either structural or functional. In this book the focus is on the
former. To this date, it is primarily the structural nanocomposites based on layered
silicates, i.e., clays (CPNC), which have been commercially produced. Clays are easily
available and their intercalation methods have been known since the 1930s [Theng,
1974]. Owing to the nanometre-size particles, CPNC show markedly improved
mechanical, thermal, optical, and physicochemical properties when compared with
neat polymers or their composites [Kojima et al., 1993a]. The improvements include
moduli, strength, heat resistance, barrier properties, flammability, etc.
Nanometre-scale structures are frequently found in biological materials with
impressive performance [Mark, 1996]. For example, bone has a structure of 4 nm
thick hydroxyapatite crystals dispersed within a collagen matrix. In the desire to
synthesise analogues to biological systems several methods for constructing
synthetic composites with a degree of nanometre-scale organisation have been
tried. Thus, elongated ceramic particles have been precipitated within polymer
matrices by drawing the polymer during the precipitation reaction, silica and
CdS have been precipitated in liquid crystal polymer (LCP) [Kovar and Lusignea,
1988; Nelson and Samulski, 1995], metals have been electrodeposited inside the
pores of commercial nanopore membranes [Martin, 1996], and polymers have
been grown within the cavities of layered inorganic structures and zeolites [Okada
and Usuki, 1995; Frisch and Mark, 1996]. Furthermore, an organic-inorganic
nanocomposite was formed by dissolving the inorganic polymer (LiMo3Se3)n in
a conventional monomer acting as the solvent, then polymerising the matrix in
situ [Golden et al., 1996].
The above mentioned methods are well suited for the preparation of a
particular composition, but they are not versatile enough to offer good control
over nanometre-scale architecture and composition in all resins. Several strategies
have been developed for constructing ordered nanocomposites with well-defined,
tunable nanoarchitecture and the ability to be used in a wide variety of polymers:
5
Clay-Containing Polymeric Nanocomposites
6
Introduction
7
Clay-Containing Polymeric Nanocomposites
comprises the latter plus the platelet thickness. For example for MMT: d001 =
interlamellar spacing + 0.96 (nm).
8
Introduction
Figure 1 XRD of PS and PS with 4.8 wt% of Cloisite® 10A (clay treated with
dimethyl benzyl hydrogenated tallow ammonium chloride (2MBHTA)) [Tanoue et
al. 2003].
Figure 2 Bragg’s law dependencies for Cu-Kα1 radiation with λ = 0.1540562 nm.
The straight line is given by Equation 3; correlation coefficient R = 1.0000.
9
Clay-Containing Polymeric Nanocomposites
10
Introduction
11
Clay-Containing Polymeric Nanocomposites
Similar results were obtained when PVME was replaced by polyethylene glycol
1/ 2
(PEG; Mn = 18 kg/mol, radius of gyration rg2 ≅ 5 nm) [Hatharasinghe, 1998].
Thus, the new system consisted of n-butyl ammonium vermiculite, PEG, n-butyl
ammonium chloride, and heavy water. In analogy to the system with PVME,
here also as PEG volume fraction increased from 0 to 0.04 the d001 spacing
(obtained by SANS) decreased from 12 to 6.5 nm (see Figure 3). However, the
addition of polymer had no effect on the phase transition temperature between
the tactoid and gel phases of the clay system, Tc = 13 ± 1 °C. As for the other
system, the PEG presence in the gel phase made the clay plates more parallel and
more regularly spaced.
The d001 spacing versus PEG volume fraction, φ, was fitted to the hyperbolic
relation with three empirical parameters ai:
d001 = a0 + a1/(a2 + φ) (9)
The least squares fit to PEG data yielded the following parameter values:
ao = 3.896 ± 1.793; a1 = 0.1363 ± 0.0995; and a2 = 0.0163 ± 0.0091 with the
standard deviation σ = 0.571 and the correlation coefficient squared, r2 = 0.9983. In
Figure 3 the data from the previously studied system with PVME are also shown.
The dependence is similar, indicating that the two chemically different polymers
bring about a similar contraction of the gel phase.
It is noteworthy that the authors generalised their d001 vs. φ data using an
exponential, instead of hyperbolic dependence:
d001 = a0 + a1 exp{-a2φ} (10)
12
Introduction
The least squares fit to PEG data yielded the following parameter values:
ao = 6.123 ± 0.743; a1 = 6.148 ± 0.737; and a2 = 74.825 ± 24.304 with the standard
deviation σ = 0.513 and the correlation coefficient squared, r2 = 0.9986. Thus, Equations
9 and 10 seem to provide similarly good descriptions for the observed phenomenon.
However, they give quite different limiting values for infinite dilution of clay platelets
at φ → 0, viz. d001 = 12.26 and 80.97 nm, respectively. As can be judged from the data
in Figure 3, the limiting value predicted by Equation 10 is not acceptable.
The explanation for the mechanism responsible for this reduction of
interlamellar spacing should be consistent with the structure of macromolecules
in suspension as well as with the rapid phase transition from gel to tactoid. In
aqueous medium, n-butyl ammonium vermiculite is expected to form hydrogen
bonds with surrounding water. In the absence of polymer, the interlamellar spacing
is about 11 to 12 nm. Since water monolayer thickness is about 0.28 nm, the
large interlamellar spacing most likely originates from the electrostatic repulsion
of butyl ammonium chloride ions associated head-to-tail with butyl ammonium
vermiculite salt. Addition of a polymer seems to cause progressive extraction of
the ionic species from the interlamellar species. It has been assumed that, because
a large number of solvent molecules must be desorbed to accommodate a single
polymer molecule, the translational entropy so gained by the system provides a
strong driving force for polymeric adsorption. However, this assumption may
not be correct in the aqueous media, where the hydrogen bonding of water
molecules is energetically preferred.
SANS has been used by Carrado and co-workers [1996] to monitor the
structural changes in synthetic hectorite upon hydrothermal crystallisation in
the presence of polyvinyl alcohol (PVAl). It was found that the PVAl coats the
small initially formed silicate particles, hindering their further growth. However,
upon removal of the polymer no change has been observed in the extended
inorganic network. Similarly, Muzny and co-workers [1996] monitored the
dispersion of synthetic hectorite in a polymer matrix. The organically modified
clay platelets were dispersed in polyacrylamide (PAA). The studies showed that a
homogeneous dispersion was achievable only with a large excess (equivalent to
five times the cationic exchange capacity (CEC) of the silicate or higher) of the
organic cationic intercalant.
Krishnamoorti and Giannelis [1997] studied the linear viscoelastic behaviour
of end-tethered poly-ε-caprolactone (PCL) with MMT intercalated with ω-amino
dodecyl acid (ADA). The dynamic shear moduli, storage (G´) and loss (G´´),
were determined at small amplitude on either freshly loaded specimens, or
pre-sheared at large amplitude. The large-amplitude oscillatory shear significantly
reduced the linear viscoelastic response, decreasing the low frequency value of
G´´ by one and G´ by two decades. Such a sharp decrease of the signal means that
in the sheared specimens the polymeric matrix controls the CPNC flow behaviour;
hence the MMT platelets are oriented. The alignment was confirmed by SANS.
Similar effects have been reported in several rheological studies (see Section 3.2)
as well as for injection moulded CPNCs [Kojima et al., 1994; 1995].
Ho and co-workers [2001] studied SANS of clay suspensions in non-aqueous
media. The stated aim was to understand and optimise the potential processing
conditions for clay dispersed in a polymeric matrix. As a model system the authors
used Na-MMT (Cloisite ® Na + ) and MMT intercalated with 2-methyl
2-hydrogenated tallow ammonium chloride (MMT-2M2HT; Cloisite® 15A or
C15A) from Southern Clay Products (SCP). Prior to experiments, Na-MMT was
13
Clay-Containing Polymeric Nanocomposites
fractionated and from Cloisite® 15A excess of the intercalant was extracted with
hot ethanol. The purified samples were dried in a vacuum oven at room
temperature for 3 days. The clays were then dispersed in chloroform, benzene,
toluene, p-xylene, cyclohexane and octane.
Both as-received and purified samples were studied. The scattering profiles
and dispersion behaviour in organic solvents of the as-received and purified C15A
were significantly different, confirming that the organic modifier was present in
excess. However, in both cases the clay platelets were fully exfoliated in chloroform
while they were only swollen in benzene, toluene and p-xylene. The scattering
profiles indicated that the swollen tactoids of purified clay were thinner, and
therefore more numerous. Neither the purified nor the as-received clay showed
any temperature effect on scattering. According to atomic force microscopy (AFM)
the average diameter of C15A platelets was in the range of 0.4-1.0 μm, giving the
aspect ratio: p = 400 to 1000.
The SANS experiments at the wave vector q ≡ (4π/λ) sin(θ/2) = 0.004 to 0.517 Å-1
(θ is the scattering angle) were carried out at the National Institute of Standards
and Technology (NIST). The measurements were conducted using either dry clay
powders or dispersions of C15A in deuterated organic solvents, with Na-MMT in
a solution of deuterated/protonated water (D2O/H2O). For well-dispersed, individual
thin circular disks, theory predicts that isotropic, total coherent scattered intensity
depends mainly on the platelet thickness, diameter, orientation, concentration, and
the scattering contrast between the solvent and the clay. The presence of the intercalant
as well as formation of stacks could also be accounted for.
In agreement with the WAXS data the interlayer spacing of purified C15A was
determined by SANS as d001 = 2.43 nm. The d001 spacing in dry Na-MMT was found
to be d001 = 0.99 nm. Both SANS and WAXS data indicated that at a concentration of
ca. 0.5 to 4 wt% in deionised water, Na-MMT platelets were fully exfoliated. The
scattering intensity varied with 1/qn, with n ≅ 2.2. This value is consistent with
calculations assuming total exfoliation of platelets, which are 1 nm thick and
have diameter of about 600 nm. For C15A in an organic solvent the thickness of
the tallow layer depended on the solvent, increasing with the solvent solubility
parameter from 1.61 nm (for toluene or xylene) to 1.86 nm (for chloroform).
Correspondingly, the calculated average number of platelets in the stack varied
from 3 to 1, hence in chloroform the organoclay was fully exfoliated.
1.3.2.3 Transmission and Atomic Force Electron Microscopy (TEM and AFM)
At limiting low scattering angle, 2θ ≅ 2°, the XRD/WAXS scattering intensity and
resolution decrease, i.e., the method is not useful for spacing: d > 8.8 nm. Within
this range TEM may be used to determine the extent of intercalation/exfoliation.
However, TEM also offers a direct method for confirming the XRD data
(micrograph in Figure 4(a)) and with growing frequency it is being used at low
magnification (micrograph in Figure 4(b)) to check on the uniformity (or lack) of
clay stack dispersion in polymeric matrix. The low magnifications are also useful
to check the purity of clay, e.g., the presence of non-layered particles such as
quartz.
Dennis and co-workers [2000; 2001] proposed a method for quantification
of TEM images. Micrographs with magnification of 130,500 were cover with a
mask in which twelve squares of 1 × 1 inch (2.5 cm × 2.5 cm) were cut out. The
degree of dispersion was expressed as the number of clay platelets per square
inch. This dispersion measure was found to correlate well with the tensile modulus.
14
Introduction
(a)
(b)
Atomic force microscopy (AFM) has been used mainly in a tapping mode at
the cantilever’s frequency of 300 kHz and amplitude of 50-100 nm. The difference
between the clay modulus and that of a polymer results in good image resolution.
Starting in 1990, high resolution TEM (HRTEM) became the preferred tool
for the determination of structure, in particular of crystalline nanoparticles, viz.
carbon (CNT) or boron nitride nanotubes (BN-NT). The magnification in
HRTEM is x106 or better, with resolution of 0.1 nm (JEOL 4000EX, 400 kV,
Cs = 1 mm, focus spread = 8 nm, divergence angle = 0.7 mrad) [Gavillet, 2001].
15
Clay-Containing Polymeric Nanocomposites
stress [Loo and Gleason, 2003], or expansion of the interlayer spacing [Cole,
2003]. The advantage of the spectroscopic methods, FTIR and Raman, is that
along with XRD they are applicable to the intercalated system, and stretch to
exfoliated CPNC that do not scatter X-rays.
To examine the interactions between the clay platelets, the intercalating agent
and polymer, FTIR provides important information. By comparing the
experimental and calculated spectra the type and intensity of interactions can be
identified [Aranda and Ruiz-Hitzky, 1999]. The method has also been used to
analyse the thermal decomposition of ammonium intercalants during the melt
compounding method of CPNC preparation [Tanoue et al., 2003]. More details
are provided in Section 3.2.
16
Introduction
17
Copper sulfide
Clay-Containing Polymeric Nanocomposites
18
Table 2 Examples of PNCs with functional properties
Polymer Nanoparticles Process and/or key characteristics References
Polyacrylic acid Copper sulfide Optical properties of films [Gotoh et al. 2001]
PS, polymethyl methacrylate Lyophilized smectic clays Free radical emulsion or solution [Hoffman et al.,
(PMMA), styrene-acrylonitrile polymerisation 2000a,b]
copolymer (SAN)
PVAl Amorphous Fe2O3 nanoparticles Uniformly dispersed super paramagnetic [Kumar et al., 2000]
nanoparticles
Poly(styrene-b- Organo-platinum or organo-silver The bound organo-metal was reduced by [Brown et al., 2000]
acrylic acid) spherical nanoclusters hydrogen
Polyvinyl acetate (PVAc) PbS Synthesis under gamma radiation [Qiao et al., 2000]
19
Introduction
20
Table 2 Continued...
Polymer Nanoparticles Process and/or key characteristics References
Hydroxyethyl methacrylate Tetraethoxysilane In situ acid-catalysed sol-gel in free radical [Hajii et al., 1999]
(HEMA) polymerisation
Poly(amido-amine) dendrimer Complexing and immobilisation of SAXS and SANS indicate CuS at periphery [Beck Tan et al.,
dendrimer particles with (CuS)15 of dendrimer molecules. 1999]
PVAl Carbon nanotubes Thermomechanical and electrical properties [Shaffer and Windle,
1999a,b]
Poly(ethylene glycol-b-lactide) Core-shell MeO-PEG/PLA- Stable core-shell type spherical, stable [Kim et al., 1999]
Clay-Containing Polymeric Nanocomposites
with a methoxy group at PEG- methacryloyl latex particles nanoparticles with a number-averaged
end and methacryloyl group at diameter of about 30 nm
PLA
Poly(4-vinylpyridine) (P4VP) MMT from Milos Protonation by acidity of MMT [Fournaris et al.,
(neutral, salt and quaternised 1999]
forms)
Table 2 Continued...
Polymer Nanoparticles Process and/or key characteristics References
7 10 [Biswas et al., 1999]
Poly-N-vinylcarbazole Colloidal nanometer size manganese DC conductivities improved 10 to 10
polypyrrole or polyaniline dioxide (MnO2) fold
(PANI)
PANI Iron oxide nanoparticles Cast film preparation of conductive NC [Tang et al., 1999]
Polystyrene sulfonate, Layered double hydroxide, Surface and interphase properties [Wilson et al., 1999]
polyvinyl sulfonate Mg6Al2(OH)16CO3 × 4H2O
Polyacrylamide Ag Synthesis of nanocomposites at RT [Zhu et al., 1998]
21
Introduction
22
Table 2 Continued...
Polymer Nanoparticles Process and/or key characteristics References
Epoxy Dispersed clay with alkylammonium Improved tensile strength and modulus at [Massam et al., 1998]
ions T < Tg
Polypyrrole or polythiophene V2O5 Interleaved nanocomposites for lithium [Goward et al., 1998]
batteries
PEG Mo 2 S Intercalation [Gonzales et al.,
1998a,b]
Latex Cellulose whiskers, 5 × 300 nm Strong effects of processing on NC [Favier et al., 1997]
performance
Carboxylated-PS Emulsion ultrasonication followed by Stable nanoparticles [Mei et al., 1997]
polymerisation
Thiol-containing polymers CdS Enzymatic synthesis [Premachandran et al.,
Clay-Containing Polymeric Nanocomposites
1997]
PP PP was blended with smectite X-ray diffraction and IR spectroscopy [Kurokawa et al.,
studies performed 1997]
Perfluoro sulfonate Ionomer SiO2-TiO2 nanoparticles Sol-gel process [Shao et al., 1996]
Table 2 Continued...
Polymer Nanoparticles Process and/or key characteristics References
PEG V2O5 intercalative nanocomposites Synthesis, structure, and reactions have [Liu et al., 1996]
been studied
Polymer electrolyte Xerogel V2O5 Synthesis, characterisation, and transport [Kloster et al., 1996]
properties
Polypyrrole γ-Fe2O3 particles Electrical and magnetic characterisations [Jarjayes et al., 1995]
PVC CaCO3, 15 to 40 nm diameter Ca(OH)2 + CO2 in rotating bed reactor + [Chen et al., 2002]
surface treatment
23
Introduction
24
Table 3 Examples of commercially important PNCs
Matrix Major players Nanoparticles Properties Applications
Polyamide, esp. Toyota, AlliedSignal, Exfoliated silicates, Compared to PA: similar Automotive (e.g., truck
PA-6 Ube, Nanocor, Unitica, e.g., 1-3 vol% Na- density, transparency, mirror housing, engine
Showa Denko, Bayer, montmorillonite. 70 °C higher HDT, 70% higher covers), tool housing, garden
BASF, and Solutia- Exfoliation is crucial tensile modulus, 130% higher equipment,
Dow. Ube CPNC is flexural modulus, 50% lower telecommunication,
commercially available; oxygen permeability, 70% lower aerospace, speciality
RTP offers to supply flammability, etc. application, barrier film for
PNC on demand food packaging, etc.
Polyolefins, esp. Basell, GM, Southern Exfoliated smectite ≤5- Low density (0.91 g/ml) with Automotive: body panels,
polypropylene (PP) Clay Products Inc., wt%. Compatibilizer stiffness equivalent to door panels, interior trim,
and copolymers Toyota, Ford, Dow is needed; e.g., Toyota composites with 35 wt% talc, instrument panels, pillars,
Plastics, and Magna uses maleic anhydride dimensional stability, low-T consoles, etc.
International modified PP impact strength, ductility to –
Clay-Containing Polymeric Nanocomposites
Ethylene-vinyl Nanocor, Mitsubishi Exfoliated smectite NC to be the central layer in Packaging films, for moisture
alcohol copolymer clay particles; loading multilayer, co-formed products and oxygen sensitive foods
(EVAl) ≤5-wt% and electronics
Polyoxymethylene Showa Denko, Bayer Montmorillonite (?) Low warpage, low shrink, high Automotive under-hood
or acetal (POM) surface quality, HDT increased applications, electronics, etc.
by 45 °C, 40% higher modulus
Polyolefins (PO) Toyota, Mitsui, Showa Polypropylene Low density, high rigidity and Automotive
Denko, Mitsubishi columnar crystals strength
25
Introduction
Clay-Containing Polymeric Nanocomposites
26
Introduction
Table 4 Continued...
Company Comments
27
Clay-Containing Polymeric Nanocomposites
Table 4 Continued...
Company Comments
Toyota Central Hold the first patents on nanocomposites. Licenses for the
R&D Laboratories, technology of PA-6 nanocomposites given first to Ube
Nagakute International and Nanocor. Other licensees for this as well
as PP-based CPNC technology followed. Toyota succeeded
in producing CPNC by melt compounding in a twin-screw
extruder.
28
Introduction
A TPO with 2.5 wt% clay is as stiff as PP with 10 times the amount of talc. The
PNC is much lighter; the weight savings can reach 20%, depending on the part
and the material that is being replaced by the TPO nanocomposite. The
nanocomposites are stiffer, less brittle at low temperatures, more durable and
more recyclable than currently used materials. Parts made of nanocomposites
cost about as much as conventional TPO, but it takes less material to manufacture
them. GMC expects the price to improve as the volume of CPNC used by the
transport industry will increase. However, for use in body panels the TPO CPNC
requires additional research.
29
Clay-Containing Polymeric Nanocomposites
interface, and particle surface chemistry) where fundamental issues will be investigated
that apply to all of the application technologies. Activities focus on coatings,
electro-optical behaviour, barrier properties, elastomers, synthesis and processing,
advanced composites and core technologies. NSF announced the Nanoscale Science
and Engineering (NSE) program for the USA universities with US$74 million budget
for FY 2001. The number of international conferences on PNC is growing
exponentially – in 2001 there were at least six major conferences in Europe and
North America. Guided by the evident industrial interests, this monograph will focus
on the PNCs developed as structural materials comprising exfoliated clay particles.
30
Introduction
The melt exfoliation process for PA-based PNCs was developed in the early
1990s at AlliedSignal [Maxfield et al., 1995, 1996; Christiani and Maxfield,
1998]. The later patents describe a three step process:
1. Treating a suspension of clay with peptising Na6P6O18 in aqueous solution
at 50-90 °C with organosilanes, organotitanates or organozirconates that
increase the interlayer spacing to at least d001 = 5 nm.
2. Saturation of the dried clay with precursor monomer then polymerising it.
3. Compounding the modified clay with matrix polymer until the desired level
of exfoliation is reached.
The complexes of organosilanes, organotitanates and/or organozirconates (with
or without onium salt) showed prolonged thermal stability at temperatures above
300 °C.
Owing to the high hydrophobicity and non-polar nature of polyolefins, preparation
of PO-based CPNC is more difficult; hence historically it followed that of PA-based
ones. The first patents from Toyota were for elastomers reinforced with clay and carbon
black (CB) [Usuki et al., 1989]. To prepare a PP-based CPNC Kawasumi and
co-workers [1997] intercalated NaMMT using an oligomeric PO with polar telechelic
hydroxyl groups. Next, a general method for the preparation of PNC with diverse
polymers was disclosed [Usuki et al., 1999]. The process involves three steps:
(i) Intercalation of clay with an onium ion rendering it compatible with a ‘guest
molecule’.
(ii) Contacting the organoclay with the ‘main guest molecule’ at T ≤ 250 °C.
(iii) Transferring the modified clay to a reactor for PO polymerisation (preferred)
or blending with a synthetic resin.
Since the guest molecule and the polymer added in the 3rd step may not be the
same, it is possible to form CPNC with a miscible blend as matrix. The patent
listed vinyl-based polymers, thermosetting resins and rubbers (e.g., PE, PP, PS,
polyisobutylene (PIB), acrylics, thermoplastic polyurethane (TPU), styrene-
butadiene-styrene terpolymer (SBS), liquid butadiene rubber (BR), polybutadiene
(PB), etc.) as the matrix. For example, maleated-PP (PP-MA) with high acid value
hence low MW) was used as the ‘guest molecule’ that resulted in good exfoliation
[Kato et al., 1997].
In a patent from Dow, PO-based CPNC was prepared by Nichols and Chou
[1999]:
(i) Intercalation with an organic, polymeric or inorganic intercalant (e.g., Si(OC2H5)4,
Si(OCH3)4, Ge(OC3H7)4, Ge(OC2H5)4) that resulted in Δd001 = 0.5-60 nm.
(ii) After drying at 50-80 °C or calcination at 450-550 °C, the intercalated material
was dispersed in a monomer or melt-blended until at least 80 wt% of the layers
were exfoliated (aspect ratio p = 10-2000). The claims mention LDPE and
linear low density PE (LLDPE) copolymers with density ρ = 850-920 kg/m3 and
a melt index (MI) = 0.1-10 g/min.
Another method for the preparation of PO-type PNCs followed similar steps
[Hudson, 1999]:
(i) MMT was functionalised in H2O/EtOH with aminosilane, e.g., amino
ethyl-dimethyl ethoxysilane;
31
Clay-Containing Polymeric Nanocomposites
32
Introduction
PE 68 125 intercalated
PVAc 70 60 exfoliated
PS 54 45 exfoliated
PC 64 29 exfoliated
PCL 54 15 exfoliated
PEG 82 10 intercalated
PVAl 80 2 exfoliated
PP 77 unknown intercalated
33
Clay-Containing Polymeric Nanocomposites
34
Introduction
Part 2
2.1
Nanoparticles of Interest to
PNC Technology
2.1.1 General
Nanoparticles used in polymeric nanocomposites have been divided into three
categories defined in terms of the number of dimensions of their nanometre size,
viz. one dimension (platelets), two dimensions (fibres and whiskers), and three
dimensions (nearly spherical particles). Layered nanoparticles that can be
exfoliated into a dispersion of individual platelets are of main interest. Out of
these, in industry the mineral or synthetic clays have a dominant position, hence
these will be discussed in greater detail.
Cyanides Ni(CN)2
interparticle spacing between layers of the layered material or fibrils of the fibrillar
material may depend on concentration – the higher the loading the smaller the spacing.
Since PNCs are mainly used as structural materials, the preferred layered
materials are phyllosilicate clays of the 2:1 type, more precisely smectites, and in
particular montmorillonite (MMT). The layer surface has 0.25 to 0.9 negative
charges per unit cell and a commensurate number of exchangeable cations in the
interlamellar galleries. The amount of this high aspect ratio nanomaterial that
needs to be added to a polymeric matrix to engender CPNC with improved
performance can be as little as 5 ppm. The aim is to totally exfoliate the platelets,
but frequently doublets and short stacks (tactoids) may also be present.
Considering the importance of MMT a more detailed description of its structure
and properties is given below.
While MMT is abundant and inexpensive its main drawback is that it is a
mineral with variable composition, which is impossible to totally purify. Variability
of CPNC has frequently been blamed on structural (particle size distribution and
aspect ratio) as well as chemical (surface reactivity) variability. Consequently,
there is a growing interest in synthetic or at least semi-synthetic layered materials
with well-controlled physical and chemical properties. While experiments with
these model systems are essential for development of a basic knowledge of
intercalation and exfoliation, the hope is that the technology can be developed to
produce synthetic layered materials on a large-scale for the manufacture of CPNC
with consistent performance characteristics.
To prepare functional PNCs other layered materials (than MMT) as well as
non-layered materials have been used, e.g., metallic particles, metal oxides, metal
sulfides, etc. The structure and size of these particles depends on the method of
preparation, which in turn is dictated by the principal application of these
materials. There is a growing interest in synthetic layered nanofillers (see Table 7).
Hectorite has a significantly smaller aspect ratio (p) than MMT, viz. p < 100, but
their synthetic homologues have even smaller diameter flakes, viz. p = 10 to 30.
By contrast with hectorite, synthetic fluoromica (FM) can be prepared with high
aspect ratio, e.g., p < 2,000 [Yano et al., 1993]. Their advantages/disadvantages
are summarised in Table 8.
A simple method for producing synthetic fluoromica (FM) at a relatively low
temperature was described by Tateyama et al. [1993]. Accordingly, a powdery
mixture of 10 to 35 wt% of an alkali silicofluoride (e.g., Na2SiF6) as the main
component (optionally with an alkali fluoride) and natural talc is heated for
about one hour at 700 to 900 °C. The resulting material has the general formula:
αMFxβ(aMgF2xbMgO)xγSiO2 where M is an alkali metal (Li, Na, K), and
0.1 ≤ α ≤ 2: 2 ≤ β ≤ 3; 3 ≤ γ ≤ 4; a + b = 1 are coefficients. For example,
swellable FM may have the composition: talc/LiF/Na2SiF6 = 80:10:10; or
talc/Na 2 SiF 6 /Al 2 O 3 = 70:20:10. The heating temperature greatly affects
swellability and the interlayer spacing. For example, the fluoromica produced
at 700-750 °C shows the XRD peak at d001 = 0.91 nm, while that produced at
780-900 °C has the XRD peak at d001 = 1.61 nm.
A one-step method for the preparation of synthetic grafted smectite clays has
been described [Carrado et al., 2001]. By contrast with the older methods that start
with a mineral precursor, e.g., talc, to produce Li-hectorite (CEC ≅ 0.8 meq/g), the
new process involves sol-gel hydrothermal transformation of an organotetraethoxy
silane (TEOS) or organotrialkoxy silane, viz. phenyltriethoxy silane (PTES). Aqueous
slurries of LiF, magnesium hydroxide, and the silane are refluxed for 2-5 days.
36
Nanoparticles of Interest to PNC Technology
37
Clay-Containing Polymeric Nanocomposites
Note: The term "synthetic" may be a misnomer, as most of these clays are based
on mineral precursors, viz. talc, which may also suffer from some disadvantages
listed for the mineral clays. Consumers beware!
The organic content in the resulting PTES-hectorite was ca. 20-25 wt%. As
evidenced by FTIR (peak at 1430 cm-1) the organics comprise phenyl groups
attached to Si via direct Si-C bonds. Furthermore, 29Si NMR peaks at -79 and
-66 ppm evidenced the presence of RSi(OMg)(OSi)2 and RSi(OMg)(OSi)(OH)
species, respectively. XRD of the synthetic hectorite (FH) showed the interlayer
spacing, d001 = 1.3 and 1.39 nm for, respectively, PTES- and TEOS-based clays.
The organoclays were found to be stable up to at least 400 °C.
38
Nanoparticles of Interest to PNC Technology
of the weight). The electrical resistivity is about 10-4 W-cm, thermal conductivity
ca. 2 kW/m/K, thermal stability in vacuum up to 2800 °C, maximum current
density = 1013 A/m2 (electric-current-carrying capacity 1000 times higher than
copper wires) [Tans et al., 1997].
A MWNT has inner diameter (ID) = 1.2 to 5 and outside diameter (OD) = 10 to
over 50 nm. MWNT are described as 2 to 10 μm long, but the limit to how long
they may grow is unknown. A MWNT looks like a rope made of bundles of
concentric single-wall CNTs. In a bundle each tube is very thin, and the coupling
between them is weak. As a result, even if one nanotube breaks, it has almost no
effect on the others – the crack is blocked, and the fracture stops. Practically, one
may expect MWNT to have the strength of 130 GPa, i.e., nearly 100 times that
of steel at 6-fold lower density [Ijima et al., 1996; Treacy et al., 1996; Yakobson
et al., 1996; 1997]. CNT are 200 times stronger than carbon fibres (CF) and
their diameter is more than 1,000 times smaller.
There are a few books on CNTs [e.g., Saito et al., 1998, Harris, 1999 and
Dresselhaus et al., 2001] and some reviews, viz. Ajayan, 1997, Dai, 1999, Sánchez-
Portal et al., 1999, Nalwa, 2000, Fisher and Brinson, 2001, Dai and Mau, 2001,
Iijima, 2002, Burstein, 2003, and Mamalis et al., 2004. Less information is
available on the use of CNTs in polymer nanocomposites, e.g., Lahr and Sandler,
2000, Thostenson, et al., 2001, Maruyama and Alam, 2002 and Wang et al.,
2003a. There are several journals dedicated to nanoscience and technology, and
since 2002 a specialised journal has been published: Fullerenes, Nanotubes, and
Carbon Nanostructures.
If the buckyball is designated C60 then the zero-length ‘carbon nanoball’ is
C70 and the carbon nanotube (see Figure 6) might be C1,000,000. From the physics
point of view a CNT is a unidirectional single crystal, with a unit cell of about
1.7 nm that keeps on propagating and repeating. The properties of nanotubes
depend on the atomic arrangement, the tube diameter and length. CNTs are
linear fullerenes that, by definition, contain only hexagonal and pentagonal faces,
satisfying the Euler’s theorem. As in a buckyball, the defectless enclosed nanotube
must have 12 pentagons [Dresselhaus et al., 1996; Chico et al., 1996].
CNTs can be described in terms of the tube chirality, defined by the chiral
vector and the chiral angle as shown in Figure 7. A CNT can be visualised as a
strip cut and rolled from an infinitely large hexagonal sheet of graphite. The
cutting can be done at diverse angles and the strip can have a range of widths.
r
These can be expressed by the chiral angle (θ) and the chiral vector ( C n ). Its unit
vectors a1 and a2 are also shown [Thostenson et al., 2001]. In terms of chirality,
armchair (n, m) = (n, n) and zigzag configurations (n, m) = (n, 0) are distinguished.
Tubes with the chiral vector (n, m) = (5, 5), (10, 10), (9, 0) and (10, 5) are
known. Depending on chirality, CNT conductivity can be metallic or
semiconducting.
39
Clay-Containing Polymeric Nanocomposites
Figure 7 A CNT as a strip cut and rolled from a large sheetr of graphite at chiral
angle, θ, and different width, expressed by the chiral vector, C n , composed of unit
r r
vectors a1 and a2 with their magnitude expressed by the integers (n, m). The latter
are the number of steps along the zigzag carbon bonds of the hexagonal lattice.
Reproduced from Thostensen et al., copyright 2001, with permission from Elsevier.
Iijima and Ichlhashi [1993] discovered SWNTs two years after reporting on
MWNTs. Since then, several methods for the preparation of SWNT or MWNT
have been developed. These include: (1) arc-discharge, (2) laser ablation, (3) gas-
phase catalytic growth from carbon monoxide, and (4) chemical vapour deposition
(CVD) from hydrocarbons. For use in composites, large quantities of CNT are
required making the first two methods too expensive. Furthermore, the CNTs
are contaminated by catalyst particles, amorphous carbon, and non-tubular
fullerenes, thus costly purification is required. The two latter gas-phase processes
(3) and (4) are more suitable for large-scale production and tend to yield CNTs
with fewer impurities [Huang et al., 1998].
Sarangi et al. [2001] have prepared CNTs starting either with diamond-like
carbon (DLC), with PE, or with CH4 + H2 gases as precursors. Microwave at
2.45 GHz with RF bias of -600 V was used. The samples were annealed under vacuum
at 1000 °C. Long MWNT were obtained from DLC (ID = 1.8, OD = 3-50 nm).
Starting with PE, short MWNT were obtained growing from metal particles.
The laboratory production rate at the National Tsing Hua University is ca. 5 g
every 40 min. The CVD method gives great purity MWNTs with high aspect
ratio [Tai, 2002]. Tangled CNTs with outer diameter of ca. 10-50 nm, can be
produced in large quantity and low cost, but with less control over the aspect
ratio and structure.
A new and simple method for CNT production was published recently [Pan
and Bao, 2002]. A common laboratory ethanol burner was used with a flame of
about 25 mm in diameter in the middle and 80 mm in height with 15 mm wick.
The metal substrate was austenitic stainless steel (SS) 20 x 10 x 10 mm with
mechanically polished down-facing surface that was pre-etched in HNO3. The
SS block was inserted into the central core of the flame where the temperature
was 610 to 780 °C. The flame was not controlled. After ca. 20 min a thick CNT
film was formed. High density, vertically aligned tubes were observed. These
40
Nanoparticles of Interest to PNC Technology
grew uniformly (by the root-growth mechanism) from nickel oxide or iron oxide
particles on the stainless steel substrate. The MWNTs were 20 to 80 nm in diameter
and 60 to 100 μm in length.
Another publication suggests that CNT may be quite preponderant – they have
been found in the exhaust gases of most (if not all) trucks or cars with high mileage
that use either diesel oil or gasoline [Lee et al., 2002a]. The authors collected
samples from silencers of unleaded gasoline cars with mileage from 1600 to 120,500.
Samples were dispersed in acetone for TEM. All showed the presence of
interconnected spherical-like carbon particles, ca. 20-40 nm. However, high
resolution TEM revealed the presence of hollow polyhedral, multilayered (2 to 6)
structures with d-spacing of 0.34 nm. The structure was similar to that generated
in the carbon-arc discharge nanotube process (at 2500-3000 °C).
Windle and his collaborators studied aqueous suspensions of CNTs [Shaffer
and Windle, 1999a]. Stable suspensions were engendered by either acid-oxidation
and/or by bromination. The process reduced the tube length by a factor of about
two and formed oxygen-containing groups. Plots of suspension viscosity versus
CNT concentration indicated the presence of an asymptote at about 3 to 4 vol%
(depending on the CNT average length). The authors fitted the dispersion data
to the Schltz-Blaschke equation, derived for polymer solutions. Thus an analogy
was proposed between entangled polymer macromolecules in solution and
entangled CNTs in aqueous suspension. At concentrations exceeding the
asymptotic value (the maximum packing volume fraction, φm), e.g., at 5 vol%,
the dispersion formed a viscoelastic gel. The data could be fitted to a relation
describing suspension viscosity, e.g., to that derived by Simha [1952], provided
that the intrinsic viscosity [η] and φm, which depend on the CNT size and aspect
ratio, are treated as adjustable.
A more thorough rheological study of these suspensions was published by
Kinloch et al. [2002]. The experimental value of strain for the linear viscoelastic
response was reported to be 1%. The steady shear flow was highly shear thinning.
In another publication from this laboratory, Shaffer and Windle [1999b] used
aqueous suspension for the fabrication of CNT nanocomposites with PVAl as
the matrix. PNCs with up to 50 wt% loading were prepared. The percolation
threshold for the electrical conductivity was found to be at a CNT loading of
5 to 10 wt%, indicating that CNT do not behave as rigid rods, but are coiled
with a rather low value of the average aspect ratio.
Song et al. [2003] reported that dispersion of MWNT (diameter, d ≅ 25 nm
and length, l ≅ 735 nm) in aqueous medium engendered a liquid crystalline (LC)
behaviour. The transition from isotropic to nematic LC took place at CNT
concentration φ > 0.043.
41
Clay-Containing Polymeric Nanocomposites
42
Nanoparticles of Interest to PNC Technology
43
Clay-Containing Polymeric Nanocomposites
the behaviour of PNC containing continuous and short nanotubes. In both cases
mechanical loading in the axial and transverse direction to the SWNT was applied.
The system with continuous SWNT was highly anisotropic, with greatly increased
modulus in the draw direction. The system with short SWNT did not show
increased modulus relative to the polymer. The MD stress–strain curves were
simulated assuming uniform strain on the entire model.
44
Nanoparticles of Interest to PNC Technology
45
Clay-Containing Polymeric Nanocomposites
they are slow. Furthermore, there are serious difficulties in developing interactions
at the nanotube/matrix interface. Thus, the use of CNTs is limited to high value
added applications and niche markets, for example, in electronics and space.
2.1.3.1.4 Sources
As shown in Table 9, numerous organisations on three continents offer CNTs.
Depending on purity, method of synthesis and geographical location, the price
varies from US$1.5 to 1,500 per gram. There is rapid progress in the preparative
methods, which results in increasing purity of the ‘as received’ CNTs. If the
presence of residual catalyst is not detrimental to the desired performance of
nanocomposites, purification may not be necessary and the cost immediately
drops by a factor ranging from 2 to 20 (for MWNT and SWNT, respectively).
Nanocyl offers functionalised CNTs for an additional €50/g. The functionalities
include: -H, -OH, -Cl, -CO, -COOH, -NH2, -SH, -SCH3, etc.
Hyperion Catalysis commercialised unpurified CNTs at US$44/kg (15-20%
purity). These are also available in masterbatches with PC, PBT, PET, PS and
PEEK. GE Co. has developed a polyphenylene ether (PPE)/PA alloy (Noryl
GTX-990EP) with ca. 2-wt% of CNT for electrostatic painting [Scobbo, 1998;
Scobbo et al., 1998]. The alloy has low density (1080 kg/m3), HDT 158 °C,
notched Izod impact strength 600 J/m2, flexural modulus of about 2.4 GMPa,
tensile strength 60 MPa, elongation at break 22%, bulk resistivity of ca. 30 Ωm
and MI = 4.8. The alloy is being used for automotive mirror housings, door
handles, gas tank caps, fuel lines and plastic fenders. The technology is being
adapted to acrylonitrile-butadiene-styrene terpolymer (ABS), PC, thermoplastic
polyester (PEST) and PA automotive compounds.
Toray Industries has developed a catalytic CVD method of producing dual-
wall carbon nanotubes (DWNT), which when commercially produced in 2004
will be available at US10¢/g. According to the Mitsubishi Research Institute, by
2020 the market for fullerenes and CNT will expand to US$3.6 billion. The
projected value of nanostructured materials in 2005 and 2010 is US$96 and
208 billion, respectively [Despotakis, 2003].
46
Nanoparticles of Interest to PNC Technology
heptagons. Defects may also occur along the tube body. These nucleate the
crystalline growth of the semiconjugated PmPV.
Sandler et al. [1999] reported that a CNT loading of 0.1 vol% in epoxy
resulted in an increase in electrical conductivity of four orders of magnitude (to
0.01 S/m). A nonionic surfactant has been used to investigate the effects of the
degree of CNT dispersion on conductivity [Gong et al., 2000].
PNCs of MWNTs (d = 80-90 nm) with polypyrrole (PPY) have been prepared
using in situ polymerisation [Chang et al., 2000]. The PNCs were characterised
using SEM, TEM, XRD, Raman scattering, thermogravimetric analysis (TGA),
conductivity, and magnetic susceptibility measuring devices. The PPY adhered to
the CNT exterior, without chemically bonding. The process affected polaron
density and the orientation of PPY macromolecules. The magnetisation of the
composite was found to be the sum of the magnetisations of the components.
The semiconductor-like conductivity of the PNC was larger than that of PPY.
The thermal stability resembled that of PPY.
CNT modification, their conversion into carbides: SiC, WC, etc., coating with
metals or organic electrically conductive polymers has been carried out for a
decade. Recently, one-dimensional PPY/CNT nanocomposites were produced by
electrochemical deposition of PPY onto CNT in well-aligned large arrays [Chen
et al., 2001a]. The coating thickness was controlled by the film-formation charge.
Uniform thickness from 10 to 93 nm was obtained, changing the morphology
from coated individual tubes to filling the gap between all CNT in an array,
forming uniform conductive material.
Unpurified SWNTs with a broad distribution of diameters (dav ≅ 1.1 nm) and
lengths was dispersed in Epon 862 to increase its thermal conductivity [Biercuk et
al., 2002]. At 1 wt% loading the PNC showed a 70% increase in thermal conductivity
at 40 K, rising to 125% at room temperature. The percolation threshold for electrical
conductivity was between 0.1 and 0.2 wt% of the SWNT loading. These results
suggest that the thermal and electrical properties of SWNT-epoxy nanocomposites
may be improved without the need to purify or chemically functionalise the nanotubes.
2.1.3.1.6 Graphite
When electrical conductivity is desired, CNT can be replaced with exfoliated
graphite. Chen et al. [2001b] applied this strategy. The authors used natural
flake graphite with diameters ranging from 50 to 1000 μm. The graphite was
first expanded by treating it with a mixture of concentrated sulfuric acid and
nitric acid for about 16 h. After washing and drying at 100 °C the material was
heat treated at 1050 °C for 15 s, thereby expanding graphite particles in the
c-axis (or orthogonal) direction by a factor of about 350 (compared to the original
graphite). The expanded graphite was mixed with styrene (St) and methyl
methacrylate (MMA) mixture (St/MMA = 70/30), in the presence of benzoyl
peroxide, then heated at 150 °C for 30 min and cooled to room temperature
(RT). A black solid was crushed, rolled on a twin-roll mixer for 5 min, and
moulded into 4 mm thick rectangular plates.
TEM showed that the graphite was dispersed in the form of exfoliated sheets
forming 10-40 nm thick stacks. The transition from electrical insulator to
semiconductor occurred when the expanded graphite content was 1.8 wt% while
at 3.0 wt% loading the electrical conductivity increased from 10-14 to 10-2 S/cm
hence by 12-decades. This enhancement may be attributed to the high aspect
ratio (p), of the dispersed graphite – from the percolation threshold concentration
47
Clay-Containing Polymeric Nanocomposites
its value, p ≅ 99, was calculated. To preserve the high value of p, hence the
electrical conductivity, extensive roll-milling should be avoided. Addition of up
to 5 wt% of exfoliated graphite linearly increased the tensile strength from 24 to
29 MPa and reduced the notched Izod impact strength from 29 to 19 J/m.
Similarly, Xiao et al. [2001] prepared PNC based on exfoliated graphite with
PS as matrix. Benzoyl peroxide was dissolved in styrene then exfoliated graphite
was added to the reaction vessel. The reaction mixture was stirred for 4 h at
85 °C then for 2 h at 150 °C. Increasing the amount of exfoliated graphite caused
the molecular weight (MW) and molecular weight distribution (MWD) of PS to
increase. The glass transition temperature (Tg) increased to ca. 124 °C. As a
control, the same compositions were prepared by compounding dry blends at
170 °C in a two-roll mill. The in situ prepared PNCs had a higher thermal stability
than either PS or PS/exfoliated graphite prepared by melt blending. The volume
resistivity versus exfoliated graphite content is shown in Figure 8. It is noteworthy
that incorporation of 5 wt% exfoliated graphite into PS, reduced the volume
resistivity by about 3 or 17 decades, respectively for the PNC prepared by melt
blending or by polymerisation. The difference in conductivities originates in the
structural differences between these two types of PNC.
48
Nanoparticles of Interest to PNC Technology
The former, reactive approach is preferred for PNC with thermoset matrix.
Most of the early work has been done on epoxy systems. For example, Schadler
et al. [1998] dispersed 5 wt% of MWNT in Epon 828, and then cured it with
triethylene tetraamine. In standard tension and compression tests only relatively
small increases of moduli were found, viz. tension increased from 3.10 (for neat
epoxy) to 3.71 GPa, while compression rose from 3.63 to 4.50 GPa. The Raman
peak position that indicates strain in the C-C bond under load, significantly shifted
under compression, but not under tension. Lourie and Wagner [1998a,b,c; 1999]
reported similar results for SWNT/epoxy PNC. These results indicate a basic
problem with load transfer in tension, particularly severe for PNCs containing
MWNT. Only the outermost layer of each MWNT may be bonded to the matrix.
The interactions between individual layers in MWNT are relatively weak, a van
der Waals-type, and the shear strength between layers is small, similar to that in
graphite (σ12 ≈ 0.48 MPa), confirmed by pullout experiments in AFM [Yu et al.,
2000a]. These authors measured the tensile strengths of MWNT using a
‘nanostressing stage’. The outermost layer showed a Young’s modulus of E = 270
to 950 GPa, and a tensile strength of 11 to 63 GPa. As the straining continued,
the outer layer broke first via the ‘sword-in-sheath’ failure.
Another reason for the relatively low enhancement of epoxy properties by
incorporation of CNT is the tendency of nanotubes to aggregate into bundles. A
nearly constant value of the Raman peak in tension was related to tube sliding
within the nanotube bundles and, hence poor interfacial load transfer between
nanotubes and the matrix [Ajayan et al., 2000]. It is the low modulus of the bundles
that controls the PNC performance, and not the axial modulus of individual tubes.
To enhance the reinforcing effects the authors suggested three methods:
1. Breaking the bundles into individual tube fragments and randomly dispersing
them in the matrix;
2. Radiation or chemical crosslinking of the tubes within bundles to increase
the bundle rigidity and eliminate the inner tube slippage; and
3. Obtaining strong carbon CNT/matrix interfacial interactions.
Cooper et al. [2001] dispersed SWNTs or MWNTs in epoxy and studied the
micromechanical properties using Raman spectroscopy. SWNTs have been
deformed in a diamond anvil pressure cell. Upon hydrostatic compression the
disordered-related peak at wavenumber 2640 cm-1 up-shifted at an initial rate of
23 cm-1/GPa. However, the band downshifted upon application of a tensile stress.
These Raman peak displacements provided evidence of the stress transfer from
the matrix to CNT, thus reinforcement effects. The authors calculated the effective
modulus of SWNT and MWNT dispersed in epoxy as > 1 TPa and about 0.3 TPa,
respectively.
Raman spectroscopy combined with mechanical testing was used to probe
the alignment of CNT in PNC [Wood et al., 2001]. SWNT (0.1 wt%) was
dispersed in a UV curable urethane acrylate oligomer by ultrasonication, mixed
with the curing agent and then sheared to induce flow orientation. The UV cured
films (~150 μm thick) were evaluated, recording the Raman spectral shifts with
strain in the longitudinal and transverse direction. The shifts obtained, in parallel
and perpendicular to the flow direction, were significantly different. The adhesion
between CNT and the polymer exceeded the shear yield strength of the matrix.
Purified MWNTs were dispersed by sonication in a 1,2-dichloroethane solution
of epoxy, polyethersulfone (PES) and 4,4-diaminodiphenylsulfone at 84 °C [Qiao
49
Clay-Containing Polymeric Nanocomposites
et al., 2002]. Then, the solvent was evaporated and the film crosslinked. The range
of MWNT loadings explored was from 0 to 40 wt%. The bending strength increased
by ca. 136% to ca. 42 MPa. The volume resistivity decreased by six orders of
magnitude from 8.59 × 105 to 0.1415 MΩcm. For the purified MWNT the
percolation threshold of electrical conductivity was high, ca. 20 wt%, indicating
that the CNT were isolated from each other by a layer of polymer.
50
Nanoparticles of Interest to PNC Technology
stress at break by 25%, indicating significant load transfer across the nanotube-
matrix interface. The observed enhancement of stiffness was found to be in good
numerical agreement with the values calculated from the relation [Hill et al., 2002]:
⎡ 3 1+ 2pK1φ 5 1+ 2K2φ ⎤
Ec /E p = ⎢ x + x ⎥
⎣ 8 1− K1φ 8 1 − K2 φ ⎦
(11)
p ≡ l f /d f ; K1 ≡
(E /E ) − 1 :
f p
K2 ≡
(E /E ) − 1
f p
(E /E ) + 2p
f p (E /E ) + 2
f p
51
Clay-Containing Polymeric Nanocomposites
demonstrated less thermal shrinkage and less creep under stress. The morphology
of these fibres suggests a co-alignment of the SWNT and PBO fibrillae within the
oriented composite fibre.
52
Nanoparticles of Interest to PNC Technology
53
Clay-Containing Polymeric Nanocomposites
2.1.3.3 Imogolite
Imogolite (from imogo = volcanic ash in Japanese) is weathered pumice, discovered
in Murakasami, Japan and described in 1962 by Yoshinaga and Aomine. This
para-crystalline phyllosilicate has a composition written either as: Al2SiO3×(OH)4;
SiAl2O5 · 2.5 H2O or Al2O3×SiO2×nH2O, with molecular weight per crystalline
unit cell of 4754. However, while the nominal Si:Al ratio is 2, the measured one
varies from 1.05:1 to 1.15:1. Imogolite occurs as tubes of several micrometers in
length, having inside diameters of 1.0 and outside diameters of 2.0 – 2.52 nm;
occasionally the tubes may branch out. The nanotubes have good rheological,
adsorptive, and surface properties due to their unique structure and functional
groups on the surface. For example, the tubes may form raft-like structures with
honeycomb-shaped cross-section [Kajiwara et al., 1986; Donkai et al., 1993].
Imogolite may also be synthesised at T = 25-100 °C from a dilute solution of
AlCl3 and Na4SiO4 via precipitation reactions. The imogolite structure has Si in
tetrahedral coordination and Al in octahedral coordination. Imogolite has been
used for reinforcing water-soluble polymers, viz. polyvinyl alcohol (PVAl)
[Hoshino et al., 1992a] and hydroxy propyl cellulose (HPC) [Hoshino et al.,
1992b]. Imogolite has several rather broad, low XRD peaks. Conclusive
identification can be made by FTIR and TEM. Its CEC is 1.7 mol/g at pH 7.0, the
calculated specific surface is 1000, while its measured value is 900 to 1100 m2/g.
The density is 2.7 g/ml, hardness = 2 to 3, refractive index (nD) = 1.47 to 1.51.
The crystals are transparent and fragile [Gabriel and Davidson, 2000].
54
Nanoparticles of Interest to PNC Technology
55
Clay-Containing Polymeric Nanocomposites
from BN should all be insulating with a band gap of about 5 volts. Another
method of preparation is by means of a solid-state process. Graphite and
hexagonal boron nitride powders were ball milled at room temperature, then
annealed below the melting points for both graphite and boron nitride, at
T ≤ 1300 °C. The latter stage leads to the nucleation, re-ordering and crystal
growth of hexagonal C and BN nanotubes of both cylindrical and bamboo-like
morphology. High energy ball milling was found to result in solid-state phase
transformations and chemical reactions [Chen et al., 1999a].
Gole et al. [2003] prepared and characterised silica-based nanospheres
(monodispersed, with d ≤ 30 nm diameter), nanotubes, nanofibre arrays, and
nanowires. The agglomeration of small nanospheres (d ≤ 10 nm) into wire-like
groupings has suggested a possibility of growing silica nanotubes (SiNT) by a
more efficient agglomeration process. The SiNT were generated from silicon
particles at 1400 oC. Their outer diameter was, OD = 70 to 80 nm, with wall
thickness of ca. 20 nm. Biaxially structured SiC-SiOx nanowires have now also
been generated from C/Si/SiO2 mixtures. Depending on the size, the Young’s
modulus of these structures is 50 to 100 GPa.
56
Nanoparticles of Interest to PNC Technology
under relatively mild, well controlled conditions, hence inorganic and organic
components can be formed at the nanometre scale, at a wide range of composition.
The hybrids usually have ≥ 10% dispersed phase. Two types of hybrids are
recognised:
1. Those where only weak interactions between the organic and inorganic species
exist (viz. van der Waals, hydrogen bonding or electrostatic interactions).
2. Where the inorganic and organic components are chemically bonded by either
covalent or ionic-covalent bonds. Examples of PNCs prepared by the sol-gel
methods are provided in Table 2.
Several methods of PNC preparation by the sol-gel method have been developed
[Brinker and Scherer, 1990]:
57
Clay-Containing Polymeric Nanocomposites
58
Nanoparticles of Interest to PNC Technology
chloride, alkoxide or silanol. However, this route does not control the placement
of the functionality on the cage. Functionalisation of fully substituted silane
compounds by hydrosilylation or chlorination also does not lead to controlled
substitution. Silylation of anionic species has been reported to produce
functionalised species, e.g., via: (a) the addition of hydrogen atoms bonded directly
to silicon atoms onto aliphatic unsaturated compounds, or (b) the addition of
sulfur onto aliphatic unsaturated compounds. The type of organic functionality
that can be incorporated on the cage is limited. These methods have low yield
and a large percentage of impurities from side reactions that must be removed.
The reaction between trisilanol with a variety of compounds of the type R´´MX3
(R´´ = alkyl, alkenyl, aryl, H; M = Si, Ge, or Sn; X = halogen or alkoxide) leads to
a variety of monomeric Σ8 silsesquioxanes.
In the early 1990s, Lichtenhan reacted trisilanol with R´SiCl 3 or
R´Si(OCnH2n+1)3 starting a new class of monomers called polyhedral oligomeric
silsesquioxanes, or POSS (see Figure 9). In this case the R´ group was polymerisable
or useful for grafting reactions, or sol-gel processing, e.g., acidic, acrylic, alcohol,
amine, α-olefin, epoxy, ester, halides, isocyanate, organo-halides, phenol, silanes,
silanols, styrenic, vinyls, etc. The process that leads to functional POSS was
patented [Lichtenhan et al., 1999]. In the presence of a metathesis catalyst an
effective amount of olefins of alkyls, cyclics, aryls, siloxyls or their isomersis able
to provide POSS with 1-8 reactive functionalities. The process has been used in
the US Air Force Laboratory to synthesise dozens of types of POSS. The products
are soluble in common solvents, e.g., chloroform, hexane or THF.
The chemical structure of POSS is: (RSiO1.5)Σn, thus as the name indicates
(sesqui = ‘one and a half’) intermediate between silicas (SiO2)n and silicones
(R2SiO)n. For most POSS: Σn = 8, but Σn = 6, 10 or 12 are also available. The size
of the cage varies from about 0.7 to 3 nm. Polyhedral siloxanes or silsesquioxanes
sensu stricto are topologically equivalent to a sphere and are also called sphero-
siloxanes. Most POSS compounds are crystalline, but changing the R-group may
result in liquid crystal or liquid-like behaviour.
The octasilsesquioxanes (Σn = 8) have cube-shaped molecules that consist of
a Si8O12 core and eight reactive sites that may be differently functionalised. From
the point of view of polymer technology the mono-substituted species, R´R7Si8O12
Figure 9 Reaction between trisilanol and a compound of the type R´SiX3 (R´ =
reactive group; X = halogen or alkoxide) leads to a variety of monomeric Σ8
silsesquioxanes, or POSS monomers [Lichtenhan et al., 1999].
59
Clay-Containing Polymeric Nanocomposites
(where R´ ≠ R are substituents) are the most interesting – the group R´ may provide
an ability to the octasilsesquioxane to enter polymerisation, copolymerisation or
grafting reaction, whereas the other functionalities, R, make the system miscible.
It should be noted that incorporation of POSS into crystallisable macromolecules
reduces the crystallinity, which in turn tends to lower the chemical and solvent
resistance.
A new type of PNC formation was recently proposed by Ricardo et al. [2001].
The authors started with octakis(hydrido dimethyl siloxy) octasilsesquioxane
Q8M8H, converting it to octa-ethylbenzyl chloride. Using bromoester as an initiator
and CuCl as a catalyst, atom transfer radical polymerisation (ATRP) was employed
to produce star-type PMMA with arms having controlled molecular weights.
The concentration of catalyst and initiator control MW, MWD and the star-star
coupling reactions. The arms had Mn = 4 to 15 kg/mol (varying with conversion),
and the polydispersity MW/Mn = 1.2 to 1.5. The number of arms per Q8M8H-unit
was found to vary from 6.2 to 7, hence less than the maximum of 8. The lower
number of arms may result from star-star coupling reactions. The new PNCs
should have unique properties, combining those of nanocomposites with those
of the controlled star-branched polymers [Roovers, 1985]. Mechanical properties
of these PNCs have not yet been reported.
2.1.4.3.2 Properties
POSS with reactive groups may be incorporated into virtually any polymer either
by compounding (as a nanofiller), copolymerisation or blending [Lichtenhan et
al., 1993; Lichtenhan, 1995; Haddad and Lichtenhan, 1996; Shockey et al., 1999;
Feher et al., 1999].
POSS may provide a variety of property enhancements to existing resin systems.
Owing to its chemical nature, POSS can be used to upgrade the thermal and
physical properties of most plastics. The following isotropic enhancements have
been reported for POSS-copolymers and blends: higher decomposition
temperature, Tg increased by 100-200 °C, lower flammability (delayed combustion
and reductions of heat evolution), bulk density reductions of up to 10%, increased
O2 permeability, reduced thermal conductivity, improved resistance to oxidation,
increased modulus and hardness while maintaining the stress and strain
characteristics of the base resin, good processability and mouldability (viscosity
reduction of up to 24% was reported) [Lichtenhan, 1996; Tsuchita et al., 1997].
Substituted POSS have been used as Wittig reagents, precursors to SiC powders,
low dielectric constant materials, alumino-and gallio-silicates, silica-reinforced
composites, a variety of microporous materials, etc. A variety of functional groups
have been attached to POSS, viz. acrylates, silanes, silanols, olefins, epoxies,
amines, esters, phenols, styrenics and thiols. Functionalised POSS was polymerised
to yield hybrid inorganic-organic homopolymers or copolymers [Tsuchita et al.,
1997].The free radical reaction of propyl-methacryl-POSS gives POSS macromers,
which can undergo hydrosilylation into oligomers and polymers with improved
mechanical properties, increased thermal stability to oxidation and resistance to
degradation by UV [Lichtenhan, 1995]. Properties and performance of POSS-
based polymers continue to be explored [Zheng et al., 2001; 2002a,b; Li et al.,
2002]. The modern POSS is only about 10 years old, but between 1993 and
2002 over 160 articles on POSS were published.
POSS have been successfully incorporated into a number of thermoplastic
matrices such as styrenics, acrylics, LCP, siloxanes, polyamides and more recently
60
Nanoparticles of Interest to PNC Technology
PO. The resins are inherently reinforced by the presence of the inorganic cages of
size between a molecule and a macromolecule. By controlling the nature of the
substituted groups, R and R´, POSS has controllable reactivity, miscibility, low
density, neutral pH and low VOC. Their polymers or copolymers are isotropic,
free of metals, and transparent.
In Figure 10, the compositional variation of Tg and the decomposition
temperature for 10 wt% mass loss (Td) is shown for a series of copolymers. These
were prepared by free-radical polymerisation of α-methyl styrene with styryl-based
POSS. The latter contained one styryl-ethyl polymerisable group and seven inert
R-groups, either cyclohexyl (-c-C6H11) or cyclopentyl (-c-C5H9). Thus, the
macromer had a spherical (Si8O12) core, surrounded by seven inert groups for
solubility and one reactive. It was found that the cyclohexyl derivative is about
twice as soluble as cyclopentyl [Haddad and Lichtenhan, 1996]. The difference
in behaviour between these two types was small, but cyclohexyl-substituted POSS
showed better performance.
Figure 11 shows the variation of Tg for two series of isobutyl-styryl-POSS
copolymers with either vinylpyrrolidone (P4VP-POSS) or acetoxylstyrene (PAS-
POSS). The Figure demonstrates that POSS may increase the Tg, but at a relatively
high POSS content – for both systems incorporation of POSS initially leads to a
reduction in the HDT. Since the ratio of molecular weight of POSS to P4VP is
8.3 the observed minimum at about 2 mol% is equivalent to 14 wt% of POSS.
The authors [Xu et al., 2002] rationalised this behaviour by noting that the POSS-
containing copolymer had reduced molecular weight and narrower molecular
weight distribution. Furthermore, the Tg depends on:
61
Clay-Containing Polymeric Nanocomposites
1. A diluent role of POSS that reduces the dipole-dipole interaction of the matrix
monomer,
2. The dipole-dipole interaction between POSS siloxane and the polar carbonyl
of organic polymer, and
3. The POSS-POSS intermolecular interaction.
At a relatively low POSS content, the diluent role dominates, thus Tg decreases.
At a high POSS concentration, the POSS-PAS, POSS-P4VP and POSS-POSS
interactions cause the Tg to increase.
Figure 12 illustrates the variation of Tg for copolymers of butyl methacrylate
(BM) with up to 50 mol% of cyclopentyl-POSS-methacrylate – a significant
increase from 50 to 245 °C was observed. The experimental data may be described
by the dependence:
[ 3/2
Tg = ( 1+ K * w 1w 2 ) ⋅ w 1Tg1
3/2
+ w 2Tg 2 ] (12)
where wi and Tgi are, respectively, the weight fraction and glass transition temperature
of component i, and K* is the binary interaction parameter between them.
The relation was derived for strongly interacting miscible blends [Utracki,
1989], thus the agreement implies that there are strong thermodynamic
interactions between the two types of mers expressed by the high value of the
binary interaction parameter: K* = 6.39 ± 0.52. Since such an effect has not been
observed in copolymers of BM with methyl methacrylate (MM), it is evident that
stiffening of the copolymer macromolecules involves the POSS units. The
correlation coefficient squared for the dependence in Figure 12 is r2 = 0.999. The
dependence predicts that Tg should decrease at POSS loadings over 50 wt%.
62
Nanoparticles of Interest to PNC Technology
63
Clay-Containing Polymeric Nanocomposites
Figure 13 Complex tensile modulus versus temperature for PP and its copolymer
with 10 wt% of [CH3SiO1.5]Σ8 [Schwab et al., 2001].
64
Nanoparticles of Interest to PNC Technology
65
Clay-Containing Polymeric Nanocomposites
2.1.4.3.3 Sources
POSS is available from Sigma-Aldrich Chemical Co. (www.sigma-aldrich.com),
Gelest Inc. (www.gelest.com), The Mather Group at UCONN (University of
Connecticut), Hybrid Plastics (www.hybridplastics.com), etc.
66
Nanoparticles of Interest to PNC Technology
2.1.4.3.4 Applications
The method of POSS incorporation depends on the category (see above) and the
expected application. Evidently, it is advisable that the molecular silicas are dissolved
in a monomeric or polymeric liquid. The dissolution should be carried out in a
suitable mixer, e.g., a twin-screw extruder (TSE), as dispersing [CH3SiO1.5]Σ8 in
molten PP [Schwab et al., 2001]. The functionalised POSS monomers are mainly
copolymerised, e.g., as butyl methacrylate with heptacyclopentyl methacrylate
(CpPOSS-MA) [Murugavel et al., 1999], but homopolymerisation, grafting and
crosslinking may also be carried out. However, since the cost of POSS is high (even
in comparison to engineering resins) the recommended use is < 50% incorporation
into high performance resins. In the case of POSS® Polymers, blending with other
resins in a TSE may provide a suitable solution.
67
Clay-Containing Polymeric Nanocomposites
68
Nanoparticles of Interest to PNC Technology
69
Clay-Containing Polymeric Nanocomposites
Applications for liquid crystal display elements, magnetic recording media and
optical fibre coatings have also been disclosed. L-POSS may also be used for gas
separation membranes, binders for ceramics and controlled release drugs as well
as additives in cosmetics and resins.
The ladder-like poly(methyl silsesquioxane)s (PMSQ) are used for coatings,
particularly in electronics and optical devices. To improve the barrier, mechanical
and thermal properties Ma et al. [2002] tried to disperse MMT in PMSQ. The
aim was to develop high heat-resistant coating. The Na-MMT was pre-intercalated
with trimethyl hexadecyl ammonium bromide (3MHDA), dried and ground.
Dispersing the organoclay in chloroform, then adding methyl trimethoxysilane,
hydrolysing it, neutralising and polymerising, resulted in the PMSQ/MMT
nanocomposite:
XRD and TEM showed that MMT was only intercalated with d001 = 3.42 nm.
Annealing the nanocomposite at 150 °C for 3 h did not change the spacing, but
annealing at 300 °C for 3 h did reduce d001 to 3.0 nm. Furthermore the relative
intensity of the peak significantly increased. The stability of interlayer spacing at
T ≤ 150 °C was explained by the molecular structure of the in situ polymerised
PMSQ. The decrease of spacing at 300 °C is most likely due to decomposition of
the quaternary ammonium ion complex on MMT. Unfortunately, the authors
did not report on the performance of these interesting materials.
The commercial success of a material depends on delivery of enhanced
performance at low cost. Currently, the PNCs available on the market contain
2 to 5 wt% of organoclay. The market price for PA-6 and PP is about US$3,000
and 1,000/ton, respectively. Assuming that a 10% increase of cost would be
acceptable (if performance warrants it), the cost of compounding and organoclay
must not exceed US$300 and 100/ton, respectively. At the current cost of
compounding (at least US$50/ton) and clay the incremental cost is ca. US$300
to 400, leaving little room for profit. Thus, in the case of CPNC the commercial
success of PNC hinges on the intercalation and compounding costs.
Applying a similar algebra to POSS with the lowest projected price of
US$33,000/ton the situation is difficult. Furthermore, to achieve an interesting
enhancement of properties relatively large amounts of POSS must be added (from
10 to 50 wt%). For applications as a structural material the cost would be
prohibitive. Obviously, the economics look better when more expensive
70
Nanoparticles of Interest to PNC Technology
71
Clay-Containing Polymeric Nanocomposites
72
Clays
2.2
Clays
73
Clay-Containing Polymeric Nanocomposites
The synthesis of clays has been extensively studied [de Kimpe et al., 1961;
Roy, 1962; Weaver and Pollard, 1973; Velde, 1977]. For example, organic
compounds facilitate the synthesis of kaolin at low temperature by condensing
aluminum hydroxide into octahedrally coordinated sheets [Linares and Huertas,
1971]. More recently, Carrado [2000] published an excellent review on synthetic
clays and the resulting CPNCs.
2.2.2.1 Kaolins
These include kaolinite, dickite, nacrite and halloysite-endellite. The structural
formulae for kaolinite and endellite are A1 4 Si 4 O l0 (OH) 8 and
A14Si4Ol0(OH)8.4H20, respectively. The kaolinite lattice consists of one sheet of
tetrahedrally coordinated Si (with O) and one sheet of octahedrally coordinated
Al (with O and OH), hence a 1:1, or a two-layer structure. A layer of OH
completes the charge requirements of the octahedral sheet. Adjacent cells are
spaced about 0.71 nm across the (001) plane. When solvated in ethylene glycol,
endellite expands to 1.0 nm in the c-direction. Halloysites are usually tubular or
scroll-shaped; they may be differentiated from kaolinite and dickite by treatment
with potassium acetate and ethylene glycol.
For example, kaolin (KGa-1) from Georgia [van Olphen and Fripiat, 1979]:
• Contains (wt%): SiO2 = 44.2, Al2O3 = 39.7, TiO2 = 1.39, Fe2O3 = 0.13,
FeO = 0.08, MnO = 0.002, MgO = 0.03, Na2O = 0.013, K2O = 0.05,
F = 0.013, P2O5 = 0.034.
• Loss on heating to 550 °C is 12.6 wt%.
• CEC = 0.02 meq/g, the specific surface area = 10.05 ± 0.02 m2/g.
• DTA: endotherm at 630 °C, exotherm at 1015 °C, dehydroxylation weight
loss 13.11% (theory 14%).
• The unit cell composition is:
(Mg0.02 Ca0.01 Na0.01 K0.01)[Al3.86 Fe(III)0.02 Mntr Ti0.11][Si3.83l0.17]O10(OH)8,
octahedral charge: 0.11, tetrahedral charge: -0.17, interlayer charge: -0.06.
2.2.2.2 Serpentines
Substituting Mg for Al in the kaolin structure results in the serpentine,
Mg3Si2O5(OH)4. Here all three possible octahedral cation sites are filled, yielding
a tri-octahedral group carrying a charge of +6. In kaolinite only 2/3 of the sites
are occupied by Al, yielding a di-octahedral group, also with a charge of +6.
Most serpentines are tubular or fibrous. Chrysotile occurs in both clino- and
ortho-structures.
74
Clays
physical properties. All micas form flat six-sided monoclinic crystals with a
remarkable cleavage in the direction of the large surfaces, which permits them to
split easily into optically flat films, as thin as one micron. When split into thin
films, they remain tough and elastic even at high temperature. The dictionary
defines mica as ‘a class of silicates having a prismatic angle 120o, eminently perfect
basal cleavage, affording thin tough laminae or scales, colorless to jet black,
transparent to translucent, of widely varying chemical composition, and
crystallising in the monoclinic system’.
Illites or micas are not pure minerals. The mica structure consists of a pair of
tetrahedral sheets enclosing an octahedral sheet. Between each such sandwich
there are interlayer sites, which can contain large cations. Considerable variation
exists in the composition and polymorphism of the illites. A basal spacing exhibited
in XRD, d001 ≅ 1.0 nm, is somewhat broad and skewed toward wider spacings.
Muscovite derivatives are typically dioctahedral; phlogopite derivatives are
trioctahedral. The cation-exchange capacity of illite is CEC = 0.2-0.3 meq/g of
dry clay. The interlayer potassium exerts a strong bond between adjacent clay
structures. Thus, mica possess a 2:1 sheet structure, similar to MMT, except that
the maximum charge deficit in mica is typically in the tetrahedral layers and
contains potassium held tenaciously in the interlayer space. As a result, micas are
difficult to exfoliate. However, once exfoliated they form dispersions of platelets
with the highest aspect ratio, thus they are particularly useful for the control of
gas or liquid permeability. Several examples of CPNC with mica are provided in
this book. Pironon et al. [2003] proposed the use of FTIR of clay-NH4+ to
distinguish illite from smectite clay.
The coordination of the octahedral sheet is completed by OH anions. The
general formula of mica group minerals is XY2-3Z4O10(OH)2, where X represents
the interlayer site, Y the octahedral sites and Z the tetrahedral sites. The octahedral
sheet can be made up in two ways: either dominantly of divalent cations such as
Mg2+ or Fe2+, in which case all three sites are filled (trioctahedral mica), or else
dominantly trivalent cations such as Al3+, in which case one of the three sites is
left vacant (dioctahedral mica). If solely Si occupies the tetrahedra, the sandwich
is charge-balanced and there is no need for interlayer cations – the resulting
minerals are talc (trioctahedral) or pyrophyllite (dioctahedral). In true micas Al
substitutes for Si in the tetrahedra, and charge balance is maintained by K, Na or
Ca, in the interlayer site. The important rock-forming micas are the trioctahedral
phlogopite and the dioctahedral ‘white’ micas:
• Phlogopite: KMg3[AlSi3]O10(OH)2
• Wonesite (or sodium phlogopite): NaMg3[AlSi3]O10(OH)2
• Annite: KFe3[AlSi3]O10(OH)2
• Eastonite: K[Mg2Al][Al2Si2]O10(OH)2
• Muscovite: KAl2[AlSi3]O10(OH)2
• Paragonite: NaAl2[AlSi3]O10(OH)2
• Margarite: CaAl2[Al2Si2]O10(OH)2
• Mg-Al-celadonite: K[MgAl][Si4]O10(OH)2
• Fe-Al-celadonite: K[FeAl][Si4]O10(OH)2
The average composition of mineral mica is (wt%): SiO2 45.57; Al2O3 33.10;
K2O 9.87; Fe2O3 2.48; Na2O 0.62; TiO2 trace; CaO 0.21; MgO 0.38; moisture
75
Clay-Containing Polymeric Nanocomposites
at 100 °C 0.25; P 0.03; S 0.01; graphite C 0.44; loss on ignition (H2O) 2.74. The
physical properties of a typical phlogopite and muscovite are listed in Table 12.
2.2.2.5.1 Glauconite
Glauconite is green, dioctahedral, micaceous, rich in Fe3+ and K+ ions. It has
many characteristics common to illite. Glauconite may contain randomly placed
expandable layers of the montmorillonite-type. The glauconitic green sands of
New Jersey have been used in ion exchange, water-softening installations, and as
a source of slowly released potassium in soil.
76
Clays
77
Clay-Containing Polymeric Nanocomposites
Na+, Ca2+, K+) sorbed between the three-layers. The cations are stoichiometric,
but held relatively loosely and are readily exchanged by other cations. The triple-
sheet layers form stacks with the interlamellar gallery between them. Their cation-
exchange capacity (CEC) is high, 0.8-1.2 meq/g of air-dried clay, and may be
used as a diagnostic criterion of the group.
Characteristically, smectites expand in H 2O or alcohol. The size and
composition of the interlamellar gallery is highly variable – its minimum thickness
is 0.26 nm, which corresponds to a monolayer of water molecules. With each of
the three sheets 0.22 nm thick, the minimum thickness of the phyllosilicate
interlayer spacing as read by XRD is d001 = 0.92 nm. The flat thin sheets of
smectite crystals have irregular shape and can be up to 1,500 nm in the largest
dimension. Thus, the aspect ratio of smectites is: p ≤ 1500. Owing to
counterbalancing ions present, the nominal value for d001 is taken as 0.96 nm. As
shown in Figure 18, the van der Waals interaction energy (EA) that holds the
stacks together depends very much on the distance between the platelets (h), or
on the interlamellar spacing.
In the early literature, the term montmorillonite was used for this group. In
the natural state these minerals are partially hydrated, with XRD basal spacing
d001 = 1.2-1.4 nm. Solvating them in ethylene glycol expands d001 to 1.7 nm,
while heating to 550 °C collapses it to 0.96 nm. The DTA curves for smectites
show three endothermic and one exothermic peak, within the ranges 150-320,
78
Clays
Figure 18 Van der Waals attraction energy between two phyllosilicate layers
separated by a distance h (nm) (after van Olphen and Fripiat, 1979).
695-730, 870-920, and 925-1050 °C, respectively. The crystal lattice is weakly
bonded. The smectite lattice is expandable between the silicate layers, hence when
soaked in water it may swell to several times its dry volume (e.g., bentonites of
Badlands). A broken surface of these clays typically shows a ‘corn flake’ or ‘oak
leaf’ texture.
There are several species of smectite clay, but the two of greatest commercial
importance and value are montmorillonite (MMT) and hectorite (HT). MMT
tends to have sheet morphology whereas hectorite has a lath or strip morphology.
Commercial availability of hectorite is limited whereas MMT deposits are large
and widely spread around the globe, e.g., 7 in Canada, 6 in the USA, two in
South America, 15 in Europe, 7 in Africa, 3 in Australia, and 8 in Asia. Typical
chemical formulae of the smectite clays are listed in Table 13.
2.2.2.6.1 Bentonite
Bentonite (named after Ford Benton, Wyoming) is rich in MMT (usually > 80%).
Its colour varies from white to yellow, to olive green, to brown to blue. Grades of
this mineral show a broad spectrum of properties and consequently find a variety
of applications and uses. Its origin is a hydrothermal alteration of volcanic ash
deposited in a variety of freshwater (e.g., alkaline lakes) and marine basins
(abundant marine fossils and limestone), characterised by low energy depositional
environments and temperate climatic conditions. The deposits date from Jurassic
to as recent as the Pleistocene epoch, but most are from the Cretaceous period
(85-125 million years ago).
Bentonite beds range in thickness from several centimetres to tens of metres
(most 0.3 to 1.5 m) and can extend for hundreds of kilometres. Bentonite is
widely distributed on all continents. In Canada large deposits are located in British
79
Clay-Containing Polymeric Nanocomposites
Montmorillonite [All.67Mg0.33(Na0.33)]Si4Ol0(OH)2
(MMT)
Hectorite [Mg2.67Li0.33(Na0.33)]Si4O10(HOOFF)2
Beidellite A12.17[Al0.33(Na0.33)Si3.17]O10(OH)2
Nontronite Fe(III)[Al0.33(Na0.33)Si3.67]O10(OH)2
Saponite Mg3[Al0.33(Na0.33)Si3.67]O10(OH)2
Sauconite [Znl.48Mg0.l4Al0.74Fe(III)0.40][Al0.99Si3.01]O10(OH)2X0.33
Note: Na0.33 or X0.33 refers to the exchangeable cation in the interlamellar gallery,
of which 0.33 equivalent is typical
Columbia (French Bar, Hat Creek, Princeton, Quilchena, etc.), Alberta (Rosalind),
Saskatchewan (three ca. 1 m thick beds of Na-MMT near Truax), and Manitoba
(Morden). In the USA, it occurs mainly in Wyoming (overburden: 12 m thick;
1997 price: US$25 to 40 a short ton; estimated deposits: ≥ 1 billion ton), Georgia,
Florida, Mississippi, South Dakota, Montana, Utah, Nevada, and California.
Other known deposits are located in Algeria, Tasmania, Mildura and Scone
(Australia; estimated deposit of 70 million tons), San Juan (Argentina), Sarigyugh
(Armenia), Campina Grande (Brazil), Guangxi and Hangzhou Linan (P. R. China),
Hamza (Egypt), Gewane, Mille and Ounda Hadar (Ethiopia), Landshut
(Germany), Milos (Greece), Kutch (Gujarat, India, estimated deposits: 15 million
ton of good quality sodium bentonite), Java - (Indonesia; estimated deposits
8 million ton), Sardinia (Italy), Annaka and Kuroishi (Japan), Pershwar (Pakistan),
Holy Cross Mountains, Upper Silesia Coal Basin and Sudetes (Poland; deposits:
3 million ton), Eskisehir and Biga Peninsula (Turkey), Tam Bo (Vietnam; deposits:
3 million ton), etc.
Main uses for bentonite are in foundry sands, drilling muds, iron ore pelletising,
absorbents, as a variety of composite liners, food additive for poultry and domestic
animals, in filtration, foods, cosmetics and pharmaceuticals. Bentonite has been
used for clarification of liquids (especially white wine and juice). Bentonite is part
of most adsorbent, bleaching and catalyst clays. About 6 million tons of bentonite
is produced annually [Harben and Bates, 1990; Carr, 1994].
80
Clays
phyllosilicate used for the production of commercial CPNC. MMT has been
known under several names, viz., smectite; sodium montmorillonite; sodium
bentonite or swelling bentonite (Wyoming bentonite (US)); sodium-activated
bentonite (UK); sodium-exchanged bentonite, etc.); the non-swelling (in water)
bentonite is calcium montmorillonite or bentonite (Mississippi bentonite (US));
Sub-bentonite (Texas bentonite, US)). Also known are magnesium montmorillonite
(Saponite & Armargosite), potassium montmorillonite (Metabentonite), lithium
montmorillonite (Hectorite), etc.
The idealised structure of Na-MMT is shown in Figure 17. The unit cell is
usually written as:
Thus, an idealised MMT has 0.67 units of negative charge per unit cell, in other
words, it behaves as a weak silicilic acid. Since the molecular weight of a unit cell
is Mu = 734 + water, the CEC of idealised MMT is: CEC = 0.915 meq/g (one ion
per 1.36 nm2), i.e., the anionic groups are spaced about 1.2 nm apart. The charge
is located on the flat surface of the platelets. As Thiessen demonstrated in 1947,
a small positive charge is also present at the platelet edges.
MMT composition varies across a relatively wide range not only with the
geographic location but also with the deposit strata [Ross and Hendrics, 1945;
Ross, 1960]. The data for 100 samples gave the following ranges of composition:
1. The octahedral layer: Al3.0 - 4.0 Mg0 - 1.4 Fe3+0 - 1.0
2. The tetrahedral layers: Al0 - 0.8 Si7.2 - 8.0
3. Exchangeable cation in the aqueous layer: Na0.67 - 0.8
Chemical analysis of a typical MMT yields: SiO2 = 51.14, Al2O3 = 19.76, Fe2O3
= 0.83, ZnO = 0.1, MgO = 3.22, CaO = 1.62, K2O = 0.11, Na2O = 0.42 and
water 22.8 wt%. Drying at 150 °C eliminates 14.81 wt% of water, with 7.99 wt%
remaining. Another chemical analysis of MMT gave: Al 9.98 wt%, Si 20.78 wt%,
H 4.10 wt%, and O 65.12 wt%. Depending on composition, MMT colour varies
from brick red (due to Fe+3) to pale yellow or blue-grey. The CEC ranges from
0.8 to 1.2 meq/g. In the montmorillonite-nontronite series, as the Fe3+ content
increases from 0 to 28%, the refractive index ranges from 1.523 to 1.590. XRD
patterns of a hydrated MMT yield typically d001 = 1.2-1.4 nm basal spacing.
These values, along with expansion to ca. 1.8 nm in glycerol, have been used for
MMT identification.
The specific surface area of MMT is Asp = 750-800 m2/g (theoretical value is
834 m2/g). From the cited values it follows that the density of the triple sandwich
is 4.03 g/ml and that the interlamellar gallery thickness is 0.79 nm, hence the
interlayer thickness of hydrated MMT should be d001 = 1.45 nm and the average
density ρ = 2.385 g/ml. Drying MMT at 150 °C reduces the gallery height to
0.28 nm (which corresponds to a water monolayer), hence the interlayer spacing
decreases to d001 = 0.94 nm and the average density increases to ρ = 3.138 g/ml.
Assuming that MMT platelets are fully exfoliated and that locally they are parallel
81
Clay-Containing Polymeric Nanocomposites
to each other, the interlayer spacing should be inversely proportional to the clay
volume fraction, φ,
d001 = h/φ
where h ≅ 0.96 nm is the thickness of a single (exfoliated) clay platelet. This
simple relation predicts that the interlayer thickness, e.g., of PA-6 containing,
respectively, 4 and 25-wt% of clay should be 32 and 4.6 nm, which is not far
from the measured values (see Figure 3).
Commercially, MMT is supplied in the form of powder with about an 8 μm
particle size, each containing about 3000 platelets with a moderate aspect ratio p
= 10 to 300. Typical properties and applications are listed in Table 14.
For example [van Olphen and Fripiat, 1979] Na-MMT from Wyoming, SWy-1,
has the composition (wt%): SiO2 = 62.9, Al2O3 = 19.6, TiO2 = 0.090, Fe2O3 = 3.35,
FeO = 0.32, MnO = 0.006, MgO = 3.05,CaO = 1.68, Na2O = 1.53, K2O = 0.53,
F = 0.111, P2O5 = 0.049, S = 0.05. Weight loss on heating to 550 °C = 1.59 and to
82
Clays
1000 °C = 4.47 wt%. CEC = 76.4 meq/100 g, principal exchange cations are Na+
and Ca2+. DTA endotherms occur at 185 °C (shoulder at 235 °C), desorption of
water occurs at 755 °C, dehydroxylation; shoulder at 810 °C, exotherm at 980 °C.
Weight loss in dehydroxylation = 5.53 wt% (theory = 5%). Cell structure is:
(Ca0.12 Na0.32 K0.05)[Al3.01 Fe(III)0.41 Mn0.01 Mg0.54 Ti0.02][Si7.98 Al0.02]O20(OH)4;
octahedral charge = -0.53, tetrahedral charge = -0.02, interlayer charge = -0.55,
unbalanced charge = 0.05.
The early treatments of MMT involved acid-treatment and preparation of
organoclays. The aim of the former was purification, replacement of Ca2+ for H+
and dissolution of some Fe, Al and Mg ions from the octahedral layers.
Manufacture of organoclays started in the 1940s (NL Industries) for use as
thixotropic additives to control flow behaviour of oils, greases, suspensions, paints,
printing inks, cosmetics, etc.
As described earlier in this text, PNC literature recognises four types of
dispersion of layered silicates in a polymer matrix (see Figure 19):
(A) conventional dispersion of non-intercalated clay particles with the basic dry
structure,
(B) intercalated form where the interlayer spacing d001 < 8.8 nm, and
(C or D) exfoliated structures where d001 > 8.8 nm with the individual platelets
either ordered (because of stress field or concentration effects) or not,
respectively.
In aqueous suspension the clay platelets may adopt more complex structures (see
Figure 20). The platelet association (flocculation) may take place by face-to-face
(FF), face-to-edge (FE) or edge-to-edge (EE) interactions [Qian et al., 2000]. Evidently,
each clay structure results in a different set of suspension properties. It suffice to note
that from the hydrodynamic point of view the encompassed volume of suspended
particles dramatically increases from structure (a) to (g), the increase that is reflected
in rheological properties. The EE and EF structures are especially significant.
83
Clay-Containing Polymeric Nanocomposites
84
Clays
85
Clay-Containing Polymeric Nanocomposites
86
Clays
A11 ⎡1 1 2 ⎤
U attraction = − ⎢ 2 + − ⎥ (13)
12π ⎢ h
⎣ (h + 2δ) (h + δ) ⎥⎦
2 2
where, A11 is the Hamaker constant, h is the separation distance between plates,
and δ is the platelet thickness. It is noteworthy that the surface energy of inorganic
solids is about 100 times higher than that of organic liquids. According to Equation
13 the interactions between two crystalline planes decrease with the inversed
square of the separation distance (see Figure 18). Thus, the logical approach to
the process of delamination is to increase the gallery space in several steps, inserting
progressively larger molecules – this is indeed the most common intercalation/
exfoliation strategy.
However, before discussing the methods developed for the intercalation and
exfoliation that lead to CPNC it is advisable to summarise the chemistry of clays.
Several books and reviews are available on the topic, viz. the ever popular early
text by Weiss [1969], Mortland’s review [1970] and other such publications
[Weaver and Pollard, 1973; van Olphen and Fripiat, 1979; Grimshaw, 1980;
Theng, 1974; Raussell-Colom and Serratosa, 1987; Mark et al., 1995], a review
on synthetic clays [Carrado, 2000], etc.
Several active sites on the MMT crystal surface have been identified. In the
absence of water, for molecules not fully coordinated Al constitutes an electron-
pair accepting site. Ions of Fe+3 and Fe+2 provide, respectively, oxidising (electron-
accepting) and reducing (electron-donor) sites (similar activity in the presence of
other metallic impurities is expected). Interactions between the clay surface and
organic molecules by van der Waals forces and by entropic rearrangement effects
have also been observed.
From the point of view of intercalation/exfoliation that may lead to CPNC
the following three active sites are the most important [Brown et al., 1952]:
1. The platelet edges have a few positive charges that attract negatively charged
ions or molecules. These sites have been used to attach organic molecules
making MMT organophilic. However, the reactions involving edge ions do
not increase the interlayer spacing, hence they are not useful for intercalation.
Evidently, once MMT is intercalated, these sites can be used, e.g., to enhance
platelet miscibility with polymeric matrix or mechanical dispersability during
melt compounding. For example, Na-MMT is able to react with weak organic
acids, viz. tannin or ligno-sulfonates. This method has been used for dispersing
clay particles in drilling mud. The reaction does not increase the interlayer
d001 spacing.
2. The –OH groups (four per unit cell) may participate in hydrogen bonding
and chemical reactions. These are mainly located at the crystal edges, bound
to Si, Al or other octahedral ions. The face surface location of –OH groups
has also been postulated [Deuel, 1952; Uytterhoeven, 1960; 1962]. The
concentration of –OH groups can also be enhanced by digesting MMT with
NaOH solution.
87
Clay-Containing Polymeric Nanocomposites
88
Clays
from the original value of d001 ≅ 1.4 nm to 1.9, 3.2 and 3.9 at a 3MHDA loading
of 1, 2, and 3 CEC, respectively. When heated at a rate of 2 oC/min the interlayer
spacing started to collapse at T ≥ 200 oC [Lee and Kim, 2003].
To ensure that free cations are in the system, the pH is usually adjusted to at
least one unit lower than pK; a too acidic medium may cause cations to leach out
from the clay and interfere with the desired exchange reaction.
The type of cation present within the interlamellar galleries affects the magnitude
and uniformity of interlayer spacing. For example, H+ and Ca2+ show a non-uniform
expansion in water, whereas Na+ and Li+ provide easy expansion up to total
exfoliation. Under ambient humidity the d001 depends on the cation, viz. for Na+ it
is 1.4 nm, for Ca2+ it is 1.5 nm and for UO22+ it is 1.48 [Giaquinta, 1997].
The fastest rates of exchange are reported for Na-MMT. The presence of
less hydrated monovalent ions (e.g., K+, Rb+, Cs+) and of multivalent ions (e.g.,
Ca2+, Mg2+, etc.) reduces the rate. It seems that multivalent cations are capable
of simultaneous interaction with anions on adjacent MMT platelets, making
intercalation more difficult. However, since the thickness of the triple sandwich
is 0.66 nm (see Figure 17) compounds having the smallest dimension below
0.6 nm may diffuse into the interlamellar gallery when d001 > 1.4 nm.
The reaction rates in water are faster than those in aqueous solutions of organic
liquids, viz. alcohols, but there are exceptions to this rule, e.g., during intercalation
with organic cations. Increased T accelerates the process, hence the recommended
range is T = 60-80 °C. Similarly, an increase of pressure (P) has been also reported
to speed up the reaction. The particle shape and size also affect the kinetics. The
reaction is diffusion controlled. It starts at the rim and the rate of the linear
diffusion down the slit of diameter d, is proportional to the diffusion time, td,
viz. δd/δtd∝td , hence the diffusion time is proportional to the square root of d.
This prediction is almost confirmed by data from Mackintosh et al. [1971]. As
shown in Figure 22 the experimental exponent a = 0.45, instead of 1/2 was found.
89
Clay-Containing Polymeric Nanocomposites
Thus, modification of clay involves mainly a reaction with the anionic silicilic
groups on the platelet surface. In the presence of strong, but small in size cations
the interaction is mainly ionic, e.g., silicilic acid with Na+. However, when the
latter ion is replaced with a quarternary ammonium one, the van der Waals
interactions become more important. Their importance increases with the
hydrocarbon chain length [Theng, 1964]. Another type of interaction involves
the disruptive effects large cations have on the hydration shell around the interlayer
cation – the entropic effects. It has been found that the effect is more important
for Na+ than for Ca2+ or Mg2+ [Theng, 1967].
2.2.4.1.1 General
Clays are hydrophilic hence the first step in their modification involves reactions in
the aqueous medium. The small and highly mobile water molecules easily diffuse
into interlamellar species, causing a lateral expansion of the clay crystals. The
process is diffusion controlled, hence to swell platelets that are twice as large requires
four times longer. The rate depends on many factors and the time required to reach
equilibrium swelling varies from minutes to days. Since water monolayer thickness
is about 0.28 nm, the first step involves expansion of d001 from 0.96 to about
1.25 nm. Further expansion up to complete exfoliation can be accomplished by
judicious control of conditions, especially the ionic strength and counterion type.
MMT exposed to water vapour expands its basal spacing in steps (which
correspond to one to four molecular layers of water) to d001 = 1.25 to 2.0 nm.
The origin of the water absorption by MMT is on the one hand hydration of the
counterions in the interlamellar galleries and on the other hydrogen bonding to
the clay surface. The work to remove the last monolayer of H2O is about 0.1 J/m2
at the equivalent pressure of 400 MPa.
Dispersing Na-MMT in distilled water causes the ions that are associated
with the clay surface to diffuse out. The osmotic pressure pulls the ions away
from the clay surface, whereas the electrostatic charge tends to hold them near
the surface. Eventually a steady state is achieved and an electrostatic double
layer is formed that keeps the clay platelets apart. The counterions in the double
layer are fairly mobile and can readily be exchanged. The reaction constant
depends on the ionic concentration in the double layer and in the supernatant
solution.
The double layer is formed by adsorption of solvated ions. Their concentration
and the associated electric potential decrease with the distance from the platelet
surface, following the Nernst equation:
Φ = (kBT/νe)ln(c/co) (14)
where: kB is the Boltzmann constant, v is the valence, e is the electronic charge, c
and co are the ion concentration in the solution and where the potential Φ = 0,
respectively.
Thus, the thickness of the double layer depends on the counterion
concentration and valency. Clay platelets can be fully exfoliated in aqueous media,
but on standing, since the surface and edges have different charge, the EF
interactions may lead to formation of a ‘house of cards’ structure. If enough clay
is present, all the water will be tied resulting in a gel formation. Shearing may
90
Clays
disrupt the structure, dramatically reducing the viscosity. The gelation is reversible,
as evidenced by the thixotropic effects [van Olphen and Fripiat, 1979].
Another type of structure that may be formed is a tactoid – a parallel alignment
of clay platelets, up to 10 nm distant from each other, forming high clay
concentration regions in suspensions. In some systems there is a sharp transition
between the gel and tactoid phase. For example, an aqueous suspension of n-
butyl ammonium vermiculite, n-butyl ammonium chloride and either PVME or
PEG has a phase transition temperature between the tactoid and gel phases of
the clay system, Tc = 13 ± 1 °C [Jinnai et al., 1996; Hatharasingle et al., 1998].
Tactoid formation is caused on the one hand by the presence of a repulsive double
layer and on the other by the attractive van der Waals forces. Tactoids have
smaller effects on flow behaviour than the ‘house of cards’ structures.
91
Clay-Containing Polymeric Nanocomposites
surface and displace the adsorbed water molecules [Hendricks, 1941; Jordan,
1949; Jordan et al., 1950]. When the chains are too long to lie flat in the available
space they may tilt, crowding within the interlamellar space. Depending on the
conditions, the hydrocarbons may crystallise, hence the spatial organisation of
the hydrocarbon segments is given by the appropriate crystalline cell unit and
the performance of such organoclay depends on temperature – whether below or
above the hydrocarbon melting point. When the hydrocarbon chains cover the
clay surface, it precipitates from the aqueous suspensions. However, the formed
hydrophobic clay can be homogeneously dispersed in organic medium.
Often the concentration of the organic cations exceeds the amount equivalent
to the clay CEC. For example, commercial organoclays contain from 98 to 153%
of intercalant per nominal CEC of MMT. The reason for the excess is to force
the reversible reaction of ion exchange towards the organocomplex and to increase
the interlayer spacing to maximum.
The orientation of the interlayer cations, hence the d001 spacing, is usually
determined by the projected surface area of the cation (in a given orientation)
provided that it does not exceed the available surface area per surface anion.
Aromatic cations assume either a parallel or an upright position between the
layers, depending on the available space. Weiss and Kantner [1960] proposed a
method of estimating the surface charge density from the d001 spacing of complexes
with mono- and di-alkylammonium cations of different chain lengths. When the
modifier molecules are large and bulky the steric effect precludes total cation
exchange. The average distance between the silicilic anions on the MMT surface
is about 1.2 nm.
However, when the concentration of the organic cations is high, their
adsorption may exceed the amount equivalent to the clay CEC. For example,
quaternary ammonium compound having long hydrocarbon chains can be
absorbed in the amount equivalent of two-and-half times the CEC. The excess
enters the interlamellar galleries in a head-to-tail configuration, profiting from
the hydrocarbon/hydrocarbon chain solubility and the tendency to crystallise.
Under these circumstances, the excess ammonium compounds form a layer with
the cationic groups facing the water phase, forming a diffused electric double
layer that prevents the particles from precipitation. Thus the resulting organoclay
is hydrophilic, hence unsuitable for use in organic medium, e.g., for the preparation
of CPNC [Cowan and White, 1958; McAtee, 1962; Diamond and Kinter, 1963].
Often, the excess modifier can be removed by washing with hot water or alcohol
solution, provided that the cations are not too large [Furukawa and Brindley,
1973]. To avoid formation of the ionic double layer the ionic intercalant is used
to stoichiometry, and then its amine is added to form the head-to-tail, non-ionic
complex.
The perfidy of Nature also provides for an opposite effect – adsorption of less
than the stoichiometric number of organic cations. This situation has been
observed for large molecules (e.g., codeine on MMT) adsorbed from dilute
solutions to form a monolayer on the clay surface, hence shielding adjacent anionic
sites on the clay surface by steric hindrance [Weiss, 1963].
92
Clays
of long-chain molecules with ionic groups usually located along the entire length
of the chain. The polyion may be a polycation with amino groups, or a polyanion
with carboxyl, sulfate, sulfonate, or other negative groups. A single polymer
molecule may contain both positive and negative groups, as is the case for proteins
with amino and carboxyl groups [Hauser, 1950].
Bio-polyelectrolytes (e.g., gum arabic, gelatin, alginates, pectin), modified
biopolymers (e.g., oxidised starch, carboxymethylcellulose) and synthetic
polyelectrolytes are becoming available, viz. polyacrylic acid [Warkentin and
Miller, 1948], polyacrylonitrile [Mortensen, 1962], polyvinyl alcohol [Greenland,
1963], etc. Addition of polyelectrolytes improves the stability of clay dispersion
in the aqueous medium.
93
Clay-Containing Polymeric Nanocomposites
interlayer d001 spacing. Both factors tend to facilitate further absorption of organic
substances by the interlamellar organic phase. The absorption may take place from
the vapour phase, from solution or from melt. It constitutes a vital element in the
strategy of CPNC manufacture.
The mechanism of the secondary absorption is based on the miscibility
principle – only the substances that either can chemically react or are miscible
with the interlamellar organic phase can be absorbed. Furthermore, the
thermodynamic free energy of mixing must be able to compensate for the energy
of increasing separation of the clay platelets. Thus, for example, absorption of a
base requires that the interlamellar phase comprises active acidic functionalities,
while absorption of nonionic compounds requires that their solubility parameter
is comparable to that of the interlamellar phase [Utracki, 1989; 2002b; Utracki
and Kamal, 2002a; Utracki, 2004]. The absorption leads to further expansion of
the interlamellar space, proportional to the total number of -CH2- groups within
the space. The process is diffusion controlled, hence a long residence time and
intensive mixing may be required.
Maximum swelling is facilitated by the organophilic nature of treated clay
and by the high polarity of the organic penetrant. Thus, the initial modification
(in the aqueous phase) should result in the exchange of at least 50% of Na+ by
organic cations and the interlamellar space should be at least 0.8 nm. The best
secondary intercalant should have high polarity and be organophilic, e.g.,
nitrobenzene or benzonitrile. When the secondary intercalant is hydrocarbon,
unsaturation is a definite asset otherwise swelling may have to be aided by addition
of a well miscible (with it) polar organic liquid [Grim, 1968].
Certain organic molecules may also penetrate the interlamellar space to form
coordinated compounds by not directly interacting with the clay surface, but
rather with the cations ionically bound to it. Two types of molecules are suitable,
with either polar or aromatic functionalities. Since this secondary intercalation
is usually conducted using air-dried organoclay (often suspended in an alcohol),
the process must (1) replace the adsorbed water, and (2) form the coordination
shell around the cation. The presence of residual moisture enlarges the
interlamellar space, hence easier diffusion, but at the same time the energetics of
step (2) must be sufficient to compensate for it. When the secondary intercalant
was either ethanol or acetone the number of molecules in a complex depended
on the interlamellar cation. Thus there were 2 for each K+, 3 for each Na+, 8-10
for each Ca2+ or Ba2+, etc. The interlamellar spacing also varied, respectively
from 1.3-1.4 to 1.7 nm [Bruque et al., 1982]. The complexes of Cu-, Ni-, Zn-,
Cd-, Hg- or Ag-MMT with PA or thiourea are highly stable [Peigneur et al.,
1978].
Complexes with water molecules forming bridges between the metal cation
and the organic molecules are known for, e.g., pyridine, nitrobenzene, benzoic
acid, aniline, nitriles, ketones or PEG. The latter compound forms complexes
with M+-MMT even in aqueous suspensions [Parfitt and Greenland, 1970]. The
presence of H2O on the one hand causes expansion of the interlamellar space,
but on the other it makes the system less stable at higher temperatures.
Complex formation of M+-MMT with neutral organic molecules results in
their protonation and stronger bonding. Protonation may originate directly from
the cations present in the system, viz. H+, NH4+ or in general M+, or from the
water molecules that are coordinated to a cation, viz. [M(H2O)x]n+. FTIR or
94
Clays
NMR readily detects protonation. The molecules that undergo these reactions
are amines, azoles or phenols [Raussell-Colom and Serratosa, 1987].
In non-aqueous systems hydrogen bonding of organic molecules to the clay
surface takes place. The positive charge deficiency in the tetrahedral layer results
in negative charge that is spread out on several surface oxygen atoms coordinated
to Al3+ or Si4+ ions [Farmer and Russel, 1971]. The molecules capable of forming
the hydrogen bonds are mainly alcohols, amines, ketones, etc. Identification of
these reactions by spectroscopic means is difficult.
In MMT at the platelet edges there is a limited number of silanol groups that
can be reacted with a diversity of organic compounds, viz. alcohols,
organochlorosilanes, isocyanates, epoxies, diazomethane:
⎧ R − OH → ≡ Si − OR + H 2 O
⎪
⎪ Cl − Si(R)3 → ≡ Si − OSi(R)3
≡ Si − OH + ⎨
⎪ O = C = N − R → ≡ Si − O − CO − NH − R
⎪⎩ R − CH (O) = CH 2 → ≡ Si − O − CH (CH 2 − OH ) − R
Since the number of silanol groups in MMT is small, only a limited number of
organic molecules can be grafted. The grafting does not affect the interlayer
spacing, but may provide for better miscibility with the organic matrix. However,
the silanol groups can also be formed by treating a suspension of MMT in alcohol
with HCl [Lentz, 1964; Zapata et al., 1972]. The treatment removes surface
cations from octahedral layers:
≡ Si − O − Mg − O − Si ≡ + 2H + → 2(≡ Si − OH ) + Mg2 +
The silanol groups in turn can be reacted with a diversity of compounds, e.g.,
having groups susceptible for subsequent polymerisation: polycondensation or
polyaddition.
95
Clay-Containing Polymeric Nanocomposites
96
Intercalation of Clay
2.3
Intercalation of Clay
2.3.1 Introduction
The first step in the preparation of clays for use in PNC is purification of the
mineral (see Section 2.2.3). Depending on the ultimate use of the resulting Na-
MMT, before intercalation the powder may be subjected to further preparatory
steps, either to reduce the particle size and/or to reduce the particle size distribution.
Since the time (t) that intercalant needs to diffuse a distance (l) is given by the
proportionality: t ∝ l2, a decrease of clay particle diameter by 30% results in
reduction of the intercalation time by half. Thus, as described in patents from
Southern Clay [Knudson and Jones, 1986; 1992a,b], the interdiffusion of
intercalating molecules is facilitated by reduction of the clay particle size – high
stresses not only reduce the diameter but may also cleave the stack, reducing the
required force to bend the middle layers during intercalation. Earlier patents similarly
focused on the reduction of clay particle size either by mechanical grinding,
comminuting or by hydrodynamic forces [Cohn, 1967; Clocker et al., 1976].
Since the exchange reaction of the inorganic cation (such as Na+) for the
organic one proceeds from the clay platelet edge toward the centre as a regular
front, reduction of platelet size reduces the time required for the intercalation
(increasing the reaction temperature to ca. 70 oC also helps) [Newman, 1987].
Ion exchange strongly depends on pH – the optimum is about one unit below the
pK-value of the organic salt.
It is noteworthy that reduction of particle diameter is detrimental for the
control of barrier properties, but it may not be essential for the other performance
criteria. Intercalation of clay that has a wide distribution of platelet size often
results in an uneven degree of intercalation, evidenced by broad XRD diffraction
peaks [Ho et al., 2001]. The peak is much sharper when more uniform size Na-
MMT particles are used.
The aims of intercalation are to:
1. Expand the interlayer spacing,
2. Reduce solid-solid interaction between the clay platelets and
3. Improve interactions between the clay and the matrix.
The first goal has been traditionally achieved by making use of the anionic charge
within the interlamellar galleries. Since the van der Waals interactions between
solid surfaces decrease with the square of the separating distance (see Figure 18),
insertion of organic or inorganic molecules into the interlamellar space greatly
helps to achieve the second aim. To reach the third goal, to compatibilise the
system, the principles developed for compatibilisation of polymer blends should
be used [Utracki, 1994; 1998; 2000; 2002a; Ajji and Utracki, 1997; Utracki and
Kamal, 2002b; Ajji, 2002; Brown, 2002].
97
Clay-Containing Polymeric Nanocomposites
98
Intercalation of Clay
99
Clay-Containing Polymeric Nanocomposites
100
Intercalation of Clay
101
Clay-Containing Polymeric Nanocomposites
102
Intercalation of Clay
Figure 23 The interlayer d001 spacing of clays with CEC = 80, 100 and 150 as a
function of the alkyl chain length in a primary ammonium salt: RNH3+Cl-.
After Hackett et al. [1998].
103
Clay-Containing Polymeric Nanocomposites
the amount of clay that was necessary for creating the desired effects two
conditions had to be met:
1. The clay had to have the largest possible aspect ratio; and
2. The organoclay had to be miscible in the matrix liquid.
In other words, the clay had to be exfoliated. Knowing the aspect ratio the required
concentration could be calculated from Equation 1 as φ > φm. The conditions for
miscibility could be calculated considering the molecular structure of the matrix
liquid and the intercalating radical using, e.g., Hansen’s solubility parameter
approach [van Krevelen, 1993], or the equation of state approach [Utracki, 2004].
104
Intercalation of Clay
105
Clay-Containing Polymeric Nanocomposites
106
Intercalation of Clay
107
Clay-Containing Polymeric Nanocomposites
for paints. The author noted that intercalation in aqueous slurry is advantageous
as ‘solvation relaxes the clay’s structure in order to permit penetration of the
organic cations’. However, it is preferable to avoid too dilute a reaction because
the slurry preparation takes time and space and dewatering of product is energy-
intensive. A new, waterless method was developed, based on reacting preblended
clay with quaternary cations by mixing the dry materials in a high pressure reaction
vessel. The process can be batch or continuous. MMT, hectorite, saponite,
attapulgite, sepiolite and their combinations can be used. The onium cation has
a formula R4M+ X-, wherein M is nitrogen or phosphorous, R is alkyl, aryl, or
alkyl-aryl and X is halogen or methyl sulfate. To facilitate the process 3-15 wt%
of a dispersant (neopentyl glycol, pentaerythritol, hydrogenated castor oil,
sulfonated castor oil, a plasticiser, toluene sulfonamide, trialkoxyphosphate, etc.)
might be added. It is preferred that the dispersant has beneficial effects on the
final product.
For example, a mixture of clay, quaternary salt and dispersant passes from a
ribbon blender to a high pressure mixing auger-extruder with a perforated die.
At the downstream end a mixing blade assembly stirs the highly compressed
mixture at pressures of 20-55 MPa. The temperature should be near, but not
above 80 °C. The mixture may be either cycled through the same or another
mixer/reactor, or it may be transferred for further processing or milled to suitable
particle size. Since the process obviates the need for slurring the clay, sand and
other particulates may be present in the product. The material (10 wt% of
organoclay with the remaining constituents) was successfully used in a cable
filling application as an oil gelling agent. The dielectric constant was almost
invariant at T = 21-148 °C.
Two years later, Jordan [1996] published a refinement of the above method.
Thus, a mixture of two quaternary cations was found to induce superior
performance in a variety of applications. The mixture comprised at least 5% of
each: X2R2N+ and XYR2N+ where X is methyl, Y is benzyl and R is an alkyl,
derived from saturated tallow oil. The clay may include 3-15 wt% of a dispersant,
e.g., hydrogenated castor oil.
The organoclay comprised 50-90 wt% of a smectite (MMT, hectorite, saponite,
attapulgite, sepiolite, or their mixture) having exchangeable, inorganic cations
at least in part substituted by a mixture of 10-50 wt% of two organic X2R2N+
and XYR2N+ cations. The composition may include 3-15% (based on clay) of a
dispersant (e.g., neopentyl glycol, pentaerythritol, hydrogenated castor oil,
sulfonated castor oil, toluene sulfonamide, trialkoxyphosphate). As in the previous
patent, the pre-blended mixture was processed using a blender and an auger-
extruder with perforated die. The product was milled to usable particle size. The
interlaminar spacing was not determined.
The modified clay was evaluated for paint and grease thickening applications.
In the first case, the thixotropic index and the number of oversized particles were
measured – the new organoclay was found to equal or exceed the best
commercially available materials made using a high-cost slurry process. The
greases were tested for consistency by utilising a Helipath instrument. Again, the
results showed that the new organoclay offered significantly better performance
than the standard materials.
Eilliott and Beall [1989] patented an organoclay composition for use as a
rheological additive in a variety of non-aqueous liquids, such as paints, varnishes,
enamels, waxes, adhesives, inks, laminating resins, gel coats, etc. To obtain
108
Intercalation of Clay
109
Clay-Containing Polymeric Nanocomposites
(iii) Transferring the modified clay to a reactor (the preferred reactive exfoliation
method) or compounding it with a resin.
The patent listed thermoplastic and thermosetting resins as well as elastomers
(e.g., PE, PP, PS, PIB, acrylics, TPU, SBS, liquid BR, PB or IR, etc.) as potential
matrix polymers. However, the main interest was to produce CPNC in low polarity
polymers, such as PO or rubbers. The guest molecule should have a polar group
at the chain-end. The following groups might be used: hydroxyl (-OH), halogen
(-F, -Cl, -Br, or -I), carboxyl (-COOH), anhydrous-carboxylic acid (maleic), thiol
(-SH), epoxy radical, or primary, secondary or tertiary amine (-NH2, -NH, -N).
In the described examples the authors used as onium salts 2M2ODA, 2M2TDA,
or TDA; as a ‘guest molecule’ hydrogenated, low molecular weight polybutadiene
with an -OH group at the chain end (HTBR), stearic acid or alcohol alone or
with HTBR, maleated PP (PP-MA with high acid value hence low MW), etc. To
ascertain good miscibility of organoclay with the matrix polymer a second ‘guest
molecule’, e.g., low molecular weight polyisoprene (IR) or oligopropylene, could
be used. The process resulted in a high degree of clay dispersion [Kato et al.,
1997].
The patent on CPNC with PA as matrix [Okada et al., 1988] described the
following method for uniformly dispersing clay platelets with interlayer distance
d001 ≥ 2.0 nm. The manufacturing process comprised three steps:
1. Intercalation of a clay (CEC = 0.5 to 2.0 meq/g, e.g., smectite, vermiculite or
halloysite);
2. Mixing the organoclay with a PA-monomer and
3. Polymerisation.
Only the first step is of interest in the present discussion.
The intercalation was accomplished by dispersing clay in an aqueous, acidified
intercalant solution, followed by washing the organoclay with water to remove
excess ions, or by mixing an aqueous suspension of clay with a cation-exchange
resin previously treated with an intercalant. The easiest to treat were the sodium-
substituted clays, viz. Na-MMT (CEC = 0.8-1.0) or Na-vermiculite (CEC = 1.8).
Inorganic (viz. Cu2+, Al3+), or organic cations were used. In the latter case α,ω-
alkyl acids H3N+ CnH2n COOH were used, with n = 12 for the preferred dodecyl
(ADA), n = 14 for tetradecyl (ATDA), n = 16 for hexadecyl (AHDA), or n = 18
for octadecyl (AODA). For example, to a suspension of 100 g Na-MMT in 10 L
of water, 51.4 g of ADA and 24 ml HCl were added, and the mixture was stirred
for 5 min. After filtration, the organoclay was thoroughly washed and vacuum-
dried. After execution of steps 2 and 3 (dispersion in a monomer, then
polymerisation) the resulting CPNC contained fully exfoliated clay platelets and
showed significant improvement of the mechanical and thermal properties. As
displayed in Figure 25 the intercalation effect on the interlayer spacing depended
very much on the paraffin chain length and the presence of monomer; only after
polymerisation was full exfoliation obtained.
A patent from Toyota [Kawasumi et al., 1989] reported that clays may be
intercalated in an aqueous medium with ammonium salt of a primary, secondary
or tertiary linear organic amine. However, owing to the envisaged use of the
organoclay in polymerisation, the preferred intercalant has remained ADA.
Several patents on the intercalation of clays with onium ions originate from
SCP. Thus, Dennis [1998] described the preparation of organoclay compositions
110
Intercalation of Clay
Figure 25 Interlayer spacing after intercalation with ω-amino acid (AA) having
n CH2 segments in the molecule. The lower curve is for intercalation with AA only,
the upper curve is for AA with ε-caprolactam at 100 °C (2 g of lactam per 0.5 g of
Na-MMT + AA). Data Okada and Usuki [1995].
useful in grease and ink formulations. The organoclay was the reaction product of
a smectite-type clay having CEC ≥ 0.50 meq/g and a branched chain alkyl quaternary
ammonium compound. Useful clays include bentonite, hectorite, as well as, synthetic
smectite-type clays, such as MMT, beidellite, hectorite, saponite and stevensite.
The branched quaternary ammonium intercalant has the formula: R1R2R3C(R4
R5R6)N+M–, where M– is an anion (preferably methyl sulfate, chloride or bromide),
R1 = R2 = -CH3, R3 is a linear or branched saturated or unsaturated alkyl group
having 12-22 carbon atoms, R4 is hydrogen or a saturated lower alkyl group of
1-6 carbon atoms; R5 is hydrogen or a linear or branched saturated alkyl group of
1-22 carbon atoms; R6 is a linear or branched saturated alkyl group of 5-22 carbon
atoms; and M is the salt anion. Especially preferred are the quaternary ammonium
salts wherein R3 is hydrogenated tallow and R4, R5 and R6 are together a
2-ethylhexyl.
Organo-MMT was prepared using the following steps:
1. Aqueous bentonite slurry (2 wt% solids) was passed three times through a
homogenising Manton-Gaulin mill (MG-mill).
2. The slurry was then heated to 66 °C and reacted for 30 min with dimethyl-
hydrogenated tallow-2-ethyl-hexyl ammonium methyl sulfate (2MHTL8, a
commercially available quaternary ammonium salt as Arquad HTL8), a blend
of Arquad HTL8 with dimethyl dihydrogenated tallow ammonium chloride
(2M2HTA, a commercially available quaternary ammonium salt as Arquad
2HT), or other quaternary amines.
3. The reacted slurry was sheared again through an MG-mill at 29 MPa.
4. The organoclays were vacuum filtered, fluid bed dried at 80 °C, and milled
through a 0.2 mm screen. Several commercial organoclays from SCP, e.g.,
Cloisite®-25A, -6A, -15A and -20A comprise these compounds.
111
Clay-Containing Polymeric Nanocomposites
The following patent [Gonzales et al., 1998a], specifically describes the preparation
of MMT organoclays to be used for the production of CPNC. The organoclay is the
reaction product of smectite-type clay having a CEC ≥ 0.50 meq/g and a mixture of
a first quaternary ammonium salt (e.g., 2M2HTA) with either a second quaternary
ammonium salt containing a -C=C- double bond, or a chain transfer agent. The
second ammonium salt has the formula: R1R2R3R4N+M–, where M– is an anion
(preferably methyl sulfate, chloride or bromide), and Ri are independently selected
from the group consisting of (a) linear or branched, saturated or unsaturated
alkyl groups having 1 to 22 carbon atoms, (b) aralkyl groups which are benzyl
and substituted benzyl moieties, (c) aryl groups, (d) β,γ-unsaturated groups having
≤ 6 carbon atoms or hydroxy-alkyl groups having 2-6 carbon atoms, and (e)
hydrogen, with the proviso that at least one of the substituents is a linear or branched
unsaturated alkyl group. The chain transfer agent may be a thiol, DL-cysteine,
α-methylketone, or a halogen compound.
The intercalation process comprises the following steps:
1. Dispersing a clay in an aqueous medium,
2. Heating the dispersion to T ≥ 30 °C,
3. Adding a first quaternary ammonium salt, then the second quaternary
ammonium compound or the chain transfer agent, and
4. Agitating the mixture to complete the reaction.
For example, MMT was intercalated with 2M2HTA and either DL-cysteine, or
N,N-dimethyl-amino-methacrylate. For the first system d001 spacing was determined
as 2.3 nm, whereas for the second two peaks were found at d001 = 1.4 and 2.6 nm
– evidently in the latter case not all MMT tactoids were intercalated.
Another patent from SCP describes the preparation of organoclays for use as
a rheological additive in an unsaturated polyester resin/styrene system [Farrow
et al., 1998]. Thus, a mixture of two clays was treated with 0.35 to 0.65 meq of
the alkyl quaternary ammonium salt per 1 g of the clay mixture. The mixture
contained 70 to 90 wt% of clay (a) selected from between sepiolite, palygorskite
and their mixtures; and 30 to 10 wt% of clay (b) selected from a smectite group
consisting of hectorite, MMT, bentonite, beidellite, saponite, stevensite and their
mixtures. The alkyl quaternary ammonium cation was either 2M2HTA,
MB2HTA, 2MBHTA or 2MHTL8, with the counterion being chloride, bromide,
methyl sulfate, nitrate, hydroxide, acetate, phosphate, etc.
Production of organoclay followed five steps:
1. The clays (sepiolite, palygorskite, hectorite) were crushed, ground, slurried
in water and screened to remove grit and other impurities.
2. Dilute (1 to 6% solids) aqueous slurry of the clays was then subjected to
high shearing in a homogenising Manton-Gaulin mill, operated with a pressure
differential across the gap from 14 to ≥ 55 MPa.
3. The clay slurries may be mixed together, e.g., 80 wt% sepiolite with 20 wt%
hectorite or 70 wt% palygorskite with 30 wt% MMT.
4. The mixture was treated with a quaternary ammonium salt.
5. The resulting organoclay was dewatered, dried and ground.
The products were found to display highly desirable properties when used as a
thixotrope in the gelling of an unsaturated polyester resin. Thus, the organoclay
(0.1 to 4 wt%) may be directly dispersed in an unsaturated polyester
112
Intercalation of Clay
(a) (b)
Figure 26 (a) The basic structure of the cyclic amidine intercalant family;
(b) Derivatives of (a) particularly suitable as intercalants (see text).
Reproduced from Zilg et al. [1999], with permission.
113
Clay-Containing Polymeric Nanocomposites
Synthetic MMT was intercalated and XRD showed that the interlayer spacing
increased from d001 = 0.94 to 2.67 (for RDI), 3.27 (for HDI and ADI), and 4.01 nm
(for MNTFA). The intercalation started with dissolution of the intercalant in
acidified, hot water, followed by addition (while stirring) of a synthetic clay
suspension. As a result of the cation exchange, flocculated clay precipitated, it
was filtered, washed (until Cl– could not be detected with AgNO3 solution), and
then dried under vacuum at 80 °C for 72 h.
According to the Ciba patent, the amidine-intercalated clays may be used for
the production of CPNC with virtually any polymeric matrix (thermoplastic,
thermosetting or elastomeric), viz. PO, vinyls, styrenics, acrylics, PA, thermoplastic
polyesters (PEST), PC, polyphenylene sulfone (PSF), polyarylethers, diverse
polycondensates or polyadducts, rubbers, etc. Preferred polymers are PEST, PU,
thermosetting epoxy and polyurethanes.
A recent invention for polymeric (primarily PEST) composition with high barrier
properties [Barbee and Matayabas, 2000; Matayabas et al., 2000] again uses
layered clay that has been cation exchanged with onium salt represented by the
formula [R1R2R3R4M]+ X-, where M is N or P; X- is a halide, hydroxide, or acetate
anion; R1 is a straight or branched alkyl group having at least 8 carbon atoms; R2,
R3 and R4 are independently hydrogen or a straight or branched alkyl group having
1 to 22 carbon atoms. The polymer barrier properties were improved by the addition
of up to 30 wt% of a mixture of onium-intercalated clay (e.g., MMT-MT2EtOH)
with an agent, which expands the interlayer spacing to d001 ≥ 3 nm and is miscible
with the polymer. The ratio of clay to the ‘expanding agent’ varied from 1:4 to 4:1.
Suitable ‘expanding agents’ are mainly low molecular weight compounds (from
monomers to Mn = 25 kg/mol), viz. PCL, PDMS, polyepoxides, PS, polyacrylates,
PC, PU, PSF, PA, PEST, polyethers, polyketones and vitamin E. The ‘expanding
agents’ used in examples were: PETG 6763, PEG (MW = 3.35 kg/mol), PCL (MW
= 2 kg/mol), carbinol-terminated PDMS, etc.
The process recommended by these authors for manufacturing PET
nanocomposites comprised:
1. Preparing the organoclay
2. Pre-swelling the organoclay with an ‘expanding agent’ and
3. Incorporating the expanded organoclay in a polyester.
For example, an aqueous suspension of Na-MMT (CEC = 0. 95 meq/g) was
mixed at 50 to 80 °C in a blender to form a 2 wt% slurry. The methyl tallow bis-
2-hydroxyethyl quaternary ammonium (MT2EtOH) (Ethoquad T/12) was added
in sufficient amount to exchange most of the cations present in the galleries. The
precipitate was filtered out, washed and dried. XRD of the product showed that
d001 = 2.0 nm. Next, the expanding agent (PET modified with 30 mol% of 1,4-
cyclohexane dimethanol available as PETG 6763) was dissolved in methylene
chloride, the organoclay was added and the mixture was blended at high speed.
Next, the suspension was poured over PET pellets, followed by evaporation of
the methylene chloride, and drying the coated pellets in a vacuum oven at 110 °C.
The coated pellets were finally compounded in a TSE at 275 °C and 200 rpm.
For the manufacture of polycarbonates, polyesters and polyphenylene ethers
(PPEs) from low viscosity macrocyclic oligomers, layered minerals were
intercalated with novel cations [Takekoshi et al., 1996]. The preferred type cations
were guanadinium and amidinium, viz. hexa-butyl-guanidinium. However, more
traditional onium cations were also acceptable, especially of pyrrolidine,
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Intercalation of Clay
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Clay-Containing Polymeric Nanocomposites
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Intercalation of Clay
by at least two C-groups. Colourless CPNC was prepared by dry blending a mixture
of clay pigments with Claytone‚ APA and PET. The well-dried mixture was extruded at
275 °C. Unfortunately, there is no information on the extent of intercalation/exfoliation
in, or the properties of the CPNC. Similarly for PET, Imai et al. [2002] developed
intercalant able to react with PET, with a cationic group to bind to clay and stable at
least up to 275 °C. The selected compound was a dimethyl isophthalate substituted
with a triphenyl-phosphonium group (dimethyl isophthalate triphenyl phosphonium,
DIP). In spite of lack of exfoliation, 8 wt% of the pre-intercalated clay increased the
matrix modulus by 80%.
TNO patented the use of dyes as intercalants [Fischer et al., 2001], such as,
e.g., methylene blue:
N
H3 C CH3
N S N+
CΓ
CH3 CH3
Virtually any polymer can be used as a matrix, but for the coating applications
the preference goes to PU, acrylics, siloxanes, polyesters and polyethers. The
new intercalants offer better thermal stability, controllable amount of intercalation,
ability to introduce functional groups for end-tethering the matrix
macromolecules, etc. The technology was commercialised for the production of
Planomers®, PlanoCoatings® and PlanoColors®. The Planomer range is an
organoclay tested in diverse polymeric matrices, viz. PO, PMMA, PA, PU, PS,
PC, phenolics, and biopolymers. The second material is used as a transparent
barrier material in packaging or for protection. The PlanoColors® are offered as
highly UV stable, clay-based, metal-free nanopigments in a variety of colours.
Conroy et al. [2002] prepared high temperature CPNC by dispersing up to
10-wt% of clay in molten phthalonitrile monomer or oligomer that in turn was
polymerised into CPNC, stable to T ≥ 450 °C. The authors replaced the customary
(and thermally unstable) ammonium intercalants by compounds with nitrile
groups. This new type of organoclay may be used with a variety of polymers,
such as, PA, PC, PO, PEI, PI, TPU, PVP, PVAl, PEG, epoxy, etc. Unfortunately,
this patent application does not provide examples of CPNC preparation or
performance characteristics.
In summary, the standard method of clay intercalation with organic cations
usually starts with purified bentonite or MMT. The clay has a layer of Al and Mg
hydroxides between two layers of silica that are negatively charged and ionically
balanced by Na+, K+, Ca2+and Mg2+. The repeating layers are 0.96 nm thick and
under ambient conditions the basal or d-space is d001 = 1.2-1.5 nm, hence the
interlamellar space in the gallery is about 0.2 to 0.5 nm. At this stage the clay is
unsuitable for use in PNC technology - the interlamellar gap is too narrow for
the diffusion of macromolecules, the solid-solid interactions between the clay
platelets are too high. The oldest and still most frequently used method has been
to replace the inorganic cations with onium ones. This increases the interlayer
distance to d001 ≥ 2.5 nm, reduces the interlayer forces, makes the clay more
hydrophobic and makes it amenable to dispersion in a monomer or polymer.
However, the most common intercalant, quaternary ammonium has limited
thermal stability. Ammonium-modified clay may be used to prepare CPNC by first
dispersing it in a monomer that in turn is polymerised by UV, acid, base or heat.
117
Clay-Containing Polymeric Nanocomposites
118
Intercalation of Clay
119
Clay-Containing Polymeric Nanocomposites
Table 16 Continued...
Organoclays from Süd-Chemie AG based on Na-MMT
Nanofil Intercalant Wt. loss Bulk density Matrix d001
(%) (g/l) (nm)
15 2S2M 35 440 EVAc, PP 2.8
948 2S2M 45 440 EVAc, PP 3.5
32 SB2M 30 300 PET, PBT 1.8
919 SB2M 35 460 PET, PBT 2.0
848 SA 25 180 EVAc, PP, PA 1.8
804 S2EtOH 30 130 PET, PBT, TPU 1.8
784 AC12A 20 180 PA-6, PA-66, PA-12 1.7
Organoclays from Rheox, Inc. based on Na-MMT
B 34 2M2TA 2.47
Note: Commercial hydrogenated tallow oil typically contains (in wt%): 2.0 C14,
0.5 C15, 29.0 C16, 1.5 C17, 66.0 C18, and 1.0 C20 alkyl groups
120
Intercalation of Clay
121
Clay-Containing Polymeric Nanocomposites
Table 17 Continued...
AODA ω-Amino-octadecanoic acid
APB 1,3-Bis(3-aminophenoxy)benzene
APTS γ-Aminopropyl-triethoxy silane
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Intercalation of Clay
Table 17 Continued...
OM-l N-[4-(4´-Amino-phenyl)]phenyl phthalimide
123
Clay-Containing Polymeric Nanocomposites
[Zilg et al., 1999]. Furthermore, it is expected that: (1) ammonium cations with
strong bonding to clay anions will show greater thermal stability, (2) the presence
of unbounded amines or ammonium salts will have deleterious effects on thermal
discolouration, (3) the ammonium ion can be shielded by more stable secondary
intercalants, e.g., epoxies.
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Intercalation of Clay
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Clay-Containing Polymeric Nanocomposites
126
Intercalation of Clay
clay aspect ratio was seriously reduced (thus reducing MMT effects on
performances), the bonding between the clay and the matrix was not strong
enough and the polyamide matrix had a broad molecular weight distribution,
viz. Mw/Mn ≥ 6 [Okada et al., 1988]. Even if the monomer molecules diffuse into
the interlamellar space they rarely bond strongly enough (by ionic or covalent
bonds) to the clay surface, and the CPNC may be exfoliated, but not end-tethered.
Several publications from the Toyota group indicate that even highly polar
and relatively small monomers, such as ε-caprolactam, do not provide sufficient
intercalation and bonding to the clay surface – Na-MMT must be pre-intercalated
[Usuki et al., 1990; 1993a,b; 1995]. The latter process was carried out with
12-aminolauric acid (ADA) in aqueous medium. Obviously, instead of ADA
another highly polar, water-soluble compound may be used, but as in any other
cation-exchange intercalation process, the initial step of intercalation seems to
require the presence of water. The intercalation with ADA results in nearly
quantitative cation exchange; hence after polycondensation the PA-6 matrix is
end-tethered and densely packed near the clay platelet surface.
Prior to the emulsion or suspension polymerisation of styrene, the clay platelets
dispersed in aqueous media (viz. Na-MMT) may be fully exfoliated. However, in
the recovered polymer the interlayer spacing is quite small, d001 ≤ 1.7 nm,
indicating re-aggregation. Thus, as a rule, to achieve a reasonable degree of
intercalation in CPNC the intercalant must bind to the clay surface. The binding
can be achieved by ionic bonding, covalent bonding (e.g., through ≡Si-OH groups)
or at least through hydrogen bonding with hydrophilic compounds.
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Clay-Containing Polymeric Nanocomposites
bonded to the clay platelets, thus increasing the interlayer spacing to d001 = 3-4.5 nm
(the most desirable spacing!). To bond, the intercalant needed either a strong
polar group (e.g., carbonyl, hydroxyl, carboxyl, amine, amide, ether, ester, sulfate,
sulfonate, sulfinate, sulfamate, phosphate, phosphonate, phosphinate) or an
aromatic ring able to form a metal-cation complex. Several types of interaction
were envisaged, viz. by metal cation electrostatic bonding, chelation of the clay
metal cations, bonding between clay inorganic cations and intercalant aromatic
rings, by hydrogen bonding to the surface -OH groups, etc.
The following water-soluble polymers or oligomers were reported useful as
intercalants:
• P4VP (MW = 1-40 kg/mol). Its solubility can be adjusted by hydrolysis or by
forming a sodium or potassium salt. Copolymers of vinylpyrrolidone and
vinyl amide or γ-amine butyric acid, can be similarly treated.
• Fully hydrolysed PVAl (MW = 2 to 10 kg/mol).
• Fully or partially neutralised salts of a polyacrylic acid (PAA) or a
polymethacrylic acid (PMAA, MW = 0.2 to 10 kg/mol).
• Polymethacrylamide, poly(N,N-dimethyl acrylamide), poly(N-isopropyl
acrylamide), poly(N-acetamido acrylamide), poly(N-acetamido
methacrylamide), their copolymers or interpolymers containing PAA, or
PMAA.
• Polyvinyloxazolidone (PVO) and polyvinyl methyl-oxazolidone (PVMO),
PEG, polypropylene glycol (PPG) and their copolymers.
• Polymeric quaternary ammonium salts.
• Sodium salts of acrylate/vinyl alcohol, olefin/maleic acid, polymethacrylate,
polystyrene sulfonate, styrene/acrylate/PEG dimaleate, styrene/PEG maleate/
nonoxynol, etc.
• Styrene copolymers with acrylamide, acrylate-ammonium methacrylate,
maleic anhydride, PVO, etc.
• Diverse copolymers, viz. cornstarch-acrylamide-sodium acrylate, diethylene
glycol-amine-epichlorohydrin-piperazine; dodecanedioic acid-cetearyl alcohol-
glycol, ethylene-vinyl alcohol, hydroxy ethyl-polyethyleneimine, polyvinyl
methacrylate-methacrylic acid, melamine-formaldehyde resin, phthalic anhydride-
glycerin-glycidyl decanoate, metal salts of acrylic and polyacrylic acid, sucrose
benzoate-sucrose acetate, isobutyrate-butyl benzyl phthalate, sucrose benzoate-
sucrose acetate isobutyrate-butyl benzylphthalate-methyl methacrylate, vinyl
acetate-crotonic acid, and polysaccharide copolymers.
• Prepolymers: urea-formaldehyde, urea-melamine-formaldehyde, etc.
In the cited patent [Beall et al., 1996a] the preferred intercalants are P4VP,
PVAl, and their mixtures at the weight ratio of intercalant-to-Na-MMT = 1:5-
1:3. By contrast with the prior publication that indicated significant difficulties
and achieved minor expansion of the interlayer space, the new intercalation in
the presence of at least 10 wt% of water proceeded quite readily using any of the
three methods. For example, to intercalate Na-MMT with P4VP (MW = 10 and
40 kg/mol) or PVAl (75-99% hydrolysed) the following processes were used:
1. Mix for 4 h aqueous 2 wt% solution of P4VP (MW = 10-40 kg/mol) with
2 wt% suspension of Na-MMT clay in water, at a ratio sufficient to vary the
weight ratio of clay to P4VP from 4:1 to 1:4, based on dry mass.
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Intercalation of Clay
2. Add the clay (ca. 8 wt% of moisture) to aqueous 2 wt% solution of P4VP in
a ratio as in method (1) and mix for 4 h.
3. Dry blend P4VP with Na-MMT, and then add 35-38 wt% H2O (based on
dry clay) and extrude the paste.
When a dry blend of Na-MMT and powdered P4VP was mixed with 75 wt%
water an exothermic reaction was observed. Apparently, the bonding reaction of
a polymer to the internal face of the clay platelets is sufficient to engender an
exothermic exfoliation.
All of the three methods resulted in intercalation of MMT. The final spacing
did not depend either on the method of preparation or MW of P4VP, but on the
quantity of polymer sorbed between platelets. Exfoliation did not take place
unless the clay contained at least 10 wt% water. The polymer-engendered
expansion of the interlayer was demonstrated by drying the intercalated samples
for 4 h at 120 °C – only a small change in the interlayer spacing was detected.
The generality of the developed technology was demonstrated in later patents
(see below), where Na-MMT was directly intercalated with insecticide or pesticide
(e.g., 2,4-dichloro phenoxy acetic acid butyl ester), provided that their molecules
were water-soluble and had strong polar groups.
As shown in Figure 28 the interlayer spacing increased with the concentration
of P4VP or PVAl in steps. When the intercalating composition contains < 16 wt%
of intercalating polymer a monolayer is sorbed between the platelets, increasing
the interlayer spacing by < 1 nm. When the concentration is in the range from
16 to 35 wt% the interlayer spacing increases by 1 to 1.6 nm. At loadings of
35 to 55 wt%, the interlayer distance is increased to about 2.0-2.5 nm, which
corresponds to three layers of intercalant sorbed between adjacent clay platelets.
At loadings of 55 to 80 wt% the interlayer distance is increased to 3.0-3.5 nm,
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Clay-Containing Polymeric Nanocomposites
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Intercalation of Clay
chain with n ≥ 6. The compound must also have a polar group, viz. hydroxyl,
polyhydroxyl, carbonyl, polycarboxylic acids and salts, aldehydes, ketones,
amines, amides, ethers, esters, lactams, lactones, anhydrides, nitrites, halides,
pyridines and their mixtures. The intercalating composition should have a weight
ratio of organic intercalant to clay ≈ 1:4.
According to the authors, bonding by the intercalant polar ends causes the
molecules to stretch in the direction normal to the platelet surface. This increases
the interlayer spacing, while consuming little of the intercalant. As a result, there
is sufficient expansion of d001 and sufficient concentration of the remaining free
cations to ascertain sorption of polymerisable monomer, oligomer, and/or polymer
molecules, e.g., of an epoxy resin. The process does not require either onium
ions or silane coupling agents. It can be applied to all resins, but it has been
specifically designed for the epoxy resins. Diluting the Na-MMT/intercalant
concentrate with a monomer or oligomer, and then curing may lead to exfoliation.
The presence of polymerisable monomer or oligomer in the clay galleries improves
miscibility with the matrix polymer, hence a masterbatch can be mixed with
additional polymer.
Alternatively, the intercalant may be dispersed into a melt processable thermoplastic
or thermosetting matrix oligomer or polymer, then clay and water added. The matrix
polymer may have DP = 10-100, and a melt index MI = 0.01-12 g/10 min at the
processing temperature. For example, Na-MMT (8 wt% water; CEC = 1.2 meq/g)
was mixed at room temperature with epoxy resin and 1-dodecyl-2 pyrrolidone
(DDP) in a 1:1 molar ratio to the Na+. Then, water was gradually added to the
mixture. The solid-like mixture was extruded using a single screw extruder (SSE)
and dried at 90-95 °C obtaining uniform powdered materials. XRD determined
that incorporation of DDP and epoxy increased the interlayer spacings of
Na-MMT, d001 = 1.23 to 3.4 nm. Similar spacing was obtained using different
mixing sequences and methods, viz. by adding DDP and epoxy to clay slurry and
then drying the mixture; by adding DDP/epoxy/water emulsion to clay, extruding
using a twin screw extruder and drying. However, when DDP was eliminated
from the formula the maximum interlayer spacing achieved by adding water and
epoxy was d001 = 1.9 nm. In conclusion, water is the essential element for the
co-intercalation by the epoxy and DDP molecules. Owing to the co-intercalation,
the free liquid phase of DDP/epoxy/water disappears and the mixture becomes
solid-like. DDP molecules bind to the interlayer Na+ and epoxy molecules diffuse
into the interlayer spacing. The co-intercalate has the molar/weight ratio:
DDP/epoxy/MMT = 1:1:0.75.
Several types of polar organic compounds can be used as intercalants, including
long chain ethers, esters or alcohols, having a polar end group that provides the
molecule with a dipole moment greater than that of water. The listed examples
include aliphatic; aromatic; aryl-substituted aliphatic; alkyl-substituted aromatic
alcohols and phenols, e.g., manufactured from coconut, tallow and/or palm oils.
Straight-chain acids can also be used, for example, stearic, oleic, linoleic, ricinoleic,
canola, castor, tallow-based, soybean or coconut. Representative aldehydes include
C6 to C28, phenyl acetaldehyde, etc. Amines (primary, secondary and tertiary) or
amides are also suitable, viz. oleylamine, soya alkylamines, hydrogenated or not
tallow or ditallow alkylamines, palmitamide, hexadecyl amide, stearamide,
oleamide, linoleamide, etc. Suitable nitrites include hexanonitrile,
n-nonadecanitrile and others. Lactones, lactams, pyridines and surface-active esters
can also be used.
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Clay-Containing Polymeric Nanocomposites
132
Intercalation of Clay
133
Clay-Containing Polymeric Nanocomposites
the clay anions not available for additional macromolecules. The surface saturation
coverage increased in the order:
partially protonated P4VP > quaternised ionene form
> completely protonated P4VP.
By contrast with neutral P4VP, the partially protonated P4VP could be adsorbed
at different levels. XRD showed that the d001 spacing increases with P4VP loading
(see Figure 29). At a concentration of P4VP > 70 wt% the XRD peak disappeared
due to delamination. The FTIR spectra provided additional evidence of P4VP
interaction with the clay surfaces.
Fischer [1999] patented the use of block or graft copolymers for the preparation
of CPNCs. By analogy to compatibiliser in immiscible polymer blends, the
copolymer must have two types of structural units, one (A) to interact with clay
the other (B) with polymer. The molecular weight of part A should be MW = 0.1 to
5 kg/mol (DP = 5 to 20), while for part B MW = 0.1 to 20 kg/mol. To interact with
clay the structural units of part A should be hydrogen-bonding, e.g., vinyl
pyrrolidone, vinyl alcohol, ethylene glycol, ethylene imine, vinyl pyridine, acrylic
acid, acrylamide. To interact with the matrix the structural units of part B should
be miscible with the matrix polymer and able to entangle. In the organoclay the
inorganic clay content ranged from 5 to 600%, while in CPNC it constituted from
2 to 55 wt%. Judging by the examples, preferably the intercalant is a block
copolymer, e.g., PS-b-PEG or PS-b-PVP. The intercalation is performed in THF,
followed by solvent evaporation and melt compounding with the matrix polymer.
Fischer et al. [1999; 2001] used this strategy to prepare CPNCs with either
natural or synthetic clay and either PS or PMMA as matrix. The authors started
directly with Na-MMT, Na-saponite, or Na- fluorohectorite (CEC = 0.85 to
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Intercalation of Clay
3.2 meq/g). Block or graft copolymers were used (viz. PS-b-PEG, PMMA-b-PEG,
PMMA-co-polymethacrylic acid, PS-b-P2VP; MWblock = 1 to 27 kg/mol) having
one part either identical to or miscible with the matrix polymer and the other
capable of intercalating with the clay. The interaction between the compatibiliser
and clay was preferentially ionic or hydrogen bonding. The intercalation was
performed either in the melt (copolymers with PEG) or in solution. It resulted in
individual clay platelets and/or short stacks containing 2-10 layers homogeneously
distributed in the matrix. As expected, better mechanical performance was
obtained for block copolymers having the miscible block with molecular weight
above the entanglement molecular weight value: MW > Me.
Several clays (e.g., sodium montmorillonite, hectorite, and laponite) were melt-
intercalated with PEG using microwave irradiation [Aranda et al., 2003]. The
process was found to depend on irradiation time and power, amount and relative
ratio of the reagents, and relative humidity. The process resulted in d001 ≅ 1.8 nm
indicating formation of a hydrated double layer of PEG within the interlamellar
galleries. Thus, 10 minutes of microwave irradiation of moderate power was able
to accomplish a similar task as shear compounding in an internal mixer or TSE.
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Clay-Containing Polymeric Nanocomposites
136
Intercalation of Clay
137
Clay-Containing Polymeric Nanocomposites
Jeong et al. [1998] and Hudson [1999] described preparing PO-based PNC
in three steps:
1. Functionalising MMT with an aminosilane.
2. Reacting the free amine with maleated PO (MW ≅ 20 kg/mol; ca. 1 wt%
MAH groups) either in solution (reaction time ca. 30 min) or in melt.
3. Dispersing the organomodified clay in a semicrystalline PO.
Cocrystallisation between the maleated and the semicrystalline PO is essential.
For example, the coupling reaction between MMT and amino ethyl-dimethyl
ethoxysilane was carried out for 2 to 4 h at T = 25-90 °C, in either ethanol and
water, or dimethyl acetamide. The monoalkoxy silane may either react with the
clay surface, self-condense to form dimer, or it may remain unreacted. Grafting
may lead to precipitation. The reaction produces ethanol, which has been detected.
Detection of the dimer by NMR is facile (resonance at 9.3 and 13.9 ppm). XRD
of the silane treated MMT demonstrated increased interlayer separation with
d001 = 2.4 to 7.3 nm. TEM showed the presence of many individual MMT-layers,
but in CPNC containing 15% clay, most were found in stacks of 2-4 layers ca.
1 μm long.
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Intercalation of Clay
Figure 5. Polymer (88 wt%), intercalated clay (10 wt%), and epoxy or PDMS
(2 wt%) were manually mixed for 30 min above either the Tg or Tm of the matrix
polymer. The XRD of B12 (no epoxy) showed the interlayer spacing,
d001 = 1.6 nm. Upon addition of epoxy the peak became wider and located at a
smaller diffraction angle, i.e., d001 increased to 2.3-1.9 nm. Thus, epoxy alone
does not exfoliate the onium-intercalated clay. For the CPNCs the percentage of
intercalation and/or exfoliation was calculated from XRD patterns as:
Exfoliation (%)
= 100×[1 - (clay peak area with epoxy)/(clay peak area without epoxy)]
The extent of exfoliation was found to increase with the mixing time, but the time
required for the completion of the process (from 4 to 120 min) depended on the type
of system. The extent of exfoliation may be related to the polymer solubility parameter,
δ, for epoxy and PDMS this is respectively, δ ≅ 9 and 8. Unfortunately, the authors
do not indicate the mechanism involved in the clay ‘swelling’ by either of these two
agents. The method was patented [Ishida, 2000].
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Clay-Containing Polymeric Nanocomposites
first step was the customary onium ion exchange, the second incorporation of
macrocyclic oligomers of these polymers [Takekoshi et al., 1996]. As in many
prior patents, the onium ion could be either ammonium, phosphonium or
sulfonium type. For example, MMT (CEC = 1.19 meq/g) was first intercalated
with dodecylammonium chloride or N-hexadecyl pyridinium chloride. Next, the
organoclay was mixed with a macrocyclic oligomer of terephthalic acid-co-
ethylene-co-butylene glycols, dried under a vacuum and then placed in an oil
bath at 190 °C. Finally, dioctyl tin dioctoxide was added to polymerise the
oligomer. The melt became viscous in about 15 s and the resulting solid polymer
composition comprised exfoliated MMT.
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Intercalation of Clay
chalcogenides: TiS2, MoS2, and MoS3; cyanides, e.g., Ni(CN)2; and oxides
H2Si2O5, V5O13, HTiNbO5, Cr0.5V0.5S2, W0.2V2.807, Cr3O8,MoO3(OH)2,
VOPO4-2H2O, CaPO4CH3-H2O, MnHAsO4-H2O, Ag6Mo10O33, etc.
2. The organic intercalant may be a water soluble polymer (e.g., PVAl, PEG,
carboxymethyl cellulose, PAA, P4VP); a reactive organosilane compound, a
cationic surface active agent such as quaternary ammonium salt having C12
to C18 moieties. The preferred quaternary ammonium cations may have such
groups as: octadecyl trimethyl, dioctadecyl dimethyl, hexadecyl trimethyl,
dihexadecyl dimethyl, tetradecyl trimethyl and ditetradecyl dimethyl.
3. The inorganic intercalant can be an inorganic polymer obtained by
hydrolysing a metallic alcoholate: Si(OR)4, Al(OR)3, Ge(OR)4, Si(OC2H5)4,
Si(OCH3)4, Ge(OC3H7), Ge(OC2H5)4, etc. The colloidal particles include the
hydrolysed and dehydrated forms, e.g., Si(OH)4 or SiO2, Sb2O3, Fe2O3, Al2O3,
TiO2, ZrO2 and SnO2, etc. The size of the colloidal particle should be about
12 nm. It is preferable to modify the multilayered material with a metallic
alcoholate, e.g., Ti(OR)4, Zr(OR)4, PO(OR)3, B(OR)3 and the like alone or
in combination, with Ti(OC3H7)4, Zr(OC3H7)4, PO(OCH3)3, PO(OC2H5)3,
B(OCH3)3, B(OC2H5)3. Metallic chlorides such as TiCl4, metallic oxychlorides
such as ZrCOCl2, and nitrate chloride can also be used.
4. The polymeric matrix can be thermoplastic, thermoset or elastomeric. The
specifically named polymers include PO (e.g., PP, HDPE, LLDPE, ultra low
density PE (ULDPE), EPR, EPDM, ethylene-acrylate acid copolymer (EAA),
EVAc), PEST, PA, PC, acrylics (viz. PMMA, methylmethacrylate-butadiene-
styrene terpolymer (MBS)), styrenics (e.g., PS, styrene-butadiene rubber (SBR),
high impact PS (HIPS), styrene-acrylonitrile copolymer (SAN), styrene-
butadiene-styrene terpolymer (SBS)), TPU, etc.
Prior to intercalating the clay is swollen in an aqueous (e.g., H2O with methanol
or butanol) or an organic liquid (e.g., DMF, DMSO, hydrocarbons, halogenated
hydrocarbons, benzene, xylene, cyclohexane, toluene, mineral liquids and oils).
For example, a mixture of swollen clay and the polymerisable inorganic intercalant
can be contacted with a hydrolysing agent for the polymerisable intercalant to
form the inorganic polymer. In general, hydrolysis is conducted at T > 70 °C.
Following intercalation, the clay is centrifuged and dried at 50-80 °C. The
intercalant may optionally be calcined at T = 450-550 °C. Intercalation increases
the original interlamellar gallery height of ≤ 0.4 to about 0.5 to 60 nm. Next, the
intercalated, layered material can be dispersed in a monomer, which when
polymerised would form the polymer matrix. Alternatively, it can be incorporated
in the molten or dissolved polymer.
Melt blending is the preferred method for preparing CPNC of a thermoplastic
polymer. Typically, the polymer is melted and combined with the desired amount
of the intercalated clay using an extruder, a Banbury or Brabender mixer, a
continuous mixer, etc. Melt blending is carried out in the presence of an inert
gas, such as argon, nitrogen or neon. Alternatively, the polymer may be dry mixed
with the intercalant, then heated in a mixer and subjected to a shear sufficient to
form the desired composite. Sufficient exfoliation is defined as when ≥ 80 wt%
of the clay platelets (aspect ratio p = 10-2000) are individually and uniformly
dispersed in the polymeric matrix.
The patent does not provide any example of CPNC preparation with a specific
polymer and there are no numerical values of performance. The claims are very
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Clay-Containing Polymeric Nanocomposites
broad, naming virtually any polymer, viz. a thermoset (e.g., phenolics, epoxy,
urethane or urea resin), or thermoplastic polymer (including PO, PC, TPU,
styrenics) or a vulcanisable or thermoplastic rubber (e.g., EPR, PU). Similarly,
the description of the performance is quite generous. The unnamed CPNCs showed
excellent balance of properties, viz. superior heat, chemical or ignition resistance,
barrier to diffusion of polar liquids and gases, yield strength in the presence of
polar solvents such as water, methanol, ethanol and the like, stiffness and
dimensional stability. They are useful in diverse applications viz. in business
equipment, computer housings, transport (automotive and aircraft), electronic,
packaging, building and construction industry, etc.
Bora et al. [2000] developed another method for the manufacture of
intercalated, thermally stable organoclay. Since the metal complexes with organic
ligands show good thermal stability, the authors expected that MMT intercalated
with an appropriate metal complex might show superior thermal stability to that
of onium cations. The aim of the work was to intercalate MMT with bulky,
three-dimensional cationic metal complexes with ligand X. Two were selected:
• Ni-CX1 ≡ [Ni{di-2-aminoethyl amine}2]Cl2 and
• Ni-CX2 ≡ [Ni{2,2´:6´,2´´-ter-pyridine}2](ClO4)2.
Na-MMT was converted to Ni-MMT by adding NiCl2 to an aqueous suspension of
Na-MMT (CEC = 1.14 meq/g). The Ni-MMT could also be complexed with
CX1 or CX2, but the structure was different from that obtained by ion exchange
between Na-MMT and either Ni-CX1 or Ni-CX2. This reaction was carried out
by adding Ni-complexes to an aqueous suspension of Na-MMT and allowing
the reaction to proceed for 0.5 h, e.g.:
Na-MMT + Ni-CX12+ → [Ni-CX1]-MMT + Na+
The product was separated, washed and then dried at 50 ± 5 °C in an air oven.
Analysis of the dried samples indicated that complexes were adsorbed by MMT
up to about 0.57 meq/g, i.e., up to stoichiometry. Oriented samples on glass
slides were dried at room temperature, 100, 150, 200, 250, 300, 350 and 400 °C
for about 1 h. XRD of [Ni-CX1]-MMT showed that on heating d001 decreased
from 1.45 at 50 °C to 1.35 nm at 250 °C. However, XRD of [Ni-CX2]-MMT
showed d001 = 1.94 at 50 °C, decreasing to 1.90 nm at about 350 °C. Accordingly,
the FTIR spectra showed characteristic bands of these complexes up to about
250 and 350 °C, respectively. Thus, the thermal stability of MMT intercalated
with Ni-CX1 and Ni-CX2 were found to be about 50 and 150 °C higher compared
to that of their metal complex salts.
The difference between Ni-CX1 and Ni-CX2 is noteworthy. In the former the
ligand is aliphatic, in the other it is aromatic. Ligands with aromatic rings in the
main chain show higher thermal stability than the aliphatic. This general
observation was confirmed by results for the free complexes and their MMT
salts. Furthermore, the interlayer spacing of [Ni-CX1]-MMT was significantly
smaller than that for [Ni-CX2]-MMT. This may be due to π-interactions between
the oxygen on MMT and the aromatic rings of Ni-CX2.
142
Intercalation of Clay
polymer. However, since melt exfoliation is rarely achieved, there is some rationale
for the term.
Melt intercalation is the preferred method for the preparation of CPNC with
thermoplastic matrix polymers. Usually, the polymer is melted and compounded
with intercalated clay using an extruder, an internal mixer, a kinetic-energy mixer,
etc. Compounding is carried out in the presence of an inert gas, e.g., N2.
Alternatively, the polymer is first mixed with a compatibiliser (e.g., its
functionalised homologue) then compounded with intercalated clay. Industrially,
CPNC is considered to be exfoliated when ≥ 80 wt% of clay layers (aspect ratio
p = 10-2000) are uniformly dispersed in the polymeric matrix in the form of
stacks comprising not more than two platelets.
It is remarkable that macromolecules with significantly larger radius of
gyration than the interlamellar gallery height:
1 /2
rg2 > d001 − 0.96
are able to diffuse into the galleries. Evidently, the process will take place only if
it leads to a decrease of the free energy (ΔG), i.e.:
ΔGintercalation = ΔH - TΔS < 0 (15)
The enthalpic (ΔH) contribution usually comes from the chemical interaction
between clay and the intercalating compound, whereas the entropic one (ΔS)
usually comes from the ‘randomisation’ of the macromolecular segments
placement, e.g., diffusion into spaces devoid of macromolecular presence.
However, the conformational energy loss caused by chain stretching from the
random coil configuration into elongated structures inside the galleys, and
associated with this the topographical and energetic constraints (e.g., caused by
adsorption of the macromolecules on the clay surface) hinders the diffusion.
Thus, it is expected that for successful melt intercalation there must be an enthalpic
driving force for the functionalised macromolecules. Furthermore, the interlayer
spacing should be large, at least the same order of magnitude as the diameter of
the macromolecular Gaussian coil, and sufficient time must be provided for the
diffusion process to reach the centre of the stacked platelets. Two relations can
be used as guides:
1. The self-diffusion coefficient, Ds ∝ 1/Mn2.
2. The distance travelled by the diffusing macromolecules is proportional to
the square root of the diffusion time, viz. ldiff ∝ t1/2.
In practice numerous factors influence the process, affecting the validity of these
simple relations.
The melt intercalation process can readily be divided into static and dynamic.
Usually, the static process takes place under vacuum at temperatures at least 50 °C
above the transition temperature (Tg or Tm) in the absence of mixing, thus often
it is also called melt annealing. Dynamic melt intercalation is more-or-less a
standard compounding operation, performed in an extruder, internal mixer and
similar processing equipment.
143
Clay-Containing Polymeric Nanocomposites
∑ (4 / α ) exp{−( D / a )α }
∞
2
Q(t ) / Q∞ = 1 − m mt (16)
m −1
where: αm is the m-th positive root of the Bessel zeroth-order function, and D/a2 is the
effective diffusion rate. Its temperature dependence was found to follow the Arrhenius
equation with the activation energy ∂ln(D/a2)/∂(1/T) = Ea ≅ 166±12 kJ/mol. The
molecular weight dependence was found to follow the dependence: (D/a2) ∝ 1/MW1.6.
The authors observed that intercalation by PS of commercial interest
(MW = 300 kg/mol) at T = 250 °C should take about 10 min. The melt annealing
would not result in exfoliation. There is no information about how the terminal
interlayer spacing depends on the molecular weight of the intercalating polymer.
In the following contribution by the same authors [Vaia et al., 1996] the
quiescent melt intercalation was conducted not only with PS (PS30 and PS400
with MW = 30 and 400 kg/mol, respectively) but also with poly(3-bromo styrene)
144
Intercalation of Clay
145
Clay-Containing Polymeric Nanocomposites
PEG chains were confined to 0.8 nm galleries. The 2H-NMR spectra were obtained
at the same temperatures for the bulk and the intercalated d-PEG. As the
temperature increased from 220 toward 250-270 K, a central peak of the
intercalated d-PEG developed earlier and became narrow. Thus, the enhanced
local chain dynamics of the intercalated d-PEG at low T may have resulted from
the absence of chain entanglements. However, within the high T-range
(T = 320-340 K), the intercalated d-PEG showed a broad base structure, whereas
the bulk d-PEG had a single narrow signal, indicating that the silicate layers
restrict macromolecular chain motion. Intercalation into the narrow interlamellar
space with height of 0.8 nm must have engendered interactions (hydrogen
bonding?) between the PEG segments and the platelet surface. Furthermore, the
narrow space between the clay layers topologically restricted the d-PEG chains.
The DSC experiments on an intercalated CPNC indicated the absence of any
thermal transitions of PEG; Tg or Tm. However, TSC suggested that the transition,
which in bulk PEG takes place at about Tg = -55 °C, upon intercalation increased
to Tg ≅ 60 °C. The TSC peak for the intercalated system was broad and shallow,
indicating a low level of molecular cooperativity near Tg.
The most comprehensive studies of the quiescent intercalation of organoclay
by molten polymers included: several intercalating organic cations, synthetic and
mineral clay, polymers (different chemically and with different molecular weight)
and annealing temperature [Vaia, 1995; Vaia and Giannelis, 1997a,b]. The
material characteristics are given in Table 18.
146
Intercalation of Clay
As before, dry organosilicate (25 mg) and polymer powder (75 mg) were
mechanically mixed and formed into a pellet using a hydraulic press at a pressure
of 70 MPa. Melt intercalation was carried out by annealing the pellet in vacuum
at T > Tg. Usually the samples were annealed to equilibrium, indicated by no
further changes in the X-ray diffraction pattern. The work brought out several
important observations:
1. Of the three clays the largest value of d001 was systematically observed for F
and the smallest for M, having, respectively, the highest and the lowest CEC
value. Note also that for the three clays there is a difference in the distribution
of the anionic charge on the silicate surface. The increased localisation of
surface charge for tetrahedrally-substituted S does not appear to affect CPNC
formation when compared to the more dispersed surface charge of
octahedrally-substituted M.
2. Li+-fluorohectorite (FH, clay F) was intercalated with the primary ODA (F18)
and subsequently annealed with each of the three PS. XRD showed intercalation
with d001 = 3.11 nm. However, while the intercalation for PS30 was achieved
after annealing for less than 6 h at 160 °C, to intercalate with PS90 took 24 h,
and PS400 more than 48 h. Since the XRD peak was quite similar for the three
polymers it was concluded that the kinetics of intercalation are strongly affected
by the polymer molecular weight, but that the structure of CPNC prepared
under quiescent conditions is independent of it.
3. The ammonium salt used in the cation exchange may have an important
effect on intercalation by molten polymer. Two aspects are worth stressing:
a. At T = 160 °C PS30 was unable to diffuse into the interlamellar galleries
of the F-clay intercalated with alkyl-ammonium chlorides having n ≤ 12.
Intercalation with alkyl ammonium with n = 6 to 12 engendered the
same initial expansion of the interlayer spacing, viz. d001 ≅ 1.8 nm (see
also Figure 23), but apparently alkyls with n < 12 do not sufficiently
shield the hydrophilic clay surface to assure PS interpenetration.
Annealing with PS30 at T = 180 °C expanded even F8 to the maximum
spacing d001 ≅ 3.1 nm, i.e., increasing the gallery height by about 1.1 nm.
This maximum value was found to be independent of the alkyl cation,
of the annealing temperature, and of the PS molecular weight.
b. The difference between primary and quaternary ammonium cations
can be evaluated by comparing the intercalation of PS30 into FC18
(primary) with that into FQ18 (secondary) and F2C18 (quaternary).
For the three compositions the interlayer spacing was found to be,
respectively, d001 ≅ 3.11, 3.64 and 3.80 nm. Thus, all three cations
facilitated the secondary intercalation by PS, but different types of
ammonium cation did influence the final gallery height. The difference
could originate in the difference in the ionic interaction strength for the
primary, secondary and quaternary onium ions as well as in the size of
the quaternary group.
4. Melt intercalation also depends on the chemical nature of the intercalating
macromolecules. Thus, in this series of styrene-derivative polymers with
M2C18 the interlayer spacing increased with the relative acid/base character
and the side-group polarisability in the order: poly(vinyl cyclohexane) (PVCH)
<< PS < PS3Br < PVP, giving d001 = 2.38, 3.20, 3.34 and 3.38 nm, respectively.
Thus, secondary intercalation was observed for all polymers, except PVCH.
147
Clay-Containing Polymeric Nanocomposites
On the other hand, none of the polymers intercalated F2C18, leaving the
initial (after cation exchange) spacing, d001 = 3.80 nm, unchanged. It is
noteworthy that the latter spacing is larger than that observed for doubly
intercalated MMT.
5. The kinetics of secondary intercalation under quiescent conditions inversely
depend on the molecular weight:Mmw , where the exponent m = 1.6 to 2.0
(exponent m = 2 is expected for pure chain reptation at T - Tg = constant).
Such dependence suggests that secondary intercalation is related to the self-
diffusion process. In the series of polymers: PS, PS3Br and PVP, even after
taking into account the differences in MW, intercalation for PS required
annealing for about 4 h, whereas that for the other two polymers for more
than 24 h. This again agrees with the self-diffusion behaviour theory, viz. the
stronger the interchain interactions the smaller the self-diffusion coefficient
[Kausch and Tirrell, 1989].
The question that remained unanswered is whether exfoliation in a quiescent
melt intercalation process is possible at all. Via and Giannelis [1997b] considered
exfoliation to be kinetically-limited, i.e., that transport of the clay platelets to
effect exfoliation would take a prohibitively long time, hence external forces are
needed (shear flow, ultrasonication, etc.). This idea found support in the work
published three years later [Huang et al., 2000] which focused on the preparation
of CPNC with PC as the matrix. The organoclay was MMT cation exchanged
with 2M2TA. The secondary intercalation was performed using either a polymer
(PC; Mw = 25 kg/mol) or a cyclic carbonate oligomer (OCC; Mw = 2 kg/mol).
The quiescent samples were prepared either in solution or in the melt. Thus,
0.5 g of organoclay was added to a solution of 10 g of either OCC or PC in
50 ml of CH2Cl2. After 5 min at room temperature, the solvent was removed
under vacuum and the residue was dried in the vacuum oven at 50 °C overnight.
As before, 10 g of either OCC or PC was mixed with 0.5 g of organoclay, pressed
into pellets with a hydraulic press and heated to 180 °C in a vacuum oven for 1 h
followed by heating at 240 °C for 15 min.
XRD showed that solution or melt intercalation with PC produced the basal
spacing d001 = 2.47 nm, virtually identical to that of organoclay. Several hours of
mixing would be required to increase the interlayer to d001 = 3.27 nm. Intercalation
with OCC was more successful as it caused the interlayer spacing to rapidly
increase to d001 = 3.62 nm. Thus, as was the case with styrene-derivative polymers,
here also the difference between the oligo- and poly-carbonate amounted to the
kinetics of intercalation. The difference in chain structure (cyclic versus linear)
may have also contributed to the intercalate formation. Next, the melt intercalated
(with OCC) organoclay was added to an internal mixer and processed at 100 rpm
at 180 °C for 1 h, then at 240 °C for 10 min, causing ring-opening polymerisation.
XRD of the material showed no peak and TEM revealed that a partially exfoliated
structure was obtained. However, when PC was similarly mixed, only an
intercalated system was obtained.
In conclusion, there is still no clear answer to the question as to whether
exfoliation in a quiescent melt intercalation process is possible. In the case of a
PC/organoclay system the initial spacing was small, which indicated an absence
of PC in the interlamellar galleries, hence exfoliation would not be expected. For
the OCC/organoclay system two elements worked in favour: (1) to start with,
much larger interlayer spacing, and (2) polymerisation that engendered
148
Intercalation of Clay
macromolecular coil formation that expanded the interlayer space the same way
as reported for the reactive intercalation of PA-6 (see Figure 25).
As will be shown in Section 3.1, the free energy of mixing as a function of the
interlamellar separation height may have a local minimum, thus intercalation
but not exfoliation is the thermodynamically favoured state. Fundamentally, flow
(energy) should help, but the magnitude of the imposed stresses must be
comparable to the attraction forces between clay platelets which hyperbolically
decrease with the interlamellar gallery height (see Figure 18). Thus, the shear
stress of about 1 kPa would not be sufficient to significantly affect the interlamellar
spacing from 2 nm, but conceivably so from 4 nm.
149
Clay-Containing Polymeric Nanocomposites
[
σ 2a = a( x ) − aav ]
2
and I s = σ 2a / aav bav (17)
150
Table 19 Melt mixing machines [Utracki and Shi, 2002]
Machine N P RTD Feeding* Dispersive Distributive
Powder Filler Sticky as such with as such with
additions additions
Internal mixer
Batch + - - + + + + +
Continuous 0 - - + + + + +
SSE + + - 0 - - - 0 - 0
TSE - CORI ++ 0 + + + 0 + + 0 +
TSE - ICRR + + + + 0 + + + - 0
TSE - CRNI + - - + + + - 0 - 0
Special
Pin-barrel + 0 0 0 - + + +
Kokneader 0 - + + + + + +
Planetary gear - - + 0 - - ++ 0
Disk + + + 0 0 - 0 + 0 +
Symbols: N - high screw speed, P - pressure generation, RTD - residence time distribution.
* Capability to be fed with difficult material, distributive and dispersive mixing without and with extra mixing elements or devices
CORI - co-rotating intermeshing
ICRR - intermeshing counter-rotating
CRNI - counter-rotating non-intermeshing
Evaluating symbols: + means good, 0 means acceptable, and - means poor
151
Intercalation of Clay
Clay-Containing Polymeric Nanocomposites
During mixing at relatively low temperatures and relatively high rotational speed
of the mixing shafts, a dynamic equilibrium may be reached, i.e., the heat from
the outside heaters is transferred to the melt, then to shafts that conduct it to the
internal drive system of the mixer. The dynamic equilibrium means that the higher
temperature is at the chamber wall and lower on the shafts’ surface. The difference,
ΔTchamber, of these two temperatures depends on the temperature difference between
that desired within the mixer and the ambient, the heat conductivity of the mixed
compound and shaft material, on screw speed, etc. Under the conditions securing
a rapid exchange of material within the mixer chamber, good mixing may reduce
ΔTchamber. However, while compounding the engineering or speciality polymers
with high Tg or Tm, the temperature drop across the chamber was determined to
be as large as ΔTchamber ≈ 100 °C.
Continuous mixing involves the continuous loading and unloading of
components. When properly performed, mixing decreases the compositional
variations to the desired level. Continuous operations have the advantage of
providing a stable process. The power consumption is usually lower than in batch
mixing. The stresses are imposed systematically, either in the shear or in the
shear-and-elongation mode of deformation. In spite of high capital costs and
complex mixing, continuous mixing is easy to justify on the basis of the production
volume (mixers with throughputs of up to 80 ton/h are available) and quality.
The continuous mixers make it possible to control: the feed rate, screw speed
and temperature, as well as the discharge orifice setting and temperature, but the
accessible range of residence times is small.
Extrusion is one of the most important forming methods in polymer processing.
Virtually all polymers go through an extruder at least once, viz. compounding
and pelletising reactor powders. The extruders are classified according to the
principal element of their construction, as:
• Single-, twin-, and multi-screw extruders.
• Single-, twin-, and multi-shaft compounders.
• Gear or disk extruders, e.g., Maxwell Melt-elasticity Extruder, Tadmor’s Disk
Extruder.
• Special extruders, e.g., Gelimat, Patfoort, etc.
Single-screw extruders (SSE) are relatively inexpensive machines for small or
medium size production lines. They are difficult to scale-up, notoriously poor
mixers with broad residence time distribution (excepting the case of plug flow of
compositions with the yield stress) and relatively long residence time. Over the
years, SSEs have been made more versatile by the introduction of special mixing
screws, by using add-on mixing devices, by utilisation of two or more extruders
operating in tandem, etc. The SSE operates under fully flooded conditions, thus
the quality and throughput depend on the screw speed, and to a lesser extent, on
feed. A summary of performance criteria of SSE and TSE is presented in Table 20.
Mechanically, a major difference between SSEs and TSEs is the type of
transport that takes place within the extruder; in the former it is drag-induced
(frictional drag in the solid conveying zone and viscous drag in the melt conveying
zone). There are many materials with unfavourable frictional properties that
pose severe feeding problems. In intermeshing TSEs the transport is by positive
displacement. Its degree depends on how well the flight of one screw closes the
opposing channel of the other screw. The most positive displacement is obtained
152
Intercalation of Clay
153
Clay-Containing Polymeric Nanocomposites
By contrast with the SSE, the TSE operates with partially filled screws. The
polymer from a feeder is transported toward the pressure zone, usually created
by a flow restrictor, e.g., a left-handed or reverse screw element. Under the pressure
the resin pellets are compressed into a solid plug, which fractures and melts
mainly by friction between its fragments and the wall. Thus, melting in a TSE is
more efficient than that in a SSE – its length can be as short as less than one
screw diameter, L ≤ D. There is evidence that melting in a TSE affects the
generation of polymer blend morphology differently to that in a SSE. The modular
design of screws and barrel is universally accepted. Many TSE manufacturers
still insist that to control the dispersive-to-distributive mixing ratio simply the
width of the mixing block should be used – a set of narrower blocks results in
more distributive, and less dispersive mixing and vice versa.
As shown in Table 21, seven types of TSE are possible; of these three (marked
in bold below) are the most popular in the plastics industry:
I. 1A, screw: L-open & C-closed, discs: L& C-open (CORI - the most popular).
II. 1B, L & C-open (rare)
III. 1C, L & C-open (rare)
IV. 2A, L & C-closed (ICRR)
V. 2B, L & C-open
VI. 2B, L-open & C-closed (rare)
VII. 2C, L & C-open (CRNI)
For many years, CORI has been the compounder of choice. Its advantage arises
from the movement of the intermeshing surfaces in opposite directions, thus the
melt free surface is continuously renewed and the screws clean each other. In
addition, since at the intermeshing the material passes from one screw to the
other (change of the drag direction) there is low probability that the material
would go through the gap. Thus, there is no calendering pressure that may cause
the screws to bend. As a consequence, CORI has been able to operate at higher
screw speeds with longer barrel than ICRR, which is considered advantageous
especially for reactive processing. However, during the last ten years or so, several
manufacturers of these two types of extruders have demonstrated that in unbiased
tests ICRR may equal or even outperform CORI as far as the compound quality
and the throughputs are concerned. Even at lower screw speed ICRR frequently
showed better performance than CORI. This resulted in renewed interest in
redesigning ICRR, e.g., providing it with higher screw speeds and longer barrels.
C. Separated
154
Intercalation of Clay
Originally ICRR was developed as a positive displacement screw pump for viscous
fluids. This is the only TSE type that is fully, axially and radially, closed. The
extrusion speed depends on the intermeshing geometry and the screw speed. The
fully intermeshing ICRR has a narrower distribution of residence times and better
precision in controlling rapid reactions between liquid reagent and molten polymer
than a CORI. The low speed ICRRs have been used for PVC compounding and
forming. At higher screw separations and speeds, the machines can be used for
the incorporation of high viscosity toughening elastomer. To make ICRR fully
competitive with the more popular CORI the calendering gap between screws
was widened, reducing the high stresses and increasing the intensity of shearing
between the screws and the barrel. For some applications, ICRR offers the unique
advantage of a strong extensional flow field, able to disperse high viscosity
ingredients in a low viscosity matrix. A summary of the relative merits of CORI
and ICRR is given in Table 22.
In CRNI the material flow is based on a drag, not positive pumping. There is a
low shear stress field, responsible for the absence of dispersive mixing. However, the
interchange of material between the screws provides good distributive mixing. The
chemical reaction proceeds on the continuously renewed surfaces, related to
reorientation of the laminar flow patterns and the total strain. CRNI is well suited
for the polymerisation of miscible, low viscosity systems. The main advantage of
CRNI is a long enough residence time, sufficient to complete slow processes. CRNI
can offer larger outputs, and more interchange of material between the two screws
than the other types of TSEs. These machines are frequently used for the preparation
of composites with fibrous fillers. It is noteworthy that the closer the clearances and
intermeshing the more rapid the build-up of pressure, the narrower the lands and the
larger the clearances between screws, the greater the longitudinal mixing.
Within a TSE the shear and extensional stresses are generated by interactions
between two screws. The stress magnitude depends on the relative direction of the
screw rotation (co- or counter-rotating), shapes of the screw elements, the degree
to which they intermesh, and the rotational speed of the screws. The modular
design of a TSE makes it possible to adjust the relative magnitude of the distributive
and dispersive mixing. The TSE performs a series of different functions. There is a
continuous pressure toward bigger machines with higher ‘free volume’, with longer
barrels and higher screw speeds. CORI with L/D = 100, D ≤ 455 mm and screw
speeds of up to 2500 rpm are commercially available [Sakai, 2002].
Recently Nanocor published a CORI screw design for the manufacturing of
CPNC with PO as the matrix [Qian et al., 2001]. A Leistritz TSE with D = 27 mm
and L/D = 36 was used at 300-500 rpm and T = 170 to 190 °C (see Figure 30 and
Table 23) [Nanocor Technical Services Group, 2001]. Two vents at 13D and
24D were used. The melt exfoliation involved a two-step process:
1. Preparation of masterbatch containing 50-60 wt% of organoclay a
compatibiliser and matrix polymer (e.g., PP-MA and PP), and
2. Dilution to the desired clay content (e.g., 2-7 wt%).
Alternatively, a single-pass procedure can be used replacing the first vent with a
side stuffer, through which the diluting quantity of matrix polymer is fed [Nanocor
Technical Services Group, 2001].
Besides the ‘classical’ extruders (SSE and TSE) there are several less well-
known compounders. Of these the planetary roller extruder is the oldest. Here,
six or more evenly spaced planetary screws revolve around the circumference of
155
Table 22 Advantages and disadvantages of CORI and ICRR type TSEs
156
Extruder Advantages Disadvantages
Co-rotating, • Self cleaning • Capital cost
intermeshing, CORI • Dispersive and distributive mixing in transverse and • Only residence times below about 10 min are
longitudinal direction economic
• Lower than in ICRR, uniform and controllable • Limited ranges of pressure and vacuum
stress are available
• Good control of resin degradability
• Local pressure control
• High screw speeds and throughputs
• Local high vacuum possibilities
• Double-walled barrel for rapid temperature changes
• High specific energy input possible
• Residence time up to one hour
Counter-rotating, • Self cleaning • Transverse mixing is moderate
intermeshing, ICRR • High dispersive mixing in the shear and extension • Longitudinal mixing is poor
Clay-Containing Polymeric Nanocomposites
• It can accommodate multi-lobal mixing elements of • Only residence times below 10 min are economic
the gear type with excellent dispersive mixing • Limited screw speed
capabilities • Capital cost
• It has better specific energy than CORI
• It has narrower residence time distribution than
CORI
• High local pressures possible
• High local vacuum possible
• Better devolatilisation capability than CORI
• High specific energy input possible
• Shorter screws than in co-rotating
• Easy separation of desired functions, viz. mixing,
devolatilisation, chemical reaction, compounding, etc.
Intercalation of Clay
157
Clay-Containing Polymeric Nanocomposites
the central or so-called ‘sun’ screw. The planetary screws intermesh with the sun
screw and the barrel. The planetary barrel section has helical grooves
corresponding to the helical flights on the planetary screws. This section is usually
a separate barrel with a flange-type connection to the feed barrel section. The
planetary roller extruders are mostly used for processing heat-sensitive
compounds, viz. rigid or plasticised PVC formulations.
More recent are the disk or screw-less extruders, based on the viscous drag
transport principle. To this category belong: stepped disk, drum, spiral Diskpack
extruders and many others. Diskpack has the inherent capability of performing
the elementary steps of plastics processing by combining differently shaped
rotating disks in a drum-like housing. Stationary channel blocks that cause the
material to transfer from one disk-gap to another provide the wiping action.
Melting, laminar mixing, venting, and the pumping functions are all separated.
Diskpack has been used for reactive processing, blending, compounding, mixing
and devolatilising [Tadmor et al., 1983].
In the early 1980s Carlew Chemicals developed Gelimat, later re-named
K-mixer (K- for the kinetic energy). This mixer uses a high-speed rotor with
staggered blades mounted on a horizontal shaft at different angles. The number
and position of the blades vary with the mixer size. The mixing is carried out at
the blade tip velocity of 30-45 m/s. There is no external heating – the kinetic
energy generated by the particles impacting on each other and the mixer elements
produces sufficient heat to flux the material within 8 to 150 s. Since polymers
have low thermal conductivity, by varying the initial particle size it is possible to
melt only the skin of a particle or engender uniform melting. Once the material
reaches the desired temperature, the infrared sensor activates the bottom doors
of the chamber. The discharged dough can either be fed to a short screw extruder
and pelletised, or be passed between rolls and diced. High mechanical properties
were obtained by compounding in Gelimat PP with non-intercalated mica flakes.
To improve the distributive mixing often a static mixer (SM) is used (see
Table 24). It operates on the principle of repetitive dividing of a flow channel
into at least two new channels, reorienting them by 90°, and dividing again during
laminar flow. Mixing by SM is related to the number of striations (Ns) generated
by a number of SM elements (ne) and the number of divisions (new channels)
engendered by each element (nc):
N s = ncn e (18)
The efficiency of a SM is determined by comparing:
1. The length-to-diameter ratio (L/D proportional to ne) required to produce
the same degree of homogeneity;
2. The associated pressure drop, ΔPrel;
3. The holdup volume, ΔVrel;
4. The relative dimensions of the device, Drel and Lrel.
The efficiency of a SM also depends on the type of liquid [La Mantia, 1996].
158
Intercalation of Clay
distributive mixing [Utracki and Shi, 2002; Luciani and Utracki, 1996]. In
processing equipment extensional flow requires non-parallel flow lines. In a SSE
extensional flow is only present in specially designed mixing elements, in add-on
torpedoes or in the convergent flow into the die. In a TSE extensional flow takes
place within the kneading disks. However, even here only about 8% of mixing
energy is used to generate an extensional flow field – the rest being consumed by
shear. The extensional flow mixer (EFM) is the only device that deliberately utilises
the elongation flow for mixing.
The EFM is a fully adjustable, general-purpose, motionless mixer. The mixing
action is provided by the development of an extensional flow field through a
convergent-divergent (C-D) flow geometry. It is primarily a dispersive mixer that
should be attached to a pressure-generating device. It efficiently homogenises
different liquid systems, even those where the components’ viscosity ratios are
large. The mixer attached to a SSE provided comparable or better mixing than
two TSE machines from different manufacturers, equipped with high mixing
screw geometry. The C-D channels are of progressively increasing intensity, with
flow in the radial not axial direction. To reduce the pressure drop, and to prevent
blockage, slit restrictions are used [Nguyen and Utracki, 1995]. A more recent
patent describes modifications of the original EFM design as well as its dynamic
version, the Dynamic Extensional Flow Mixer (DEFM) [Utracki and Luciani,
1997]. EFM has been used for: polymer blending, incorporation of elastomers
into resins, and dispersion of high viscosity resins or ‘gel particles’ [Utracki and
Luciani, 2000; Luciani and Utracki, 1996] as well as for dispersing organoclays.
Recently, preliminary tests were conducted to evaluate the suitability of EFM
for CPNC manufacture. The tests were conducted using the available device,
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Clay-Containing Polymeric Nanocomposites
optimised for melt blending not for dispersing nanosized solid particles.
Nevertheless the results in three different laboratories have been encouraging.
The tests were conducted attaching an EFM to a CORI by a gear pump [Garcia-
Rejon and Simard, 2002]. The modulus of the resulting CPNC (PET with 5 wt%
organoclay) was twice as large in the presence of an EFM than without it. CPNC
containing PP with maleated-PP and organoclay were compounded using either
a TSE + EFM or a SSE + EFM. In both cases the presence of an EFM resulted in
significantly better dispersion of the clay platelets, as shown in high resolution
TEM [Song, 2002].
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Intercalation of Clay
took place. The incorporation of clay affected the crystalline form of PA-6 –
whereas in neat polymer only the α-form was present, after compounding with
organoclay the γ-form was also found. A good set of properties was reported.
Dennis et al. [2000; 2001] carried out fundamental studies of melt intercalation
in a PA-6 (Mn = 30 kg/mol; MI = 12) matrix. In the study 5 wt% of Cloisite® 15A
(C15A; MMT-2M2HTA) or Cloisite® 30B (C30B; MMT-MT2EtOH) (organoclay
properties are listed in Table 16) were used. A SSE and several TSE machines
with different screw combinations were employed. The organoclay powder
(particle size d ≅ 8 μm) was dry-blended with the PA-6 pellets. The mineral content
in the CPNC generated from C30B and C15A was 3.7 and 3.1%, respectively.
However, since melt blending of PA-6 with C30B resulted in easy exfoliation, the
studies were conducted with C15A.
Experimental studies of melt intercalation were carried out using four extruder
types: SSE, CORI (low and medium shear stress screw configurations), ICRR
(low medium and high shear stress screw configurations), and CRNI (low medium
and high shear stress screw configurations). The effects of mixing were evaluated
by XRD, TEM and tensile tests. It was found that the XRD peak position did not
change much (d001 = 3.2-3.8 nm), but its intensity varied, indicating diversity of
the dispersions. TEM micrographs were used to quantify the degree of dispersion
(DD) by counting the number of clay platelets or their stacks in twelve, 25 ×
25 mm squares. Evidently, the higher the number the more dispersed is the CPNC.
The results of this evaluation are shown in Figure 31.
Clearly the data from different mixing devices can be approximated to r2 = 0.86
by a simple two parameter equation:
{
DD = 4.37 × exp 0.00972 × t }; R = 0.86 (19)
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Clay-Containing Polymeric Nanocomposites
Better correlation may be found when not only t , but also the variance of the
residence time distribution (σ 2a ; see Equation 17) is considered [Dennis et al.,
2000]:
162
Intercalation of Clay
163
Clay-Containing Polymeric Nanocomposites
The linear regression gave the correlation coefficient squared, r2 = 0.991, hence
the postulated dependence represents the reported data reasonably well. The
analysis gave the following parameter values: a0 = -231 ± 48, a1 = 9.5 ± 5.7, and
a2 = 196 ± 33. Note that since the equation parameters, a1 and a2 are positive the
specific degree of dispersion increases with clay content and the molecular weight
of the matrix, thus with the matrix viscosity. If the melt intercalation were diffusion
controlled, the value of the a2 parameter should be negative! Thus, the data
indicate that contrary to expectation, the higher the molecular weight of PA-6
the easier the dispersion. This conclusion is supported by the TEM micrographs
shown in Figure 4 of the original paper [Fornes et al., 2001]. The CPNC with
either high or medium MW PA-6 have homogeneously exfoliated structures with,
on average, 1.3 or 1.5 platelets per stack, whereas that with low MW polymer
has large residual stacks and 2.4 platelets per stack.
The positive effect of MW on the mechanical dispersion process is even more
striking when the differences in the residence time and the residence time
distribution are taken into account. Using the values listed in Table 25, DD was
computed from Equations 19 and 20. The results plotted versus MW showed a
strong negative effect of MW on DD:DD∝Mn-1.6, in agreement with the diffusion-
controlled mechanism. The only conclusion from these seemingly contradictory
observations is that during melt intercalation in a compounding machine two
simultaneous processes take place: thermodynamically-driven diffusion of
macromolecules into the interlamellar galleries, and mechanical peeling off of
platelets or short stacks in which the diffusion-controlled intercalation sufficiently
reduced the solid-solid interactions between the adjacent clay platelets. It is
noteworthy that the zero-shear viscosity of the three polyamides varies nearly by
a factor of 8, thus higher shear stresses are acting on weakened stacks in high
molecular weight matrix. Since the organoclay value, d001 = 1.8 nm is small, the
diffusion of macromolecules must rapidly expand it for the shear stresses to be
effective.
Cho and Paul [2001] used SSEs and TSEs to prepare CPNC with 5 wt% of
MMT-M2REtOH in PA-6 as a matrix. The residence time distributions for the
SSE and TSE were quite different, narrow with a peak at about 2.5 min for the
former and very broad with a peak at about 5 min for the latter, just opposite to
what one could expect for flow of polymer melt through SSE and TSE. This may
164
Intercalation of Clay
be caused by the plug flow of CPNC through SSE. XRD of the organoclay showed
a strong peak at d001 = 1.8 nm – compounding in a SSE reduced the peak to a
barely discernible shoulder, while that in a TSE pushed it to low angle values,
2θ < 2°, i.e., d001 > 4.4 nm. The presence of short stacks in both products indicated
that exfoliation was not complete. Improved mechanical properties were reported,
e.g., addition of 3.16 wt% of inorganic clay resulted in 38% higher modulus and
30% higher strength (than PA-6) keeping the Izod impact strength about the
same.
Intercalated and exfoliated CPNC of PA-6 with organoclay were prepared in a
TSE at T = 250 °C [Varlot et al., 2001]. The organoclay was Na-MMT cation-
exchanged with methyl octadecyl bis-2-hydroxyethyl ammonium methyl-sulfate
(MODA2EtOH) and dimethyl dioctadecyl ammonium chloride (2M2ODA), which
resulted in the interlayer spacing of d001 = 1.96 and 3.68 nm, respectively. After
compounding, the CPNC specimens were found, respectively, exfoliated and
intercalated into short stacks containing 2-4 MMT platelets. The nanocomposites
were anisotropic. The preferential orientation of the MMT platelets as determined
by SAXS was parallel to the flow direction during injection moulding. The orientation
of the MMT plates and the PA-6 lamellae is expected to play a major role in the
mechanical properties. In the CPNC the matrix crystallised preferentially in the
γ-form.
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Clay-Containing Polymeric Nanocomposites
technique. The large resin manufacturers are pursuing the development of the
polymerisation-intercalation method with moderate success.
During the last decade, PP technology underwent a dramatic evolution that
resulted in a rapid increase of PP application in various industries, including
transportation. Thus, it is of no surprise that PP-based CPNCs have been of interest
to researchers around the globe.
The early work on PO-based CPNC was published by the Toyota group. Its
strategy was based on a multistep intercalation:
1. Primary intercalation of clay by cation exchange with onium salt;
2. Secondary intercalation with a compatibiliser, e.g., PO macromolecules grafted
with a polar compound (such as MAH); and
3. Melt compounding with the matrix PO.
The two critical steps are the selection of the organic cation (able to react with
clay anions and interact with the compatibiliser), and selection of the polar
compatibiliser, which will react with organoclay and remain miscible with the
basic resin. Some success was also obtained by combining steps 2 and 3 into one,
by modifying the PO only slightly, and compounding it directly with organoclay
as a polar matrix.
In studies by Usuki et al. [1997] (which provided the basis for the first patents
in this field [Usuki et al., 1996; 1999]) Na-MMT (CEC = 1.19 meq/g) was
intercalated with 45.8 wt% of dimethyl distearyl ammonium chloride (2M2ODA),
which increased the MMT interlayer spacing to d001 ≅ 3.28 nm. Next, the
organoclay was suspended in toluene and blended at a weight ratio of 1:1 with
the compatibilising ‘main guest molecule’ (hydroxylated
oligo-olefin: OO-OH; e.g., hydrogenated polybutadiene with telechelic -OH
groups, Mw ≅ 3 kg/mol, Polytail H from Mitsubishi) then dried. The interlayer
spacing increased to d001 ≅ 3.87 nm, but when the ratio of OO-OH-to-organoclay
increased to 10 the XRD peak disappeared altogether, indicating that d001 ≥ 8.8 nm.
Still better results were obtained by either reducing the molecular weight of the
OO-OH compound, or by replacing the -OH groups by either -COOH, acid
anhydride or epoxy (Polytail EP from Mitsubishi Kagaku). Next, PP (Mw = 30 kg/mol)
was melt-compounded in an internal mixer at 220 °C with either: Na-MMT, the
MMT-2M2ODA organoclay or the exfoliated OO-OH/organoclay material. The
TEM images taken of these three compounds showed, respectively, a micron-level
dispersion, the presence of large stacks, and exfoliation with only short stacks.
Thus, good dispersion of clay platelets in molten PP was achieved when prior to
compounding the clay platelets were exfoliated by the combined effects of onium
ion and the OO-OH compatibiliser. The authors stressed good miscibility of the
MMT-2M2ODA organoclay with PO, e.g., PP, butyl rubber (BR), polyisoprene
(IR), polybutadiene, etc.
In another publication [Kato et al., 1997] two-step exfoliation was carried
out. Thus, Na-MMT was intercalated with octadecyl ammonium chloride (ODA),
which increased the MMT interlayer spacing to d001 = 2.17 nm. Melt blending it
with either maleated PP (PP-MA; Mw = 30 kg/mol, acid value = 52 mg KOH/g) or
hydroxylated PP (PP-OH; Mw = 20 kg/mol, OH value = 54 mg KOH/g) was carried
out in an internal mixer at 200 °C for 15 min, with the ingredient ratio changing
from 1:3 to 3:1. The interlayer spacing of CPNC containing 50 wt% of organoclay
was d001 = 3.82 and 4.40 nm for the PP-MA and PP-OH matrices, respectively.
However, for an organoclay concentration of 25 wt% d001 = 7.22 nm was
166
Intercalation of Clay
obtained. Note, that the PP-MA matrix had lower molecular weight than
commercially desirable, but still above the entanglement molecular weight:
(Mw > Me = 2.8 kg/mol [Porter, 1995]). Furthermore, under the same conditions
the same resin with lower acid value (PP-MA; Mw = 12 kg/mol, acid value = 7 mg
KOH/g) was unable to expand the organoclay spacing. The authors concluded
that to obtain intercalation one polar group per 25 PP mers is required.
Unfortunately, there is no explanation of the MAH group reaction(s) with the
organoclay – is it with the primary ammonium ion, with clay surface -OH groups,
or the surface cations at the platelet edges?
In the following publications from Toyota [Kawasumi et al., 1997; Hasegawa
et al., 1998] again a three-step melt intercalation was used. Thus, Na-MMT was
first intercalated with ca. 32 wt% ODA, which increased the interlayer spacing
from d001 = 1.2 to 2.2 nm. The same procedure was repeated with synthetic
fluoromica (FM) (Somasif ME100 from CO-OP Chem.). As the ‘main guest
molecule’ two grades of PP-MA were used (Yumex 1001 and 1010 from Sanyo,
with Mw = 40 and 30 kg/mol, acid number = 26 and 52 mg KOH/g, Tm = 154 and
145 °C, respectively). The powders of organoclay (7.3 wt%), PP (melt flow rate
MI = 16 g/min; 70.8 wt%) and Yumex (21.9 wt%) were dry-blended, then
compounded in a TSE at 210 °C. About 5 wt% of the clay (MMT or FM) was
incorporated. The miscibility of PP with PP-MA was examined at 200 °C by
means of an optical microscope – Yumex 1001 was found miscible while Yumex
1010 was immiscible. The degree of clay dispersion in injection-moulded
specimens was determined by XRD and TEM. It was found that compounding
organoclay with PP caused a reduction of the interlayer spacing, while that with
either PP-MA increased it to d001 = 5.9 and 6.4 nm for MMT and FM, respectively.
In three-component systems (organoclay/PP-MA/PP) a significant difference in
the degree of dispersion was observed for systems with Yumex 1001 and 1010.
In the first case, the miscibility of the PP/PP-MA blend resulted in a high degree
of dispersion (displayed in TEM micrographs), but with residual short stacks
detected as a shoulder on the XRD (d001 ≅ 3.3 nm). In the case of the immiscible
PP/Yumex 1010 system the XRD peaks indicated reduced interlayer spacing to
d001 ≅ 5.5 and 5.9 nm for MMT and FM, respectively. The authors stated that
there is ‘strong hydrogen bonding between the maleic anhydride groups and the
oxygen groups of the silicates’, suggesting that MAH groups react with the clay
surface -OH functionalities.
Evidently, preparation of CPNC with such non-polar polymers as PP requires
thermodynamic compatibilisation. The ‘compatibilising’ molecules (e.g., PP-MA)
must be selected considering several aspects:
1. Interaction with pre-intercalated clay;
2. Miscibility with the matrix polymer;
3. Ability to entangle with the matrix, and
4. The effects on the crystallinity of the matrix.
As Kawasumi et al. have shown [1997] the miscibility of PP-MA with PP is of
great importance. As expected, when the MAH content exceeds a critical acid
value (≤ 52 mg KOH/g) the immiscibility with PP results in a micron-size dispersion
of PP-MA/organoclay phase in PP. Thus, a high degree of maleation leads to
immiscibility and poor results. Similarly [Kato et al., 1997], when the degree of
maleation is too small, there is insufficient interaction with the organoclay and
167
Clay-Containing Polymeric Nanocomposites
168
Intercalation of Clay
Figure 33 Tensile and impact strength (at 5 °C) versus organoclay content for
PP/PP-MA/organoclay [Zhang et al., 2000b].
was generated. The CPNC was partly intercalated – shearing improved the degree
and homogeneity of dispersion. However, this improvement was at a cost of
platelet orientation in the flow direction. Some bent MMT platelets were observed
under TEM. As a result the improvement of tensile strength was modest,
decreasing with clay loading from positive 19% to negative 19% for 1 and 10 wt%
of organoclay, respectively.
Several modifications of these procedures have been proposed. For example,
the interlayer spacing of an ammonium-intercalated MMT was expanded by
swelling with an organic solvent with boiling point: BP = 100-200 °C, viz. ethylene
glycol, naphtha or heptane [Wolf et al., 1999]. The swollen organoclay was then
compounded with PP in a TSE at 250 °C, replacing the solvent molecules by PP
segments and evacuating the solvent. The extent of dispersion is unknown, but
the authors reported absence of an XRD peak in the 2.0-4.0 nm range.
The aspect of the thermal stability of the organic cation used to intercalate
Na-MMT was also analysed [Lee et al., 2000a]. PP (Mw =278, Mn = 72 kg/mol),
PP-MA (Mn = 23 kg/mol, 2 wt% MAH) and organoclay (Cloisite® 20A or 30B,
i.e., MMT with 2M2HTA or MT2EtOH, respectively) were melt-mixed for 10 min
at 210 °C in an internal mixer at the weight ratio of about 70:22:8, respectively.
The XRD of the mixtures with C20A showed that the interlayer spacing increased
from that of organoclay (d001 = 2.47 nm) to 3.4 nm for C20A with PP-MA, and
to full exfoliation for the three-component CPNC. The opposite trend was seen
for mixtures with C30B. After compounding with PP-MA and/or with PP/PP-MA
the C30B interlayer spacing (d001 = 1.86 nm) was reduced to about 1.4 nm.
Furthermore, it was found that compounding under a blanket of N2 or in air
gave different results. The effect was also observed for binary PP mixtures with
organoclay (without PP-MA) where a change of the interlayer spacing was not
169
Clay-Containing Polymeric Nanocomposites
170
Intercalation of Clay
was compounded with 20 wt% of PP-MA (type E: Mw = 22.9 kg/mol, Mw/Mn = 2.6,
MAH = 2.9 wt% or type H: Mw = 32 kg/mol, Mw/Mn = 8, MAH = 4.2 wt%) and
0, 5 or 10 wt% of the organoclay in a CORI at 300 rpm and T = 190 to 230 °C.
Only C12, C16 and C18 amines produced organoclays (d001 ≥ 1.68 nm) that could
be dispersed in the compatibilised PO matrix. The interlayer spacing was found
to increase with MAH content, viz. 10 wt% of FM intercalated with either C16-
or C18-amine, when blended with 20 wt% PP-g-MA (type-H) and 70 wt% PP
gave the best performance, viz., increase of Young’s modulus by 129%, yield
stress increase by 32%, notched Izod impact strength decrease by 18% and
elongation at break decrease by 99%. XRD and TEM indicated that full
exfoliation was not achieved. The miscibility of PP-MA with PP was not examined.
Manias et al. [2001] reacted Na-MMT with either 2M2ODA or ODA
obtaining two organoclays. PP was grafted with ca. 0.5 wt% of p-methylstyrene
(PP-MS; Mw = 200 kg/mol), then the p-methyl group was converted into either
-(CH2)3-OH (PP-OH) or -CH2-maleic anhydride (PP-MA). A block copolymer
of PP with PMMA was also prepared (PP-b-PMMA; Mw = 15 kg/mol). CPNCs
were:
(i) Extruded at 180 °C using a SSE with residence time up to 10 min,
(ii) Compounded in an internal mixer at 170 to 180 °C for up to 20 min, or
(iii) Ultrasonicated in trichlorobenzene.
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Clay-Containing Polymeric Nanocomposites
According to XRD and TEM all three methods resulted in similarly structured
CPNC: intercalated tactoids and exfoliated platelets. Thus, reacting MMT-
2M2ODA with PP-MA resulted in expanded interlayer spacing from d001 = 2.4 to
3.0 nm, whereas mixing it with either PP-MS or PP-OH gave d001 = 3.4 nm. The
MMT-ODA was found to expand when blended with PP-b-PMMA from d001 = 2.2
to 3.2 nm. The short note does not contain either the postulated mechanism of
reaction between the functionalised PP and the organoclay or information about
how the chemical structure and blending time affected the exfoliation. It seems
that in the series of MMT-2M2ODA with grafted PP the interlayer expansion
was controlled by the presence of the styrenic group – the presence of MAH gave
lower expansion than that obtained from the non-polar -CH3 group. MMT-ODA
with PP-b-PMMA also showed a similarly modest expansion of the interlayer
space by Δd001 ≅ 1 nm.
Oya et al. [2000] examined the role of clay as well as a secondary intercalant
on the degree of dispersion and mechanical properties of CPNC with PP. Thus,
synthetic hectorite (FM), MMT and mica (MC) were intercalated with a
quaternary ammonium ion (2MHDODA) of the formula:
(CH3)2N+(C16H33)(C18H37). Next, the organoclay was dispersed in a toluene
solution of diacetone acrylamide (CH2=CHCONHC(CH3)2CH2COCH3; DAAM)
with a free radical AIBN initiator. After polymerisation of DAAM a solution of
PP-MA was added, the product was precipitated, washed, dried, and finally melt
compounded with PP. In parallel, CPNC was similarly prepared without DAAM.
In all cases only intercalation was obtained – the largest interlayer spacing (and
the overall best dispersion) was obtained for doubly intercalated FM prepared
with poly-DAAM. However, the best mechanical properties at 3 wt% of clay
loading were these of CPNC with MC. The authors speculated that the difference
originates in the relatively high modulus of MC pristine platelets. In conclusion,
mica may be a better nanofiller than FM, but the performance of CPNCs with
MMT was nearly as good. The additional polymerisation step did not result in
the expected improvement of dispersion and/or mechanical performance.
Intercalated nanocomposites of PP-MA with 2, 4 and 7.5 wt% clay were prepared
via melt extrusion at 200 °C in a TSE [Nam et al., 2001]. The organoclay was
synthesised by an ion exchange reaction between Na-MMT (CEC = 1.10 meq/g;
d001 = 2.31 nm after ion exchange) and ODA. The PP was modified by grafting
with 0.2% MAH (PP-MA; Mw = 195 kg/mol and Mw/Mn = 2.98). It was found
that the interlayer spacing (as measured by XRD) decreased with the clay
concentration (from d001 = 3.24 to 2.89 nm), while the thickness of the short clay
stacks increased (see Figure 35). The XRD and TEM data indicated that the
extent of exfoliation and/or stacking is controlled by the amount of clay. The
grafted MAH-groups in the PP-MA chains promoted interactions with the clay
particles by diffusion of PP chain into the space between the silicate galleries.
The authors focused on the effect of the organoclay on PP-MA crystallinity
and hierarchical structure formation. The hierarchical structure starts with the
intercalated clay spacing of 2¯3 nm, to crystalline lamellae thickness of 7-15 nm
and spherulitic texture of 10 μm diameter. Two important observations were
made. After crystallisation at 80 °C, the PP-MA formed a rod-like crystalline
texture of about 10 μm length consisting of an interfibrillar structure. The total
volume fraction of the crystalline phase was about constant, but with the increasing
clay content the γ-phase crystalline content increased from zero to 10.5%. The
formation of the γ-phase originates in the reduction of the PP-MA chain mobility
172
Intercalation of Clay
Figure 35 Interlayer spacing, d001, stack thickness, t, and its aspect ratio, p, in
PP-MA/stearyl ammonium-MMT. Data [Nam et al., 2001].
173
Clay-Containing Polymeric Nanocomposites
were observed. In the presence of C6A the XRD showed the presence of multiple
peaks, indicating non-uniform structure.
Melt-blending the two organoclays with PP and PP-MA (Polybond 3150 from
Uniroyal Chemical) resulted in a reduction of the XRD peaks’ intensity. This was
particularly evident with C6A; for N1 the interlayer spacing shifted to a higher
value (d001 = 2.7 nm), but the reduction of intensity was not as pronounced.
Thus, both systems did not exfoliate, but the degree of dispersion was better in the
presence of C6A. However, as data in Figure 36 and Table 26 indicate, it is N1 that
yields higher rigidity. The effect may originate in the different type and/different
content of the crystalline phase or the platelets’ aspect ratio. The performance of
PP was enhanced by incorporation of PP-MA and organoclay. About a 35%
increase in the tensile modulus and about a 10% increase in the tensile strength
were observed. The thermal decomposition temperature increased from 270 to
about 400 °C (for C6A). The most interesting observation is the dramatically
different large-scale morphology for PP and CPNC based on it; while PP3 crystallises
in well-known spherulites, the presence of PP-MA/organoclay (PP3/PB/6A) changed
it into a fibrillar structure. After prolonged crystallisation the fibres grow in length
and diameter, but do not revert to the spherulites. Furthermore, the PP/clay system
crystallises at temperatures higher by ca. 10 to 20 °C than neat PP, suggesting
strong nucleating capabilities of the organoclays.
In another study from the same laboratory [Hambir et al., 2002], three grades
of PP and two of PP-MA were used (see Table 26). Judging by XRD spectra, melt
intercalation with PB was superior to that of VB – evidently the acidity of the
latter graft copolymer was insufficient. The data also indicated that the use of
lower MW PP resulted in a higher degree of dispersion (judged by the reduction
of the peak areas).
Tethered PP/organoclay CPNCs were prepared via melt compounding in a
TSE at T = 180, 190, 200 and 190 °C (from hopper to die), at a screw speed of
174
Intercalation of Clay
180 rpm. For testing, dried pellets of the nanocomposite were injection-moulded
at 200 °C with a mould temperature of 30 °C [Liu and Wu, 2001]. The organoclay
was prepared from Na-MMT (CEC = 0.80 meq/g) by ion exchange reaction with
trimethyl hexadecyl ammonium bromide (3MHDA). In the presence of dibenzoyl
peroxide the product was compounded in an internal mixer for 60 min with glycidyl
methacrylate, at a weight ratio of 13:2. This epoxidised product (E-MMT) was
then compounded with PP. XRD of Na-MMT, 3MHDA and E-MMT gave the
following interlayer spacings: d001 = 1.24, 1.96 and 2.98 nm, respectively. XRD
of PP with 5 wt% of 3MHDA indicates that the d001 peak of the organoclay
remains at the same position, i.e., PP does not intercalate into the organoclay. By
contrast, XRD of PP with different loadings of E-MMT (1, 3, 5, and 7 wt%)
showed expansion of the interlayer spacing, viz. 4.92, 5.09, 4.61 and 4.75 nm,
respectively. Thus, E-MMT can lead to intercalation but not to exfoliation. The
mechanical properties of the CPNC improved with addition of organoclay,
increasing the storage modulus (by 40% at 7 wt% loading), not affecting the
impact strength and slightly reducing Tg. The addition of clay did not change the
crystal structure of PP, however silicate layers acted as nucleating agents, increasing
the crystallisation peak temperature of PP from Tc = 110.5 °C to about 120 °C.
Nanocor recently recommended CORI screw design for the manufacture of
CPNC with PO as a matrix [Qian et al., 2001]. A Leistritz TSE with D = 27 mm
and L/D = 36 was used at 300 to 500 rpm and T = 170 to 190 °C. Two vents at
13D and 24D were used. The recommended configuration is given in Table 23.
The process involves two-steps:
1. Preparation of masterbatch containing about 50 wt% of organoclay, a
compatibiliser (ca. 25 wt%), and a matrix polymer (e.g., PP-MA and PP).
2. Dilution to the desired clay content (e.g., 2 to 7 wt%).
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Clay-Containing Polymeric Nanocomposites
The latter process may be carried out using either a TSE or a SSE [Cho et al., 2002].
For example, first, organoclay/PP/PP-MA masterbatch was prepared. It contained
50 wt% Nanomer® I.30P (MMT-ODA) with 25 wt% PP-MA and 25 wt% PP.
Next, dilution of the masterbatch with PP (to 6 wt% organoclay in the final
CPNC) was carried out in either a SSE (containing different mixing screws or
add-on mixers) or in a CORI. For comparison, PP nanocomposites were prepared
following a single-step procedure. Thus, PP, PP-MA and 6 wt% I.30P were
compounded in a CORI. The interlayer spacing of all six CPNC batches prepared
by different methods was small, viz. d001 = 2.7 to 2.8 nm. Thus, intercalation not
exfoliation was obtained. The mechanical properties of the neat resin, CPNC
prepared by dilution of the masterbatch either in a SSE or in a TSE, as well as of
CPNC prepared by direct compounding are presented in Table 27. CPNC prepared
by the two-step method showed slightly better performance than that prepared
by direct compounding in a TSE, but dilution in a TSE results in a marginally
better performance than that in any SSE configuration (independent of which
mixing unit was installed). The difference between the two-step and single-step
is most likely related to the difference in d001. The origin of the increased interlayer
spacing may be related to the total residence time of the CPNC subjected to melt
compounding. Since the stated aim of the process is exfoliation, more detailed
discussion can be found in Section 2.4 and Part 4.
By contrast with the customary use of ammonium-intercalated clays, Pozsgay
et al. [2001] treated Na-MMT with N-cetyl pyridinium chloride. Melt
compounding of this organoclay with PP in an internal mixer produced rather
disappointing results as the tensile strength of PP was found to decrease with the
organoclay loading (from 1 up to 10 wt% clay). The decrease superimposed on
data obtained for a PP mixture with neat Na-MMT, indicated a lack of miscibility
between PP and the cetyl C16H33-paraffin group of the intercalant.
As reported by Wang et al. [2001a], organoclay may also act as a compatibiliser in
polymer blends. The authors dispersed 10 wt% of Nanomer I.30 TC (MMT-ODA).
Comparing the binary blend PA-6/PP = 9/1 with the three-component system
PA-6/PP/I30 = 9/1/1 it was found that addition of organoclay significantly improved
the tensile properties, viz. modulus increased from 2.5 to 4.7 GPa, tensile strength
176
Intercalation of Clay
177
Clay-Containing Polymeric Nanocomposites
The dependence of t1/2 versus 1/d presented in Figure 37 confirms that at the same
volume fraction the efficiency of a nucleating agent depends on its surface area.
The dependence is not linear, suggesting that as the particle size is reduced to
nanosize, additional factors start to play a role, viz. particle shape, aspect ratio,
curvature, increased proportion of the high energy surface atoms at a cost of the
shielded atoms in the interior, etc. The smallest CaPO3 particle with d = 7 nm (i.e.,
specific area, Asp = 69 m2/g) has a surface area one order of magnitude smaller than
MMT (Asp = 700-800 m2/g). However, it is organoclay not neat mineral that gets
incorporated into the PP matrix hence the shielding effect of the organic intercalant
plays an important role – often the clay surface is fully shielded from the matrix.
Another point that often escapes attention is the actual location of the
nanoreinforcing platelets in the semicrystalline polymer matrix. The
thermodynamics of crystallisation require that any foreign material should be
expelled from the growing crystal. Hence, the organoclay must be located mainly
in the non-crystalline part of the CPNC, in the liquid phase of PP at T > Tg ≅ 0 °C
or in the glassy part at lower temperatures. Since the crystallinity of PP in CPNC
may be as high as 68%, the clay concentration in the non-crystalline phase may
be three times higher than average. Owing to the crowding effect, the interlayer
spacing in this case may be reduced by a factor of up to 3. Thus, on the one hand
large effects of organoclay addition into a semi-crystalline matrix may not be as
significant as those in an amorphous one and on the other the mechanism of the
nanoclay nucleating activity should be taken into account.
The key information from the relatively large number of reports on melt
intercalation of PP/organoclay systems is summarised in Table 28. As far as the
tensile modulus is concerned, the data indicate that at low clay loading it increases
linearly with clay content. For exfoliated CPNC with PA-6 as the matrix the
dependence (up to 10 wt% of clay) may be expressed as:
E R ≡ E / Ematrix 1 + a0 w ; a0 = 0.2 (22)
where w is clay (inorganic part only) content.
178
Table 28 Summary of melt intercalation in PP matrix
Clay Intercalant Compatibiliser Polymer Process d001 (nm) Performance Ref.
Na-MMT 2M2ODA Hydroxylated PP 30 Internal mixer > 3.87 to Telechelic diol or PP-MA Maxfield et al.,
polybutadiene or kg/mol at 220 °C exfoliation should have good 1995,
PP-MA chemical affinity to Usuki et al., 1997
2M2ODA
Na-MMT ODA PP-MA; acid = 52; none Internal mixer 7.22 for 33 wt% Optimum when one polar Kato et al., 1997
or PP-OH; OH = at 200 °C of organoclay group per 25 PP-mers is
54 present
Na-MMT ODA PP-MA (Yumex PP TSE at 210 °C; 5.9 & 6.4 for Miscibility of the PP/PP- Kawasumi et al.,
or FM 1001, acid # 26) and injection MMT & FM MA blends is of critical 1997; Hasegawa
moulded importance eet al., 1998
MMT Aminosilane PP-MA, 1-5 wt% PP In xylene at 2.4 to 7.3 The key is bonding Hudson, 1999
H2NR1 MAH; Mn = 20 120 °C, or in through co-crystallisation
-SiR2R3R4 kg/mol melt between the grafted PP
and the main PP
MMT Ammonium Solvent with BP = PP TSE at 250 °C No XRD peak in Wolf et al., 1999
intercalated 100 – 200 °C (solvent the range 2.0-4.0
evaporation) nm
Na-MMT ODA PP + 0.2 wt% none TSE at 200 °C Exfoliation + Tensile modulus up by a Hasegawa et al.,
MAH; Mw = 210 shoulder factor of 1.9 (at 5% 2000a
kg/mol d001 ≅ 3.4 loading), tensile strength
up by 19%
179
Intercalation of Clay
Table 28 Continued...
180
Clay Intercalant Compatibiliser Polymer Process d001 (nm) Performance Ref.
Na-MMT ODA PP + 0.2 wt% none TSE at 200 °C Exfoliation + Relative tensile vs. T: E´ = Hasegawa et al.,
MAH; short stacks at 1.5 to 2.5 with max at T = 2000b
Mw = 210 kg/mol 5.3 wt% clay 50 °C. Note that Young’s
modulus E(PP) = 780,
E(PP-MA) = 429 MPa
Na-MMT 2M2ODA PP-MA; 1 wt% PP TSE at 200 °C Exfoliation + Tensile strength from 29 Zhang et al.,
MAH shoulder 3.4 to 31 MPa 2000b
Cloisite® 2M2HT PP-MA, 2 wt% PP Internal mixer Exfoliation at Good performance Lee et al., 2000a
C20A MAH at 210 °C 8% C20A
Cloisite® MT2EtOH PP-MA, 2 wt% PP Internal mixer 1.4 Bad performance – Lee et al., 2000a
C30B MAH at 210 °C composite
Clay-Containing Polymeric Nanocomposites
Cloisite® 2M2HT PP-MA, 0.55, 1.1, PP Internal mixer 3.2 at 5 wt% Best for low MW PP & Kim et al., 2000
C20A 3, 5 % MAH at 200 °C C20A the lowest MAH content
Cloisite® 2MHTEtOH PP-MA, 0.55, 1.1, PP Internal mixer 1.8 at 5 wt% Worst case Kim et al., 2000
C25A 3, 5 % MAH at 200 °C C25A
FM n-alkyl PP-MA, MAH = PP CORI, 300 Exfoliation? Young's up by 129%, Reichert et al.,
amines 2.9 wt% rpm, 190 to yield stress up by 32%, 2000
C4 – C18 5 & 230 °C Izod impact down by
10 wt% 18%, elongation down by
99%.
Na-MMT 2M2ODA PP-OH or PP-MA - SSE at 180 °C; Stacks (3.4 nm) Improved mechanical Manias et al., 2001
ultrasonics + platelets properties and reduced
(US) in solvent flammability
Table 28 Continued...
Clay Intercalant Compatibiliser Polymer Process d001 (nm) Performance Ref.
Na-MMT ODA PP-OH or PP-MA - SSE at 180 °C; Stacks at 3.2 + Improved mechanical Manias et al., 2001
US in solvent platelets properties and reduced
flammability
MMT, 2MHDODA Polyacrylamide + PP 2.3 to 3.8 At 3 wt% clay modulus Oya et al., 2000
FM, or PP-MA increased by 67%, TS by
mica 26%, Izod by 95%
Cloisite® 2MBHT Styrene PP Internal mixer Exfoliation? Ultrasonics caused Ryul et al., 2001
C10A at T = 180 °C copolymerisation of
+ US styrene
Cloisite® 2M2HT Styrene PP Internal mixer 3.65 Ultrasonics caused Ryul et al., 2001
C20A at T = 180 °C copolymerisation of
+ US styrene
Na-MMT ODA PP with 0.2% PP TSE at 200 °C Intercalation; PP-MA formed rod-like Nam et al., 2001
MAH 2.9 to 3.2 crystals; higher modulus
MMT ODA PP-MA, 2.5 wt% PP Internal mixer Intercalation Best results with ODA and Marchand and
MAH at 180 °C 10 wt% PP-MA Jayaraman, 2001
Cloisite® 2M2HT; 4 PP-MA Polybond PP SSE at 160 to 1.2 to 3.3 Better dispersion than for Kodgire et al.,
6A wt% 3150; 1 wt% 200 °C Nanoclay, but poorer 2001; Hambir et
MAH performance al., 2001; Hambir
et al., 2002
Nanoclay ODA; 4 wt% PP-MA Polybond PP SSE at 160 to 2.7 Higher modulus than with Kodgire et al.,
3150; 1 wt% 200 °C 6A (increased by 42%); 2001; Hambir et
MAH TS increased by 10% al., 2001; Hambir
et al., 2002
181
Intercalation of Clay
Table 28 Continued...
182
Clay Intercalant Compatibiliser Polymer Process d001 (nm) Performance Ref.
Na-MMT 3MHDA; Organoclay PP TSE at T = 180, 5.09 with Storage modulus up by Lui and Wu, 2001
5 wt% grafted with 190, 200 °C, epoxidised 40% (7 wt% loading),
glycidyl 180 rpm; IM organoclay same impact strength, Tg.
methacrylate Down Tc up by 10 °C
Nanomer® ODA; PP-MA PP CORI for master 2.7 to 2.8 Flex modulus up by 67%, Sakai, 2002; Cho
I.30P 6 wt% batch, then flex strength up by 36%, et al., 2002; Lan
either CORI or HDT up by 19 °C and Quiqan, 2000
SSE for diluting
to 6 wt%
Na-MMT N-cetyl None PP Internal mixer ? Tensile strength of PP Pozsgay et al.,
pyridinium down with organoclay 2001
loading
Nanomer ODA PP-MA; 1.5 to 5.8 PP/PA-6 TSE at T = 180- 3.7; organoclay Modulus increased by Wang et al., 2001a
Clay-Containing Polymeric Nanocomposites
I.30 TC wt% MAH 230 °C, 90 rpm as compatibiliser 36%, tensile strength by
15%, impact strength,
down 70 to 13 J/m.
Nanomer OD A PP-MA; 0.2 wt% TSE at 200 °C 3.03 at 4 % Okamoto et al.,
of MAH organoclay 2001
Cloisite 2M2HT; AA-g-PP PP 6100 TSE at 200 °C, 3.5 Improved: Flex strength: Ton-That et al.,
15A 2 wt% (Polybond 1001), 200 rpm 13%, modulus: 22%; 2002
4 wt% tensile strength: 1%;
modulus: 15%, Izod: 45%
Cloisite 2M2HT; MA-g-PP PP 6100 TSE at 200 °C, 3.5 Improved: Flex strength Ton-That et al.,
15A 2 wt% (Polybond 3150), 200 rpm 16%, modulus 32%; 2002
4 wt% tensile strength 3%;
modulus 9%, Izod 25%
Intercalation of Clay
183
Clay-Containing Polymeric Nanocomposites
184
Intercalation of Clay
lesser extend on the type of clay [de Siquira et al., 1999]. The authors explained
the observed changes in the interlayer spacing as caused by molecular
rearrangement of the ammonium radicals, melting of the n-paraffin groups, or
changes of hydration.
Information on the effects of pressure (P) is even more difficult to find.
However, there are indications that with increasing P the interlamellar gallery
height decreases. High-resolution data were obtained using time-of-flight neutron
diffraction of hydrated Ca- and Na-smectite and vermiculite [de Siquira et al.,
1999]. The measurements were conducted in a special Ti/Zr cell that could
withstand simultaneously T ≤ 350 °C and P ≤ 200 MPa.
The data are presented in Figure 39. One of the more interesting conclusions
from that work was that the interlayer water is denser than that in the bulk: ρinterlayer
= 1.06 versus ρ bulk = 0.874 g/ml. In other words, there is a reduction of free
volume in the vicinity of the clay particle surface. If so, the compressibility should
also be reduced. The transitionless reduction of the interlayer spacing of Ca-smectite
gives the isothermal volumetric compressibility of the hydrated clay: κ = 4.8-10-5
MPa-1, to be compared with bulk water compressibility of κ = 4.5-10-4 MPa-1 – a
reduction by a factor of 9.
185
Clay-Containing Polymeric Nanocomposites
2.3.10.1 Kaolinite
The structural formula for kaolinite is A14Si4Ol0(OH)8, and it is a 1:1 type clay,
hence different from the commonly used 2:1 type smectites. Its lattice consists of
one sheet of tetrahedrally coordinated SiO4 and one sheet of octahedrally
coordinated AlO2(OH)4. Kaolinite has a low value of CEC = 0.02-0.04 meq/g
and large aspect ratio. In neat kaolinite the adjacent cells are spaced about 0.71 nm
across the (001) plane. A layer of -OH covers the octahedral sheet forming strong
hydrogen bonds between the layers, hence only a limited number of polar guest
species, viz. N-methyl formamide (NMF) or dimethyl sulfoxide (DMSO), can be
introduced. However, once the layers are separated, the -OH functionality may
be used for hydrogen bonding with some polymers. Thus, kaolinite has quite a
different structure than MMT, viz. one side of the interlayer space is covered
with hydroxyl groups of the AlO2(OH)4 octahedral sheets and the other side is
covered by oxygen atoms of the SiO4 tetrahedra. As a result, CPNC with kaolinite
are expected to exhibit different behaviour from those with MMT. In 1996 Tunney
and Detellier provided an overview of the earlier work.
The first incorporation of a polymer into kaolinite was reported in the early
1990s. In a series of publications Sugahara and his colleagues [Sugahara et al.,
1992] intercalated kaolinite with monomeric acrylonitrile, acrylamide or
vinylpyrrolidone then induced thermal polymerisation. However, this method
did not provide a means for controlling the molecular weight and its distribution.
The first direct intercalation of kaolinite with macromolecules took place more
recently [Tunney and Detellier, 1996]. The motivation for this work was a search
for anisotropic ionic conductivity. In other layered materials two-dimensional
confinement of PEG provided the desirable performance. In other words, here
total exfoliation was neither expected nor desired. The applied method consisted
of two steps:
1. Intercalation of kaolinite with a solvent, and
2. Compounding the intercalated kaolinite with a polymer, which progressively
displaced the solvent molecules in the interlamellar galleries.
The authors have shown that it is possible to prepare two distinct ethylene glycol
phases of kaolinite, with d001 = 0.94 and 1.08 nm. The former intercalate had the
ethylene glycol unit covalently bound to the interlayer aluminol surface, while
the other had a more weakly bound intercalated phase.
The logical next step was to intercalate larger oxyethylene-based molecules
into kaolinite. Thus, first DMSO or NMF was used to intercalate kaolinite, and
then PEG-3400 or PEG-1000 displaced the low molecular weight intercalant.
This was accomplished by heating PEG with ca. 17 wt% DMSO-intercalated
kaolinite in a round-bottom flask for 9 days at T = 155 °C. The product was
purified and dried in an oven at 100 °C for 3 days. Elemental analysis: carbon
7.90%; hydrogen 2.63%. XRD gave d001 = 1.112 ± 0.004 nm. The calcination
weight loss was 29.1%.
Several samples were prepared from combinations of clay, intercalating
solvents and melt-intercalating PEG resins. Their interlayer expansion was
comparable, ranging from d001 = 1.085 to 1.119 nm, i.e., providing an interlamellar
space of Δd001 ≅ 0.37-0.41 nm. This indicates that the intercalated oxyethylene
units are arranged in a flattened monolayer conformation. It is noteworthy that
intercalation, using PEG-1000 dissolved in either water or 1,4-dioxane, was
186
Intercalation of Clay
unsuccessful. The success of the intercalation by the melt method could be due to
a strong concentration effect of the polymer and lower stabilisation energy of
polymer segments.
Larger interlayer expansion was obtained by reacting kaolinite with phenyl-
phosphonic acid (PPA) in a water/acetone (1:1) solution at 95 ± 5 °C for up to
19 days [Guimarães et al., 1998]. The topotactic reaction was stoichiometric,
viz.:
Al2Si2O5(OH)4 + 4 H2O3PPH → Al2Si2O5(OH)(HO3PPH)3×2H2O + 3H2O
As a result of reaction the interlayer spacing increased from that of kaolinite
(d001 = 0.716 nm) to the spacing of the kaolinite phenyl-phosphonate (KPP):
d001 = 1.502 to 1.645 nm, i.e., providing an interlamellar space of Δd001 ≅ 0.786-
0.929 nm. The analysis suggested that phenyl-phosphonate groups were grafted
to the kaolinite platelets. The materials were stable up to ca. 450 °C.
In another report [Guimarães et al., 1999] hydrated kaolinite phenyl-
phosphonate (KPP-hyd) was reacted with hexylamine. The reaction produced a
stable light-yellow compound (KPP-hex). XRD gave d001 = 1.636 nm, consistent
with the size of the intercalating hexylamine. The thermal analyses showed that
at T ≅ 230 °C hexylamine molecules decomposed, but the resulting KPP remained
stable up to 498 °C, at which temperature the grafted phenyl phosphonate started
to decompose and dehydroxylation of kaolinite takes place.
In 1999 Gardolinski et al. [1999] intercalated kaolinite in two steps, first
reacting it at 60 °C with an aqueous solution of DMSO. After washing and
characterisation, the resulting complex: Al 2 Si 2 O 5 (OH) 4 (DMSO) 0.4 was
stoichiometrically reacted at RT with N-methyl-2-pyrrolidone (NMP). The product
was Al2Si2O5(OH)4(NMP)n (where n = 0.39 ± 0.02). XRD gave d001 = 1.231 nm,
i.e., an expansion of 0.11 nm over the DSMO complex. The presence of NMP
molecules in the interlamellar space resulted in a notable enhancement of the
thermal stability – while the DMSO-complex decomposes at 175 °C, the NMP
complex remains stable up to 431 °C.
In the next publication from this group, first kaolinite was reacted with DMSO,
producing a kaolinite-DMSO complex. The complex was subsequently reacted with
either PEG or bacterial polyhydroxybutyrate (PHB) in the molten state at 130 or
180 °C, respectively [Gardolinski et al., 2000]. The displacement of DMSO molecules
took several days – highly ordered polymer/kaolinite CPNC was obtained. In the
interlamellar galleries of kaolinite, PEG macromolecules formed a polymeric
monolayer. The characteristics of the kaolinite-complexes are listed in Table 29.
As mentioned above, Sugahara and his colleagues synthesised several kaolinite-
polymer compounds (viz. kaolinite-PAN, kaolinite-PAAM, or kaolinite-P4VP)
by first intercalating kaolinite with the appropriate monomers and then
polymerised by thermal treatment. The serious drawback of this procedure is the
lack of control of the degree of polymerisation of the resulting polymers.
Recognising the problem, the authors developed an alternative intercalation
method [Komori et al., 1999b]. The publication is particularly valuable as that
the authors also reported the unsuccessful attempts. The process resembles the
‘common solvent method’ discussed in the next Chapter. Thus, pre-intercalated
kaolinite at room temperature is dispersed in a polymer solution. For example
when kaolinite-ammonium acetate was used as the intermediate for the
intercalation of P4VP (Mw = 10 kg/mol) dissolved in water, the displacement was
187
Clay-Containing Polymeric Nanocomposites
188
Intercalation of Clay
compositions in the table are of interest. Taking into account different clay loadings,
the performance ratio of PA-6/kaolinite-PA-6 to that of PA-6/MMT (per 1 wt% of
clay) is: 1.18, 1.28, and 1.2, for the tensile strength, tensile modulus and impact
strength, respectively. Evidently, the properties are not proportional to the clay
content, thus the performance ratios showing about 20% better performance for
CPNC with kaolinite than with MMT may not be correct. However, it is intriguing
that kaolinite with only slightly expanded interlayer spacing offers at least
comparable performance to that of commercial-grade CPNC with exfoliated
MMT. Since kaolinite in the PA-6/kaolinite-PA-6 material is not exfoliated, the
enhancement of properties must be related to the surface effects. The surface of
kaolinite particles is covered by -OH groups, which interact with PA-6 via
hydrogen bonding. The particle size of kaolinite is larger than that of MMT,
which might also contribute to the enhanced properties.
189
Clay-Containing Polymeric Nanocomposites
190
Intercalation of Clay
flux direction. As shown in Figure 40, the permeability reduction (at constant
concentration of clay in PI matrix) is fully accounted for by the clay platelets’
aspect ratio. Furthermore, addition of 2 wt% of synthetic mica reduced the PI
thermal expansion coefficient at 100 °C by 40%. Smaller factors were obtained
for the other clays with smaller aspect ratio.
The same intercalation method was successfully used for Na-MMT and
synthetic fluoromica (FM, Somasif ME-110 from CO-OP Chem. Co.) [Kawasumi
et al., 1997; Hasegawa et al., 1998]. First the clays were intercalated with ODA,
then organoclay powder (7.3 wt%), PP (melt flow rate = 16 g/min; 70.8 wt%)
191
Clay-Containing Polymeric Nanocomposites
and PP-MA (21.9 wt%) were dry-blended, then compounded in a TSE at 210 °C,
incorporating about 5 wt% of clay (MMT or fluoromica). It was shown that
compounding organoclay with PP caused a reduction of the interlayer spacing,
while in the presence of PP-MA it increased to d001 = 5.9 and 6.4 nm for MMT
and FM, respectively. In other words, neither one of these two clays was exfoliated,
but the degree of dispersion was higher for the system with FM. The authors
presented a strong case for the critical importance of PP/PP-MA blend miscibility
– well dispersed clay platelets were evident in TEM micrographs for miscible
systems, with a shoulder on the XRD spectrum indicating the presence of tightly
spaced short stacks.
In 1998 Katahira et al. [1998a,b,c,d] published a series of articles on the use
of mica for the production of PA-6-based PNC. Thus, purified Na-mica flakes
were dispersed in hexanoic acid-ω-ammonium phosphate, prepared by treating
ε-caprolactam with phosphoric acid. The intercalation was rapid even at 20 °C,
but the exchange of Na+ was accelerated by heating to T > 60 °C. The monomer-
intercalated mica showed d001 = 1.47 nm. During polymerisation (under low or
high pressure) the mica exfoliated. Owing to the high dispersion of high aspect
ratio clay platelets excellent amelioration of the bending strength and modulus
were obtained for the CPNC. Thus, the formation of CPNC consisted of three
steps:
1. Protonation of ε-caprolactam by phosphoric acid,
2. Intercalation of mica by ion exchange of Na+ with protonated lactam,
3. Polymerisation at T ≥ 260 °C which expanded the interlamellar spacing all
the way to exfoliation.
Badesha et al. [1998] prepared CPNC with fluoroelastomer matrix and dispersed
in it mica-type clay (SCPX-984 from SCP). The aspect ratio of mica platelets
ranged from p = 50 to 1000. The clay was first intercalated with 2M2ODA. The
fluoroelastomers of interest were copolymers and terpolymers of vinylidene
fluoride, hexafluoropropylene, and tetrafluoroethylene, known commercially as
Viton, Fluorel, Aflas, Tecnoflon, etc. These may be cured with, e.g., a bisphenol
and organophosphonium salt (accelerator). Other additives, such as colouring
agents, processing aids, conductive fillers, initiators and accelerators may also be
added. The intercalated mica could be dispersed in the matrix by compounding,
e.g., milling prior to curing. During compounding the fluoroelastomer chains
penetrate the organophilic clay, causing each platelet to be surrounded by polymer,
hence exfoliating. The exfoliated nanocomposite may be formed with or without
going through the intermediate stage of intercalation. An example describes
addition of 10 phr of organoclay to 100 parts of Fluorel, and then milling the
compound for 15 min on a two-roll rubber mill with a tight nip at 27 to 38 °C.
XRD indicated that no intercalation had taken place. However, when the milling
temperature was increased to 50 °C, the interlayer spacing increased to d001 = 3.3 nm
– hence intercalation. However, at still higher milling temperature, T = 66 °C,
fully exfoliated CPNC was produced.
Zilg et al. [1999a] investigated the correlations between the polymer
composition, type of clay, its concentration and mechanical properties. The matrix
was based on diglycidyl ether of bisphenol-A (DGEBA) cured with
hexahydrophthalic anhydride. Three types of clay were used:
1. Synthetic fluoromica (FM; Somasif ME 100 from CO-OP Chem.),
192
Intercalation of Clay
2. Purified Na-MMT (particle diameter 15 μm, BET surface area 25 m2/g from
Südchemie AG) and
3. Synthetic hectorite (FH; Optigel SH from Südchemie AG).
The clays were made organophilic by ion exchange with various alkyl ammonium
ions: dodecylamine (DDA), N,N-dimethyl didodecyl amine (2M2DDA),
N,N,N-trimethyl dodecyl ammonium chloride (3MDDA), N-methyl dodecyl
N,N-bis(2-hydroxyethyl)-ammonium chloride (MD2EtOH; AKZO Ethoquad
C12), 12-aminododecanoic acid (ADA), a,x-bis(aminopropyl)-terminated
oligo(propylene oxide), known as Jeffamine of the D series (JAD 130, 300, 500,
800), N,N,N,N-dimethyl dioctadecyl ammonium chloride (2M2ODA) and
N,N,N,N-dimethyl benzyl-octadecyl ammonium chloride (2MBODA). Upon
intercalation the interlayer spacing of FM increased in the expected sequence,
e.g., after ion exchange with MD2EtOH the neat clay spacing of d001 = 0.94
increased to 1.74 nm, and then upon matrix polymerisation to d001 = 6.79 nm.
The authors reported that (at 5 wt% of clay content) FM was difficult to disperse
beyond short stacks. Easier to disperse (but still in form of short, intercalated
stacks) was MMT, while FH exfoliated quite readily.
Enhanced toughness was associated with the formation of dispersed
anisotropic laminated nanoparticles consisting of intercalated silicates. The
authors confirmed the earlier report from Pinnavaia’s laboratory that d001 spacing
increases with the onium salt alkyl chain length, and that primary amines increase
the interlayer spacing more than the quaternary ones. During curing, the former
most likely reacted with epoxy which the latter were unable to do. With 10 wt%
of the ammonium salt used on the silicates, not all were properly intercalated,
i.e., XRD showed a diffraction peak indicating intercalation. On the other hand
(e.g., for FH intercalated with 2MBODA) TEM micrographs showed randomly
dispersed individual platelets, suggesting exfoliation. An interesting observation
came from comparing the spacings calculated from XRD and AFM micrographs,
viz. 6.8 and 11 nm, respectively. The explanation offered is that the individual
clay platelets are quite flexible and bend under the force of the AFM test tip.
The mechanical properties of four series of epoxy-based CPNCs are
summarised in Figure 42. Surprisingly, there is little improvement of properties
by 2MBODA intercalation – the tensile strength of neat MMT or FH is higher
(mid-concentrations) than that after intercalation. The best fracture toughness
was reported for FM and MMT, intercalated or not.
In another publication from the same laboratory [Zilg et al., 1999b], CPNCs
based on a PU matrix were prepared by dispersing synthetic fluoromica (FM;
Somasif ME100 from CO-OP Chem. Co.). The clay was manufactured by heating
Na2SiF6 with talc. The FM lamellae consist of a sheet of octahedral alumina
sandwiched in between two sheets of tetrahedral fluorosilica. Because in the
octahedral sheet Mg2+ ions substituted for some Al3+ ones, the lamellae are
anionically charged. Similarly, like MMT, FM behaves as a weak silicilic acid, with
Na+ as counterions in the interlamellar gallery. During dispersion, the fairly large
FM particles of average diameter around 5,000 nm (aspect ratio p ≤ 5,000) were
broken down into anisotropic nanoparticles resembling short fibres of 500 nm
length and 20 to 50 nm diameter, thus the effective aspect ratio (peff) for the clay
was only peff ≅ 20 to 50. Two series of CPNC samples were prepared, with non-
intercalated and with intercalated FM. In the latter case, FM was intercalated with
2MBODA (Ethoquad C12) in aqueous medium. Dry, intercalated FM was dispersed
193
Clay-Containing Polymeric Nanocomposites
194
Intercalation of Clay
The clay lamellae were well dispersed within the matrix, but without full
exfoliation. The mechanical behaviour of the two series of PU/FM nanocomposites
is presented in Figure 43. Intercalation significantly improved the tensile strength
(by 60-240%) and elongation at break (by 130-400%), but it had a negative effect
on modulus. The CPNC seems to have clay platelets bonded to PU. In conclusion,
dispersion of intercalated synthetic fluoromica in a polyurethane matrix results in
the formation of intercalated (not exfoliated) structures that offer significant
improvement of mechanical properties (in comparison to neat PU).
An interesting use of PA-6-based CPNC was reported by Cheng et al. [2000].
The authors found significant differences in the suitability of PA-6 and its CPNC for
the preparation of microporous membranes. While neat PA-6 generated asymmetric
membranes with tight skin and a porous sublayer, the intercalated mica/PA-6 system
(PA-6/mica nanocomposites, M1030D from Unitika; Mn = 15 kg/mol, MI = 19)
produced skinless microporous membrane with an open, bicontinuous structure
that could easily be adjusted. Hence, while PA-6 produced membrane useless for
microfiltration, the mica-filled CPNC engendered perfectly adjustable, useful
products.
To close this discussion on CPNCs with non-MMT layered nanofillers, the
use of layered double hydroxides (LDH) should be mentioned. A recent review
described the synthesis and characterisation of these materials [Leroux and Besse,
2001]. The LDH ideal structural formula is:
[MIIxMIII1-x(OH)2]intra[Am-x/m·nH2O]inter
where MII and MIII are metal cations, A is the anion, and intra and inter denote
the intralayer domain and the interlayer space, respectively. The structure consists
of edge-sharing M(OH)6 octahedra. Partial MII to MIII substitution induces a positive
charge for the layers, balanced with the presence of the interlayer anions. LDH are
195
Clay-Containing Polymeric Nanocomposites
often prepared via coprecipitation using MII and MIII salts at constant pH, mostly
basic conditions. Their charge density is significantly higher than that of Na-MMT,
viz. 0.25 to 0.40 nm2/charge versus 0.70 nm2/charge for the latter. Correspondingly,
the CEC for the LDH material ranges from 0.6 to 4.8 meq/g, whereas that for
Na-MMT is about 1 meq/g. A lower CEC makes exfoliation easier.
There are three principal methods of LDH intercalation:
(a) Using such monomers as aniline, pyrrole, ω-aminoacid, methyl methacrylate,
vinylbenzene sulfonate, vinylpyrrolidone, vinyl acetate, etc.;
(b) Direct intercalation of extended polymer chains in the host lattice, for
example, PEG/MoO3, poly(p-phenylene)/molybdenum bronze, PANI/MoS2,
or PEG/NbSe2. Sometimes, a two-step intercalation (as for MMT) may have
to be used;
(c) Transformation of the host material into a colloid and precipitation in the
presence of the polymer.
Thus, numerous methods for the preparation of LDH/polymer systems have been
used, viz. coprecipitation, exchange, in situ polymerisation, two-step surfactant-
mediated incorporation, hydrothermal treatment, reconstruction, or restacking.
The latter method, effective via the exfoliation of the LDH layers, appears to be
more appropriate for the capture of monomers. Examples of polymer/LDH
systems are given in Table 31.
These multicomponent systems are thermally more stable than the pristine
inorganic compounds, leading, for example, to potential applications in flame
retardant composites. A large variety of LDH/polymer systems may be tailored
considering the highly tunable interlayer composition coupled to the choice of the
organic moiety. DNA may be stabilised in the interlayer space of (Mg2AlNO3) as a
gene reservoir. Some of the intercalated polymers present excellent physical
properties such as conductive properties (PANI), insulation (PS), or ion-gate
properties (polypyrrole (PPY)), but are difficult to process because of a lack of
mechanical strength. Numerous studies have focused on the use of conductive
polymers as capacitor, rechargeable battery materials or in electrochromic windows.
Hsueh and Chen [2003] prepared LDH (by co-precipitation in NaOH solution
of Mg(NO3)2·with Al(NO3)3), with polyimide (PI) and epoxy matrix, respectively.
According to TEM and XRD, in both nanocomposites the LDH were exfoliated.
In parallel, the mechanical performance of these systems was enhanced. In CPNC
with a PI matrix the elongation at break (εb) and maximum tensile strength (σy)
were obtained at ca. 4 and 5 wt% organoclay loading, respectively. Similarly, for
CPNC with epoxy matrix εb reached maximum at about 3 wt%, while σy
continuously increased up to the highest organoclay concentration of 7 wt%.
For both systems the tensile modulus and thermal decomposition temperature
also increased, while the thermal expansion coefficient decreased with LDH
loading. The fine dispersion of the inorganic component was illustrated by
photographs, which showed that in the whole range of LDH concentration the
epoxy nanocomposites remain transparent.
While exfoliation of any layered nanofiller is easier in a matrix with polar
groups, dispersion of clay or LDH in non-polar polymers is difficult. For these
reason two publication from B. Qu laboratories are of particular interest [Chen
and Qu, 2003; Chen et al., 2004]. The first describes exfoliation of Mg3Al(OH)8-
(C12H25SO4), or MgAl-LDH for short, by intercalation with PE-g-MAH in a
solution of xylene under reflux.
196
Intercalation of Clay
197
Clay-Containing Polymeric Nanocomposites
The platelets of LDH were about 0.48 nm thick and ca. 70 nm in diameter. The
nanocomposites containing 5 wt% LDH had a higher decomposition temperature
(by ca. 60 °C), and greater thermal stability than PE-g-MA. In the second
publication Zn3Al(OH)8(C12H25SO4), or ZnAl-LDH for short, was prepared by
spontaneous self-assembly in an aqueous solution of Zn(NO3)2, Al(NO3)3, and
C 12H 25SO 4Na at pH ≅ 10. As before, the exfoliation of ZnAl-LDH was
accomplished by refluxing its suspension in a xylene solution of (unmodified!)
LLDPE for 24 h. The exfoliated nanocomposites contained up to 20 wt% of
ZnAl-LDH. Better thermal stability was observed. The method is expected to be
applicable to other polymers, viz. PP, PS, rubbers, and the polar ones.
Another interesting layered material is Zr(HPO 4) 2·H 2O, α-zirconium
phosphate (α-ZrP). Clearfield et al., synthesised it in 1964 and for years studied
its ion exchange ability [Clearfield et al., 1969; 1972]. In comparison to MMT
the α-ZrP has higher charge (CEC = 2), smaller interlayer spacing (d001 = 0.76 nm),
and it can be prepared with a desired aspect ratio (at least 100) and particle size
distribution. Crystalline α-ZrP has the layers formed by Zr and O atoms of the
phosphate groups, with one -OH group pointing into the interlamellar galleries.
More recently, to study the interrelations between CPNC structure and
performance, the team prepared the first nanocomposites with exfoliated α-ZrP
in epoxy [Sue et al., 2004]. Thus, α-ZrP was synthesised, intercalated with
monoamine-terminated polyether (Jeffamine M715), and then 1.9 vol% of the
intercalated α-ZrP was incorporated into DGEBA. According to TEM, XRD
and the optical transparency of the cured nanocomposites, full exfoliation was
achieved. The influence of hydrogen-bonded α-ZrP intercalate on the mechanical
properties of epoxy was investigated. The volume percentages of the specimen
components were: α-ZrP = 1.9, Jeffamine = 18.7 and DGEBA + curing agent =
79.4 vol%. Thus the cured specimen contained a large amount of the plastifying
intercalant: CH3O(CH2CH2O)14CH2CH2NH2. The rubbery plateau modulus of
the nanocomposite was about 4.5 times higher than that of the matrix. Upon the
addition of 1.9 vol% α-ZrP, the tensile modulus increased by 50%, and the yield
strength improved by 10%, but the elongation at break was drastically reduced.
However, the mode-I critical stress intensity factor, KIC, indicated that the fracture
toughness is not significantly affected by the addition of the intercalated nanofiller
– the epoxy resins are inherently brittle and/or notch-sensitive.
Nanocomposites of PA with up to 65 wt% of hydroxyapatite have been
prepared for use as a load-bearing bioactive material for bone repair or substitution
[Jie et al., 2003].
198
Intercalation of Clay
199
Clay-Containing Polymeric Nanocomposites
Table 32 Continued
Clay Intercalant d-spacing (nm) Comments
A layered Hydrolysed alcoholates: ⇒ exfoliation For PO-based
material, e.g., Si(OR)4, Al(OR)3, CPNC (Dow)
MMT Ge(OR)4, Si(OC2H5)4,
Si(OCH3)4, Ge(OC3H7)4,
Ge(OC2H5)4
Clay filler Amino-functional silane + ⇒ exfoliation For PO-based
carboxylated or maleated CPNC
semicrystalline PO
Acidified clay; Lewis bases, esp. primary ⇒ exfoliation Tested for epoxy-
H+MMT amines and PU-based
CPNCs
Synthetic Aq. solution of Intercalation 2 weeks
smectite ethylenediamine + polyol, intercalation for
then oleophilic solution of fire-resistant clays
triethyl phosphate (TEP)
MMT Aq. solution of PVP (at 1.5-11.0; 3-4.5 Thickener or for
least 10% of water is is optimum drug-delivery
needed)
MMT Polar, water soluble ⇒ exfoliation For CPNC as well
compounds
Smectite Aq. solution of AlCl2(OH) 2-6 (rigid) For catalyst support
+ ZrOCl2
MMT Waterless PEG in 2-6 h 1.77
Organoclay Monomer or polymer ⇒ exfoliation For PA-type
200
Exfoliation of Clays
2.4
Exfoliation of Clays
201
Clay-Containing Polymeric Nanocomposites
2.4.1 Principles
The layered inorganic materials that are to be used as nanofillers, e.g., natural or
synthetic clays, have strong ionic and van der Waals interactions and small
interlamellar spacing, much too small for allowing organic molecules, monomers,
oligomers or polymers, to diffuse into. Expansion of the interlayer spacing to
total exfoliation is accomplished in several steps.
Since clays are strongly hydrophilic, the first step is suspending them in an
aqueous medium. Few types of hydrophilic, highly polar, low MW polymers
(viz. PEG or P2VP) may be used to exfoliate directly such a swollen clay. For the
great majority of CPNCs with hydrophobic polymeric matrices the swollen clay
must be intercalated with one or two intercalants (e.g., onium salt and silane or
an epoxy compound). The hydrophobic monomers and polymers require that
the nanofiller is pre-intercalated, and often compatibilised.
The following four pathways have been distinguished [Usuki, 2001]:
1. Hydrophilic matrix with strong polar groups, e.g., P2VP or PEG:
water hydrophilic polymer
clay swollen clay CPNC
202
Exfoliation of Clays
intercalant(s)
clay intercalated clay + compatibiliser
compounding
+ non-polar polymer CPNC
The difficulty in achieving exfoliation increases in the sequence from pathways 1
to 3. The key to good performance is on the one hand obtaining initial expansion
of the interlayer galleries for penetration by monomer(s) or polymer, and on the
other good thermodynamic miscibility between the preintercalated clay platelets
and the polymeric matrix. In the case of the reactive exfoliation processes
(pathways 1 and 2a) an important additional condition is that the polymerisation
inside the gallery is at least as fast as that outside it. When this condition is not
met, the polymer formed outside the interlamellar galleries may hinder expansion
of the interlayer space, leading to intercalation but not exfoliation. It is noteworthy
that the clay and the intercalating onium salt often affect the polymerisation rate
– one must ascertain that these effects are positive, i.e., that these catalyse the
reaction. Another often forgotten requirement is the stability of the clay-matrix
bond. The CPNC must survive the forming stage! There are very few polymers
that can be processed below 200 °C. Above this temperature the ammonium
intercalants (especially quaternary) are not thermally stable (especially in the
presence of oxygen and shear field). Reaggregation of clay platelets (that were
exfoliated during in situ polymerisation) during melt processing of CPNC has
been reported.
As the listed pathways indicate, either a single one- or a two-step sequential
intercalation-cum-compatibilisation may be required. Thus, the pathways focus
on the chemical aspects of intercalation. Unspecified in these are the contributions
of physics: the thermodynamics that controls the phase behaviour as well as P
and T effects on the interlayer spacing, molecular diffusion, flow which introduces
dispersive forces, radiation-absorption which may accelerate the exfoliation
process under the influence of, e.g., ultrasonics, etc.
Pathway 1 has been presented in sufficient detail in Section 2.3.5.2, hence
there is no need to discuss it again. Pathway 2a is pertinent to virtually any
polymeric nanocomposite, with thermoplastic, thermoset or elastomeric matrix
hence a brief description of these systems will be given. Finally, pathways 2b and
3 belong to the most important mechanical exfoliation methods and need more
detailed analysis.
203
Clay-Containing Polymeric Nanocomposites
204
Exfoliation of Clays
where hclay is the platelet thickness, ρclay and ρpolymer are densities, and wlocal is the
local clay concentration (in wt%), a 0 and a 1 are corresponding equation
parameters.
Owing to the tendency of the clay platelets to align parallel to each other in
local stacks, the clay concentration within the stack is not known, hence the
parameters in Equation 25 cannot be calculated from first principles. However,
since it can be assumed that the concentration within stacks is proportional to the
average, global concentration: wlocal ∝ w (wt%), d 001 should be inversely
proportional to the clay content. Thus, for organoclays with large aspect ratio
the formation of local stacks takes place at low concentration, and the interlayer
spacing may be small, not because of a lack of exfoliation, but due to the crowding
effects. It is worth noting that at φ > φmax the interlayer thickness is independent
of the aspect ratio – p only dictates the concentration at which the local stacking
starts.
Okada and Usuki [1995] published data on the interlayer spacing in PA-6/clay,
measured by XRD and TEM. Using Equation 25 the maximum packing for free
platelet rotation is predicted for organoclay content below 1.13 wt%. From the
relation, at a clay content of 2 wt% the interlayer spacing d001 is 44.2 nm (see
Figure 44). Evidently, starting with ω-aminoacid end-tethered CPNC were
produced.
Emulsion polymerisation was used to prepare CPNCs with PMMA as a matrix
[Choo and Jang, 1996]. Thus, MMA was polymerised in the presence of Na-
205
Clay-Containing Polymeric Nanocomposites
206
Exfoliation of Clays
207
Clay-Containing Polymeric Nanocomposites
208
Exfoliation of Clays
209
Clay-Containing Polymeric Nanocomposites
2.4.2.4 Co-Vulcanisation
Toyota was the first to develop a process for producing polyolefin (PO)-based
CPNC [Usuki et al., 1989]. However, the patent claims extend to ‘vinyl-based
polymeric compound, a thermosetting resin and a rubber’. Ammonium salt having
a terminal vinyl group was used to intercalate MMT. The product was mixed
with a vinyl-based monomer and/or oligomer, e.g., ethylene, propylene, butadiene,
methylmethacrylate, styrene, etc. The mixture could be polymerised either in
bulk, suspension or in solution reaction, by a radical, cationic, anionic,
coordination or condensation mechanism. Polymerisation took place within the
interlayer space, expanding the interlayer distance to d001 > 3.0 nm.
However, to prepare exfoliated CPNC with a rubber, first MMT was reacted
with low molecular weight liquid rubber. For example, in an aqueous solution of
DMSO a liquid acrylic rubber (amino-terminated butadiene-acrylonitrile rubber
(ATBN), MW = 3400, 16.5% AN), HCl, and Na-MMT (clay platelet thickness
= 1.0 nm, p = 1000, CEC = 1.19 meq/g) were dispersed. The reaction product
was filtered and dried. Pulse NMR indicated that a strong bond was formed
between MMT and ATBN, with ca. 20% of the rubber molecules restricted near
the interface. XRD indicated that the (001) peak of MMT had disappeared,
d001 > 8.8 nm, and the MMT platelets were uniformly dispersed in the matrix.
Next, the complex (containing 32.5 wt% of MMT) was cooled with liquid N2,
crushed by a hammer mill and mixed with NBR (AN = 33%). The blends
(containing 5 or 10 wt% MMT) were vulcanised with sulfur. Superior
performance in tensile, dynamic viscoelastic, and swelling tests were observed.
A similar method has been used to prepare ATBN-intercalated MMT,
subsequently mixed with NBR and vulcanised [Kojima et al., 1993a]. TEM of
the resulting CPNC showed intercalated, well-dispersed short stacks of MMT
dispersed in the matrix. The permeability reduction for H2 and H2O through the
CPNC (containing 3.6 wt% of MMT) when compared to a standard rubber
with 10 vol% of carbon black was reduced by 37 and 26%, respectively.
210
Exfoliation of Clays
The intercalated clay was than dispersed in dimethyl formamide (DMF) and the
LC was added. The solvent was slowly evaporated at 50 °C under vacuum, while
stirring. When the clay had good affinity for LC, the system was homogeneously
dispersed. The CPNC exhibited a bi-stable and reversible electrooptical effect
between a light scattering state and transparent state, which could be selected by
changing the frequency and voltage of the applied electric field.
In 1999 Yang et al., further examined the common solvent method for the
preparation of CPNC with PI as matrix. The work focused on the influence of
the intercalation agents upon dispersability of organoclay in a selected solvent
(DMAc) as well as that in PI. First, Na-MMT was intercalated with either amino
acids, primary aliphatic amines or quaternary ammonium salt, viz.: (1)
p-aminobenzoic acid (ArNCO), (2) ethanolamine (HONH), (3) N,N-dimethyl
aminoethyl methacrylate (DMAEM), (4) dodecylamine (12CNH), (5) 1-hexadecyl
amine (16CNH), (6) hexadecyl-trimethyl amine (3MHDA) and (7)
6-aminohexanoic acid (6NCO). The interlayer spacing of the organoclays
increased from d001 = 1.26 nm (Na-MMT) to, respectively, 1.27, 1.29, 2.16,
2.87, 3.70, 4.05, and 4.96 nm. However, the dispersability did not follow the
same order – the best dispersability in DMAc and PI was observed for the
intercalants 1, 2, 5 and 7, the worst for 3 and 6. Evidently, the dispersability
depends on the type of functional groups present in the solvent or PI and the
bulky group of the intercalation agent. Thus, one can disperse clay aggregates
(or tactoids) well without exfoliation, but the CPNC properties depend on the
homogeneous dispersion of MMT platelets.
The organosoluble PI was based on pyromellitic dianhydride (PMDA) and
4,4´-diamino-3,3´-dimethyl-diphenyl methane (MMDA). The organoclay was
added to DMAc and agitated for 3 h at 90 °C before adding it to MMDA solution
in DMA, which was followed by addition of PMDA. The mixture reacted at
room temperature for 6 h then it was cast on a glass and heated at 100 °C for
6 h, 150 °C for 4 h and 270 °C for 2 h under N2 to obtain MMT/PI hybrids.
The properties of the final product greatly depended on the degree of
dispersion. Only when the MMT was well dispersed did the CPNC show good
performance, e.g., simultaneous high strength and toughness, improved thermal
stability, decreased thermal expansion coefficient, retention of the solubility of
the polyimide matrix and high optical transparency. The chemical structure of
an intercalation agent imposes great influence on the dispersion of MMT. MMT
modified with 1-hexadecyl amine (HDA) showed the best dispersion behaviour
and the best set of properties.
Tyan et al. [1999a,b] observed that imidisation of polyamic acid (PAmA) is
accelerated by the presence of organoclay. The organoclay was prepared by
intercalating Na-MMT (CEC = 0.764 meq/g) with p-phenylene diamine. During
the intercalation only one amine group was converted into a cation (–NH3+).
The other -NH2 group was able to react with the dianhydride end group of
PAA when these molecules diffused into interlayer galleries. PAA was synthesised
by dissolving 4,4´-oxydianiline (ODAn) and pyromellitic dianhydride (PMDA),
in DMAc at 25 °C under N2. To a viscous PAmA solution a suspension of
organoclay in DMAc was added then mixed to obtain PAA/organoclay/DMAc.
During the reaction, the intercalant became an integral part of the PI molecules,
making these nanocomposite more thermally stable and mechanically stronger.
The spin-coated films containing 0, 2, 5 or 7 phr of organoclay were dried then
heated at 150, 200, 230 and 250 °C. XRD indicated that the interlayer spacing
211
Clay-Containing Polymeric Nanocomposites
of organoclay was d001 = 1.549 nm, but all PAA/organoclay systems were
exfoliated. In the presence of organoclay the imidisation temperature and the
imidisation time were reduced. For example, the imidisation temperature was
reduced from 300 to 250 °C, while at 250 °C the reaction time was reduced to
15 min (for 7 phr of organoclay). Initially, the reaction followed the first-order
kinetics:
ln(1-p) = -kt (26)
where p is the extent of reaction at a reaction temperature T, k is the rate constant
and t is the reaction time. The temperature effects were well-described by the
Arrhenius dependence:
k = A exp{-Ea/RT} (27)
where A is the pre-exponential factor, R is the gas constant, and Ea is the activation
energy (see Figure 46).
In the next paper 4,4´-oxydianiline (ODAn) was used as an intercalant [Tyan
et al., 2000]. After drying in a vacuum oven at 80 °C TGA indicated the presence
of 5.41 wt% structural water and 29.0% of the intercalant. The interlayer
spacing of the organoclay was d001 = 1.5 nm. PAmA was prepared by dissolving
ODAn in DMAc under N2 then adding 3,3´-4,4´-benzophenone tetracarboxylic
dianhydride (BTDA). The system was stirred for 1 h, which produced a viscous
PAmA solution to which different quantities of organoclay suspension in DMAc
were added (to yield 0, 1, 2, 3, 5, and 7 wt% of organoclay in the product),
and then mixed for 12 h. The organoclay-PAmA suspension was cast, and then
solvent was removed under vacuum at 30 °C over 48 h. Imidisation was carried
out in an air circulation oven at 100, 150, 200, and 300 °C for 1 h and then at
400 °C for 5 min. In the final product full exfoliation was obtained. The
Figure 46 Arrhenius plot of the imidisation rate constant for 0, 2, 5 and 7 phr of
organoclay in the CPNC. Parameters of the Arrhenius equation are listed. Data
[Tyan et al., 1999a,b].
212
Exfoliation of Clays
modulus, the maximum stress and the elongation at break of these CPNCs are
increased with organoclay content – see Figure 47.
CPNC with PI as a matrix has also been produced starting with MMT
(CEC = 1.15 meq/g) intercalated with N-hexadecane pyridinium chloride (HP-MMT)
[Gu and Chang, 2001]. PAA was prepared in a THF/MeOH solution, dissolving
in it at room temperature first ODAn then pyromellitic dianhydride (PMDA)
and mixing the resulting solution for 3 h. Then a solution of triethylamine (Et3A)
was added and the process took another 3 h of stirring to complete. Next, to a
stirred viscous pale-yellow solution a suspension of HP-MMT was added at 30 °C.
After 6 h of stirring, the solution was coated on a glass plate to a thickness of
250 μm. The film was dried at 25 °C for 30 min, 40 °C for 30 min, and 80 °C for
2 h, and then cured at 150, 200, and 300 °C under N2 to produce a transparent
PI-based CPNC film with a thickness of 26 ± 2 μm. Results showed that the
organoclay was fully exfoliated in the polymer matrix, had high modulus
(2.38 GPa), tensile strength (110 MPa), elongation at break (11%), and low
coefficient of thermal expansion (35%, compared to 100% for neat PI).
In the next paper from the group, the same HP-MMT was used to prepare
CPNC with PI as a matrix using two methods [Gu et al., 2001]:
1. Blending a DMAc solution of ODAn with the organoclay dispersion in DMAc
before adding PMDA; and
2. Blending a DMAc solution of PAmA with the organoclay dispersion in DMAc.
Compositions containing 1, 3, 5 and 10 wt% of organoclay were prepared – the
interlayer spacing was: d001 = 2.2 to 1.4 nm, respectively. Tensile, thermal, dielectric
and water absorption properties of these CPNCs were studied. The properties
depended on the clay type, clay concentration, and the method of preparation.
The best performance was obtained using 3 wt% HP-MMT prepared by the
213
Clay-Containing Polymeric Nanocomposites
second method: tensile strength = 110 MPa, tensile modulus = 2.35 GPa,
elongation at break = 14.5%.
Delozier et al. [2002] used several methods to prepare PI-based CPNC, with
MMT that was intercalated with a long chain aliphatic quaternary ammonium
cation. The methods included:
1. Mixing the organoclay into a high molecular weight poly(amide acid) solution;
2. Mixing as in (1), followed by sonication; and
3. In situ preparation, starting with dispersion of organoclay in N-methyl-2-
pyrrolidinone (NMP), then addition of 4,4´-oxydianiline (ODAn) and
3,3´,4,4´-benzophenone tetracarboxylic dianhydride (BTDA) to prepare high
molecular weight poly(amide acid). The imidisation step involved a high-
temperature treatment (i.e., 1 h each at 100, 200 and 300 °C in air or N2).
The best results were obtained using the latter approach - the specimen obtained
using the other methods had aggregated clay particles that caused film failure in
tensile tests (stress concentration). However, high shear mixing using a
homogeniser improved intercalation and exfoliation, but the films were extremely
brittle making mechanical properties impossible to measure.
The CPNCs that contained 3-8 wt% of organoclay, were characterised by DSC,
TGA, TEM, XRD and thin film tensile properties. After thermal treatment of amide
acid films that caused imidisation, the films with clay were darker than those without
and the interlayer spacing was reduced. During imidisation at T = 200 to 300 °C
thermal degradation of the quaternary ammonium took place. The effect was less
pronounced when imidisation was carried out under N2. The degree of dispersion
was assessed from TEM micrographs. There is evidence that in the in situ prepared
CPNC exfoliation dominates. The exfoliated particles were 200¯700 nm long and
1¯10 nm thick. However, XRD analysis indicated that the interlayer spacing was
about constant, d001 = 1.34 nm - the peak intensity increased with clay content. It
is noteworthy that this spacing is closer to that known for Na-MMT than for the
organoclay (d001 = 2.37 nm). The polyimide/organoclay hybrid films exhibited
higher room temperature tensile moduli, but lower strength and elongation to
break than the control films. The Tg for the neat ODAn¯BTDA system was 283 °C
and remained constant within 4 °C for the hybrid films. At 5 to 8 wt% of clay the
temperature for 5% weight loss was ca. 517 °C.
Chang et al. [2001b,c] studied the preparation of CPNC in polybenzoxazole
(PBO) matrix. The common solvent method was chosen with DMAc as the solvent.
MMT (CEC = 1.19 meq/g) was intercalated with primary hexadecyl ammonium
salt (MMT-HDA). Polyamic acid (PAmA) was synthesised in DMAc, then the
suspension of MMT-HDA in DMAc was added. The solution was cast, solvent
was evaporated at 50 °C and the films, 10-15 μm thick, were thermally treated.
The conversion to PI was carried out at 300 °C for 1 h under N2. The final conversion
to PBO was accomplished at 550 °C. CPNCs with 0, 1, 2, 4 and 8 wt% of organoclay
were prepared. Good exfoliation in systems containing up to 4 wt% MMT-HDA
was found, although short stacks were visible in TEM micrographs. The specimens
were thermally stable up to 611 °C, retaining about 75% of weight at 900 °C
– clay presence hardly affected these properties. However, the tensile strength was
doubled for 4 wt% loading and modulus increased by 37%.
A one-step method for the solution preparation of PI nanocomposites was
also proposed [Huang et al., 2001a,b]. First, MMT was intercalated with primary
(dodecyl or hexadecyl, DDA or HDA, respectively) or quaternary (trimethyl
214
Exfoliation of Clays
215
Clay-Containing Polymeric Nanocomposites
clay loading of 3 wt%. XRD showed the presence of a peak for all specimen with
corresponding values of d001 = 1.20 to 1.31 nm, with the largest value for CEC
≅ 0.7 meq/g. However, TEM showed a random dispersion of individual clay platelets
and short stacks. Using these selected clays, the second series of specimens was
prepared with clay loading of up to 8 wt%. A small enhancement of the tensile
modulus was accompanied by reduction of strength and elongation at break. TGA
showed a significant increase of thermal stability.
Better dispersion was obtained by dispersing MMT-DDA in a NPM solution of
photosensitive polyamic acid (PAA) [Hsu et al., 2003]. The latter was prepared by
polymerising pyromellitic dianhydride, oxydiphthalic anhydride, and oxydianiline.
The photosensitive formulations contained 2,3,4-tris(1-oxo-2-diazonaphthoquinone-
5-sulfonyloxy)-benzophenone as the photosensitiser and 3 wt% organoclay. The
films were transparent and tough. XRD and TEM indicated exfoliation before
and after thermal imidization. The thermal expansion coefficient was 23% lower
than that of film that did not contain the organoclay. The tensile modulus increased
by 14%, while the strength and elongation at break decreased by 15 and 33%,
respectively.
An intrinsically photosensitive PI/MMT system was prepared by solution
polymerisation at 180 °C of 4,40-diamino-3,30-dimethyldiphenylmethane
(MMDA) with benzophenone-3,30,4,40-tetracarboxylic dianhydride (BTDA) and
isoquinoline in the presence of MMT-HDA [Liang et al., 2004]. The solution
was either cast or spin coated, devolatilised and imidized at T ≤ 280 °C. XRD
and TEM indicated exfoliation in the full range of MMT concentrations. Excellent
mechanical properties were obtained – in the full range of MMT content (0 to
3 wt%) the modulus, tensile strength and elongation at break increased by 211,
48 and 11%, respectively. At the same time the thermal expansion coefficient
was reduced by up to ca. 32%, and Tg increased by 6 °C. While the addition of
organoclay did not affect the inherent PI solubility, the presence of MMT
significantly reduced the rate of solvent absorption. Finally, the photolithographic
properties of PI remained unaffected by the clay presence, but only for
concentrations up to 2 wt%.
Polybenzoxazines are thermoset phenolic resins developed to overcome the
shortcomings of the novolacs and resoles. They show excellent properties, viz.
heat resistance, good electrical properties, flame retardance, dimensional stability,
toughness, stable dielectric constant, and low moisture absorption - all these at
relatively low cost. They can be synthesised from inexpensive raw materials,
cured without strong acid or base catalyst, and do not release by-products during
polymerisation, thus they are attractive candidates for many applications [Riess
et al., 1985].
Agag and Takeichi [2000] prepared CPNC of polybenzoxazine (PBOa) by
first intercalating Na-MMT with octyl (OA), dodecyl (DDA) or stearyl (ODA)
ammonium chloride, then mechanically mixing with different amounts of a
PBOa precursor, bifunctional bis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl)
isopropane (B-a). The ring opening polymerisation of pristine B-a started at
223 °C, while in the presence of organoclay at T = 177 to 190 °C. According to
XRD, the MMT intercalated with either DDA or ODA became totally exfoliated
in the product. Viscoelastic measurements showed that the Tgs of the CPNCs
were higher than that of neat PBOa. Increased storage modulus, decomposition
temperatures and thermal stability were also noted. However, as the authors
216
Exfoliation of Clays
remarked, the method was difficult because of the high viscosity of the monomer
and the small difference between its gelation temperature and the melting point.
More recently, several types of CPNCs with PBOa as a matrix have been
prepared [Takeichi et al., 2002]. The authors described the effects of the
preparation method and that of type and content of organoclay on the CPNC
properties. Two monomers were used: B-a and monofunctional 3-phenyl-3,
4-dihydro-2H-1,3-benzoxazine (P-a). These produced crosslinked PB-a and linear
PP-a matrix, respectively. Na-MMT (CEC = 1.19 meq/g) was intercalated with
ammonium salts of such amines as tyramine, 2-phenyl-ethyl amine, aminolauric
acid, and DDA.
The nanocomposites were prepared either by melt or solution method. The
melt method involved incorporating organoclay into B-a or P-a above its melting
point (Tm = 100 and 60 °C, respectively). The solution method involved dispersing
the organoclay in a solvent NMP or tetrahydrofuran (THF) at 80 °C for 1¯2 h
and then blending with either B-a or P-a at 80 °C for 3 h. The blends were cast
on glass plate, dried at 60 °C for 16 h, then cured at 100, 150, 200 and 240 °C
for 1 h each. Good dispersion was obtained in NMP, but poor in THF. The
CPNCs were transparent, red-wine coloured with thickness ranging from 0.2 to
0.4 mm.
The intercalation increased the interlayer spacing, from d001 = 1.24 nm of
Na-MMT only to ≤ 1.83 nm. Thus, it is remarkable that using either method a
high degree of exfoliation in the cured nanocomposites was obtained. Evidently,
changing the solvent, concentration and procedure affected the result, viz. when
THF was used, a small XRD peak remained indicating intercalated clay, but
when NMP was used total exfoliation was achieved. As before, increasing the
organoclay concentration reduced the level of platelet dispersion. The effect of
clay addition on P-a was much larger than on B-a. The smaller P-a molecules
penetrated into the clay galleries more easily and the number in contact with the
catalytic clay surface should be larger than with the bigger B-a molecules. The
melt method also resulted in exfoliated structures [Agag and Takeichi, 2000].
DSC showed that the incorporation of any type of organoclay lowered the
curing temperature. The effect was particularly large for a small amount of
organoclay - addition of 5 wt% reduced the onset curing temperature by ca.
50 °C, suggesting a catalytic effect of the organoclay on ring opening
polymerisation. A plot of Tg versus clay content showed a maximum at about
4 wt%, with all the CPNC values higher than that of neat resins. As evidenced
by TGA, an addition of organoclay improved the thermal stability – the best
results were obtained for MMT intercalated with tyramine (p-ethyl-amine phenol).
In summary, the work on PBOa-type CPNCs illustrates the importance of
miscibility and chemistry on the exfoliation process. Even when the organoclay
had small expansion of the interlamellar galleries (Δd001 ≤ 0.59 nm), but was well
dispersed in a solvent and/or monomer, good exfoliation was achieved after curing.
As in thermoplastic systems, here also the best results were obtained when the
matrix polymer was chemically bound to clay by reactive intercalant (tyramine).
High energy shearing may help, but it does not replace good thermodynamics
and chemistry of the system.
The common solvent method has also been used to prepare POSS-type
nanocomposites in PI matrix [Tsai and Whang, 2001a]. The polyimide/
polysilsesquioxane-like (PI/PSSQ-like) films had 3D structure with linear PI blocks
217
Clay-Containing Polymeric Nanocomposites
and a crosslinked PSSQ-like structure. The system showed higher thermal stability
and char yields than pure PI from 4,4´-diamino-diphenyl ether and
3,3´-oxydiphthalic anhydride (ODPA). In a series of X-PIS films (PI modified
with p-amino-phenyl tri-methoxysilane (APTS), where X is the molecular weight
of each PI block), decreasing the PI block length enhanced the storage modulus,
tensile modulus, and Tg but reduced the α-relaxation damping peak intensity,
density and elongation. The change in the moduli and Tg may be caused by an
increase in the crosslinking density and rigidity of the network. The changes in
the peak intensity and density may be caused by increased free volume or the PI
interblock separation and decreases in the interblock PI chain interaction. The
decrease in elongation is related to increased rigidity. The activation energy of
the α-transition depended on the length of the PI block. A maximum value was
reached for the chain length of 10 kg/mol because of two opposing factors:
crosslinking density and free volume.
In a series of X-PIS-y-PTS (X-PIS modified with phenyl trimethoxysilane (PTS),
where y is the weight-ratio percentage of PTS to APTS-polyamic acid) films with
a constant PI block length, the storage modulus, tensile modulus, Tg, density,
and α-relaxation damping peak intensity decrease with the PTS content. This
could be because of the increase of the PSSQ-like domain size with the PTS content,
which leads to the introduction of more free volume or interblock separation
and to a decrease in the interblock chain interaction force.
218
Exfoliation of Clays
for magadiite intercalated with either the primary or secondary onium ions (n = 0 or
1). In the case of higher amines (n = 2 or 3) XRD indicated an interlayer spacing of
d001 = 7.82 and 4.10 nm, respectively. The observed strong effects of the intercalant
structure was interpreted as due to the high acidity of ODA, which is reduced by the
presence of methyl groups, especially when n = 2 or 3. The acidity is responsible for
the intercalant’s catalytic effects on the curing reaction within the interlamellar galleries,
which lead to exfoliation. Good enhancement of the tensile strength was reported.
The enhancement was shown to depend on the degree of exfoliation, e.g., at 10 wt%
of clay the tensile strength increased by a factor of 4.8, 3.5, and 2.3 for the exfoliated,
ordered exfoliated and intercalated systems, respectively (n = 1-3). The transparency
and high barrier properties makes these CPNCs attractive as packaging materials
and protective films.
The early work resulted in several patents [Pinnavaia and Lan, 1998a,b]. The
authors observed that the extent of epoxy resin diffusion into the interlamellar
galleries depends on the hydrophobicity controlled by the chain length of the
alkylammonium cations. Thus, to start with Na-MMT was cation exchanged
with alkylammonium cations with different alkyl chain length (CnH2n+1, where
n = 4, 8, 10, 12, 16 or 18). Equivalent amounts of the epoxy resin (Epon 828
27.5 wt %) and the polyether-amine (72.5 wt %) were mixed at 75 °C for 30 min,
then 10 wt% of the organoclay was added, mixed and cured. The XRD results
indicated that the clays with alkyl chain length n ≥ 10 were exfoliated. The
mechanical performance was significantly enhanced by exfoliation.
In later patents [Pinnavaia and Lan, 1998c; 2000a,b], Na-MMT was treated
with HCl to prepare protonated clay, H-MMT (d001 = 1.05 nm). Next, polyether-
amine was added to the aqueous suspension and stirred at room temperature for
6 h (d001 = 4.6 nm). After evaporation of the suspending medium the gel of
intercalated clay was mixed with Epon 828. The XRD pattern showed absence
of the clay diffraction peaks, suggesting exfoliation. The tensile strength and
modulus were superior in comparison to CPNC prepared with alkylammonium
cation intercalated clay (see Figure 49). However, it is worth stressing that the
presence of ≥ 5 wt% MMT reduced the heat of reaction [Butzloff et al., 2001].
Exfoliation was observed only at a MMT concentration below 2.5 wt% – above
this limit the system was progressively less exfoliated and more intercalated.
Intercalated CPNCs in glassy epoxy resin were obtained by dispersing
Nanomer I.28E (MMT-3MODA) into Epon 825 at 65 °C, degassing and curing
with a stoichiometric amount of Jeffamine D400 at 65 °C for 15 min [Zerda and
Lesser, 2001]. The XRD data indicated that the interlayer spacing of organoclay,
d001 = 2.28 nm, increased during pre-swelling in Epon to 3.42 nm, then shrank
during curing to 3.21 nm. The tensile modulus increased from 2.8 GPa for neat
resin to 3.2 GPa at 12.5 wt% of clay. However, the tensile stress was reduced
from 70 to 46 MPa. For the middle range of organoclay concentration (2.5 to 10
wt%) the fracture energy nearly doubled. The results are understandable
considering the presence of large scale (10-30 μm) aggregates, evident in SEM
micrographs. The measured fracture energy release rate (G1C) was shown to
depend on the generated surface area, as measured by AFM.
Lü et al. [2001] studied the dispersability of MMT intercalated with either
CH3(CH2)17NH3+- (ODA) or CH3(CH2)17N(CH3)3+ (3MODA) in epoxy resin,
which was a reaction product of the diglycidyl ether of bisphenol-A (DGEBA;
MW = 380 g/mol) with p,p´diaminodiphenylmethane (DDM) or methyl-
tetrahydrophthalic anhydride (MeTHPA). The CPNC was prepared in two steps:
219
Clay-Containing Polymeric Nanocomposites
220
Exfoliation of Clays
was d001 = 2.3 nm, increasing upon dispersion in Epon to 3.9 nm. Addition of the
curing agent and heating for 2 h at 80 °C did not change the latter spacing.
Heating the mixture at 135 °C for additional time caused progressive expansion
of the interlamellar space toward exfoliation: d001 ≥ 20 nm. The latter spacing
was observed for less than an equimolar amount of the curing agent and clay
concentration up to 5 wt% (for 20 wt% clay d001 = 8.3 nm). When Epon was
cured with more than equimolar MPDA, exfoliation was suppressed – high curing
agent concentrations seem to favour extragallery crosslinking. Exfoliation was
obtained for the amount of curing agent ranging from zero to less than its
stoichiometric amount. The time-dependent SAXS measurements indicated that
exfoliation proceeded by progressive delamination of the stacks.
While most authors prepare CPNC with epoxy (DGEBA cured with acid
anhydride) matrix using either MMT-ODA or MMT-3MODA, recently MMT
pre-intercalated with an ‘alkyl ammonium salt with hydroxyethyl groups’ was
used [Zhang et al., 2004]. According to TEM, at 3 wt% of organoclay loading
only intercalated stacks with d001 ≅ 5.5 nm were obtained. However, in spite of a
lack of exfoliation, excellent performance was obtained: impact strength increased
by around 85%, tensile strength by 22%, storage tensile modulus (at T < Tg) by
33% and Tg increased by ca. 14 °C.
A new approach to clay exfoliation in epoxy matrix involves the use of
aromatic amine hardener as the clay intercalant, dispersing such organoclay in
epoxy, and then curing the system [Ma et al., 2004]. For example, m-xylylene-
diamine (m-C6H4(CH2-NH2)2 or MXD for short) was acidified and used to
pre-intercalate Na-MMT. The epoxy (DGEBA) was added to the desired quantity
of purified organoclay suspension, and after stirring the mixture was dried. Finally,
CPNC was obtained by curing the mixture with a stoichiometric amount of
4-aminophenyl sulfone (DDS). Within 2θ = 1 to 9o XRD did not show any peak
that may have indicated exfoliation. However, TEM showed the presence of
randomly dispersed, ca. 3 nm thick clay platelets, possibly bridged by acidified
MXD. The authors speculated that the disorderly exfoliated structure originated
from the large crosslinked epoxy molecules connected to the clay platelet via the
MXD hardener-intercalant. No information on performance of this CPNC was
given.
Kornmann et al. [2001] studied the effect of the cation-exchange capacities
(CEC) on the formation of CPNC in epoxy matrix. Two MMTs with CEC = 0.94
and 1.4 meq/g (MMT09 and MMT14, respectively) were intercalated with ODA.
Epon 828 and a polyoxyalkylene diamine curing agent (Jeffamine D-230) were
used. First, the epoxy was mixed with the desired amount of organoclay at 75 °C
for several hours, and then a stoichiometric amount of Jeffamine was added. The
mixture was outgassed under vacuum, poured into a mould, then cured for 3 h at
75 °C and post-cured for 12 h at 110 °C. The dispersion was studied using XRD,
SEM and TEM. The interlamellar spacing of the two clays increased from
d001 = 0.97 for MMT09 to 1.72 nm for organophilic MMT09-ODA, and from
d001 = 1.21 for MMT14 to 2.14 nm for the MMT14-ODA. Surprisingly, swelling
the former organoclay in Epon resulted in exfoliation (d001 > 8.8 nm), whereas the
latter slowly intercalated to reach d001 = 3.47 nm after 24 h. The high surface
energy of MMT is known to attract polar species such as epoxy molecules hence
they diffuse into the interlamellar galleries. If these are able to polymerise, the next
molecules are able to diffuse into the interlamellar galleries causing exfoliation,
hence self-polymerisation of epoxy in MMT09-ODA may be postulated. Within
221
Clay-Containing Polymeric Nanocomposites
222
Exfoliation of Clays
the interlamellar galleries, compressing them by Δd001 = 0.7 nm. Apparently, FH-
W75 is immiscible with some components of the epoxy matrix. At least part of
the reason for immiscibility is that only partial ion exchange took place during
intercalation. None of the nanocomposites produced contained fully exfoliated
clay. TEM confirmed the interlayer spacing deduced from the XRD data – indeed,
the largest average spacing was observed for FH-RDI, but some nonintercalated
platelets were also visible. The SEM micrographs also indicated the presence of
clay aggregates, particularly bad (some as large as 20 to 30 μm) for FH-W75 and
FH-ODA. This is an important observation! Without the evidence of SEM one
would concentrate the interpretation of data on the nanometre-scale morphology,
whereas for a number of performance characteristics (for example the impact
properties) the micron-scale aggregates may be more important.
The tensile properties of the nanocomposites were examined. The clay
concentration effect on the tensile modulus is shown in Figure 50. The results for
FH-W75 are clearly the worst, falling even below the microcomposites with
nonintercalated FH. Of the remaining three systems, the best is the one with FH-
RDI and the worst with FH-ODA – here at last the expected correlation with the
degree of platelet dispersion is observed. The fracture energy for all the intercalated
systems was found to be higher than that for the microcomposite with FH, but
again the data for FH-W75 were the lowest and these of FH-RDI the highest. At
5 vol% clay loading the fracture energy was nearly twice as large as that for the
neat matrix resin.
Epoxy resins are inherently brittle and several methods have been used to
improve toughness without loss of stiffness. Since CPNC with an epoxy matrix
frequently show improved modulus and reduced ductility, a growing number of
publications have appeared, trying to solve this problem. Thus, for example,
Ratna et al., 2003 used a combination of linear (DGEBA) and 11-arm star
branched epoxy to prepare CPNC with 5 wt% of MMT-ODA. A high degree of
intercalation was obtained. In spite of the phase separation between the two
epoxies, good performance was reported, viz. enhancement (in comparison to
223
Clay-Containing Polymeric Nanocomposites
224
Exfoliation of Clays
2.4.2.7.2 Silica
A series of PU nanocomposites was prepared with 0-50 wt% of silica, having a
particle size of about 12 nm [Havni and Petrovic, 1998]. SEM showed regular
distribution and small spacing between neighbouring particles at all
concentrations. For all samples XRD showed a single broad maximum at about
6° and a shoulder at 20°. The Tg of PU increased with the silica concentration. A
parallel series of PU filled with micron size silica had higher density, hardness
and modulus than nanosilica filled systems, but the tensile strength and elongation
at break were dramatically better for the latter systems. Composites with nanosilica
were clear and transparent while those with micron size silica were opaque.
Petroviç et al. [2000] prepared PU nanocomposites by dispersing amorphous
SiO2 particles (average diameter 12 nm) in MEK. Next, PPG was added, MEK
was removed, MDI added and the system was cured at 100 °C for 16 h. The final
concentration of SiO2 was up to 50 wt%. Properties of these nanocomposites
were compared to those of microcomposites containing crystalline SiO2 with an
average particle diameter of 1.4 μm. The nanocomposites showed 3-fold higher
tensile strength and elongation at break, but lower modulus and hardness.
The sol-gel process has also been used to generate nanosized silica particles
within a PU matrix [Goda and Frank, 1997]. At lower concentration the silica
penetrated the hard segment domains of PU, at higher it disrupted its ordered
structure.
2.4.2.7.4 Organoclays
Several already cited broad patents on CPNCs have stated that the invented
technology is also applicable to PU [Usuki et al., 1989; Nichols and Chou, 1999,
Beall et al., 1996a; 1999b]. One of these general patents was granted to Pinnavaia
and Lan [2000a,b]. However, the cited examples are only for epoxy-based CPNC.
The patent information will be discussed later on in this book.
PUs are prepared by the reaction of isocyanate and polyols:
HO-R-OH + OCN-R´-NCO → -(-CO-NH-R´-NH-CO-O-R-O-)n-
The polyol component -R- usually contains a base, such as a secondary or tertiary
amine. Therefore, these may react with the protons within the clay interlamellar
gallery enhancing the intercalation.
225
Clay-Containing Polymeric Nanocomposites
d001 (nm)
Notes:
a
Glycerol propoxylate (Voranol from Dow);
b
Molecular weight of polyols;
c
Calculated basal spacing for a vertical orientation of the onium paraffin tails
226
Exfoliation of Clays
227
Clay-Containing Polymeric Nanocomposites
Figure 52 Tensile (ASTM D412) and lap-joint strength (ASTM D1002) test data
for PU containing dispersed PCL-based CPNC. Data [Chen et al., 1999b].
228
Exfoliation of Clays
ADA and MMT-BZD, respectively [Chen et al., 2000]. The intercalated clay was
washed, dried under vacuum at 80 °C for 12 h, then ground and screened through
a 325-mesh sieve. In a parallel operation, MDI and polytetramethylene glycol
(PTMG) at a molar ratio of 2:1 were dissolved in DMF and heated to 90 °C for 2.5
h to form a prepolymer. To the prepolymer 1,4-butanediol was added with rapid
mixing at 90 °C for 10 min. Next, an appropriate amount of organoclay (to give 1,
3 or 5 wt% of organoclay in CPNC) was dispersed in 10 ml of DMF, added to the
prepolymer mixture and the reaction was allowed to proceed to completion in 3 h
at room temperature under mixing. The final concentration of PU in DMF was 30
wt%. After removing DMF at 80 °C and degassing the mixture an elastic film was
obtained.
XRD of MMT-ADA and MMT-BZD gave d001 = 1.7 and 1.54 nm, respectively.
The difference was attributed to the size of the intercalant molecule. The PU-based
PNCs prepared with 1, 3 and 5 wt% MMT-ADA, as well as with 1 and 3 wt%
MMT-BZD were all exfoliated. This conclusion was supported by TEM
micrographs – randomly placed, about 1 nm thick layers of organoclay were
observed. However, the PNC with 5 wt% MMT-BZD had a broad peak of
d001 = 2.47 nm indicating intercalation.
The molecular weight of PU in neat resin and in CPNC prepared in the presence
of MMT-ADA or MMT-BZD was Mn ≅ 11 kg/mol. Similarly, for all seven samples
the glass transition temperature was -58 ≤ Tg ≤ -59 °C. Also, as expected, the
water absorption was found to vary from 1.3 to 1.7 wt%. Surprisingly, TGA
analysis of PU-based CPNC containing MMT-ADA showed that it started to
degrade faster than neat PU. This may be due to the presence of extra ADA
unattached either to clay or to PU. However, at higher temperatures (T > 350 °C)
the PU/clay nanocomposite displayed higher thermal resistance than that of PU.
The stability of the MMT-BZD/PU system was better than that with MMT-ADA.
229
Clay-Containing Polymeric Nanocomposites
The mechanical properties of the PU-based PNC are shown in Figure 54. Addition
of MMT-ADA only slightly improved the tensile strength and elongation at break
over that of neat PU. However, the effect of MMT-BZD was quite significant –
improvement of the tensile strength by a factor of 2.0 and the elongation at break by
a factor of 2.8. The large contrast between the effects of MMT-ADA and MMT-
BZD was explained by the interactions between the intercalant, clay and PU matrix.
ADA has one terminal -NH2 group that might form a complex with Na-MMT and
still be able to react with a -NCO to form urea. BZD had two terminal -NH2 groups
that can participate in these interactions/reactions. Therefore, ADA can form linear
chains while BZD a crosslinked one. Schematics of these interactions/reactions are
presented in Figure 55, which illustrates the molecular structure in PU-based PNC
formed in the presence of (a) MMT-ADA and (b) MMT-BZD.
Ma et al. [2001] prepared elastomeric PU based nanocomposite starting with
MMT (CEC = 0.9-1.0 meq/g, with particle size of about 40-70 μm) intercalated
with trimethyl hexadecyl-ammonium chloride (3MHDA). Three types of polyol
of different MW and functionalities were used: PPG1, and PPG2 having Mn =1
and 2 kg/mol, respectively, and glycerol propoxylate (GPO3, with Mn = 3 kg/
mol). Dry organoclay was dispersed in GPO3 for 2 h. The degassed dispersion
was mixed with the PU prepolymer, prepared by reacting PPG1 and PPG2 with
toluene diisocyanate (TDI) at 80 °C. The mixture was cured at 80-90 °C for 2 h.
CPNCs containing either PPG1 or PPG2 were also prepared. The XRD data
indicated that MMT was intercalated with the interlayer spacing d001 ≤ 4.6 nm.
The tensile strength and elongation at break reached maximum values at ca.
8 wt% clay. The maximum improvement of the tensile strength and elongation
at break was by a factor of 2 and 5, respectively (based on neat PU). TGA showed
that the temperature for the maximum thermal decomposition increased from Td
= 377 (PU) to 385 °C. The best properties were observed for CPNC comprising
GPO3. Nanocomposites prepared by first dispersing the organoclay in low MW
polyol had better mechanical properties than those prepared by dispersing
organoclay in high MW polyol.
In 2001 Hu et al., reported a similar degree of dispersion. The authors first
expanded the interlayer spacing of MMT-3MHDA in PEG and then added TDI
and caused polymerisation. The reported interlayer spacing was: for MMT
d001 = 1.26; for organoclay 1.96; and for CPNC with (10 wt% organoclay)
d001 ≤ 4.85 nm. In accord with these observations, only intercalation could be
expected in systems containing clay intercalated with quaternary ammonium ions.
An interesting strategy has been used by Yao et al. [2002]. Different
amounts of Na-MMT (from Nanocor) were mixed with modified polyether
polyol (MPP) at 50 °C for 72 h. The mixture was then blended with a known
amount of modified 4,4´-diphenylmethylate diisocyanate (M-MDI) and moulded,
curing it at 78 °C for 168 h. Thus, MPP was used as an intercalating agent that
expanded the interlamellar galleries from Δd001 = 0.14 to 0.64 nm – evidently,
only a moderate level of intercalation was achieved. It was observed that with an
increasing amount of clay the heat of reaction was reduced. The reduction was
ascribed to immobilisation of MPP that intercalated the clay, being strongly
bonded to the solid surface.
In spite of the low degree of dispersion, the CPNC showed significant improvement
of the tensile strength and strain at break, increasing with the amount of clay. At a clay
loading of 21.5 wt%, tensile strength increased by ca. 44% and the strain at break by
20%. The storage modulus at T < Tg of the soft segments increased by 350%.
230
Exfoliation of Clays
231
Clay-Containing Polymeric Nanocomposites
The thermal conductivity initially decreased with clay loading (by ca. 10% for
17% clay) then returned to the original level.
MMT is known to be hygroscopic and, as TGA experiments indicate, it may
contain a significant amount of adsorbed and chemically bound water [Ogawa
et al., 1992; Menéndez et al., 1993]. The -NCO groups readily react with water,
for example, and 1.0 g of water will consume 18.0 g of toluene-diisocyanate
(TDI). Cloisite® 10A (MMT-2MBHT) was de-watered by dispersing it in toluene
followed by azeotropic distillation for 6 h [Zhang et al., 2003]. Next, the
dehydrated organoclay was dispersed in PEG, reacted with TDI at 80 °C for 4 h,
and then cured at 90 °C for 15 h under vacuum – the clay concentration ranged
from 0 to 7 wt%. The authors reported that only about 4.1% of the organoclay
-OH groups were able to react with -NCO groups of TDI, hence grafting the PU
matrix directly to the clay surface. The reaction was detected by FTIR. XRD of
Cloisite® 10A and the CPNC gave d001 values of about 2.3 and 3.5 nm, respectively.
In spite of the lack of exfoliation the mechanical properties were found to be
greatly improved, viz. the dynamic tensile modulus, E, increased by a factor of
10, the tensile strength and the elongation at break by about 160%. These
improvements in the intercalated systems are clear evidence of the benefits of
direct matrix-filler bonding.
232
Exfoliation of Clays
characterised by XRD, TEM and TGA, were reported intercalated with d001 =
3.71 nm. Thus, the ordered organosilicate structure of clay was still present in
the CPNC, forming stacks that were ca. 50 nm thick and uniformly dispersed in
the silicone rubber matrix. The mechanical properties and thermal stability of
the hybrids were very close to those of aerosilica-filled silicone rubber. Melt
intercalation/exfoliation of hydrophilic polymers, such as P4VP, PEG or PVAl is
relatively easy. The strategies used have been described in Section 2.3.5.2.
More recently, Zanetti et al. [2000a,b] described the melt exfoliation of
fluorohectorite (fluoromica, FM) in a PVAc matrix. The melt-produced CPNCs
show a similar set of properties as those obtained by the reactive route, viz.
superior heat, chemical or ignition resistance, barrier to diffusion of gases and
polar liquids such as water, methanol, ethanol etc., yield strength, stiffness and
dimensional stability. These CPNCs may be useful in diverse applications viz. in
business equipment, computer housings, transport (automotive and aircraft, viz.
in under the hood and exterior body trim applications), electronic, packaging,
building and construction industry, etc.
However, this method is at an early stage of development with numerous
unanswered questions still remaining. A consensus emerges that the clay platelets,
e.g., individual lamellae of MMT, should be treated as any other structural plates,
with their own value of mechanical performance characteristics, e.g., modulus,
maximum strain at break, etc. There is TEM evidence that in shear the clay
platelets tend to bend. The work on FM showed extensive reduction of the aspect
ratio, but it is not known whether the phenomenon is general and which
mechanism controls the attrition.
233
Clay-Containing Polymeric Nanocomposites
Melt compounding was also used by Liu et al. [1999] to prepare PA-6/organoclay
PNC. First, Na-MMT was intercalated with octadecyl ammonium chloride
(ODA), which increased d001 from 0.98 to 1.55 nm. Next, PA-6 was dry blended
with ≤ 17 wt% of the organoclay, then melt-compounded in a TSE and injection
moulded. Melt blending increased the interlayer spacing to d001 = 3.68 nm and
reduced XRD peak intensity, indicating a partial exfoliation. Similar results were
claimed by the RTP Co. for melt compounded PA-6 [Dahman, 2000]. In the
latter study various organoclays were used at different concentrations. Melt
exfoliation was carried out in a TSE.
As described in Section 2.3.8.2.4, Dennis et al. [2000; 2001] reported that melt
blending of PA-6 with Cloisite® 30B (2M2EtOH) resulted in exfoliation, thus the
fundamental studies on the intercalation processes were conducted with PA-6/Cloisite®
15A (2M2HTA) as a model system. The work has shown that at least for this
organoclay/polymer system, intercalation depends solely on the residence time and
the residence time distribution inside the processing equipment.
The observed difference in the ability of Cloisite® 30B and Cloisite® 15A
organoclays from SCP to exfoliate demonstrated the importance of the chemical
treatment of the clay, which controls the clay/polymer interactions. As shown in
Table 16 the exfoliating Cloisite®-30B (methyl-tallow-bis-2-hydroxyethyl) differs
from the intercalating Cloisite® 15A (bis-methyl-bis-hydrogenated tallow) on three
accounts:
1. It contains one (non-hydrogenated) tallow group versus two hydrogenated
in C15A,
2. It contains two hydroxyethyl groups versus two methyl groups of C15A and
3. It has lower substitution of organic ions (0.9 for C30B versus 1.25 meq/g for
C15A).
In short, C30B has a lower density of the organic intercalant within the interlamellar
galleries than C15A and at the same time it has higher polarity, which originates
from two -OH groups and unsaturation of the tallow group. Thus, Cloisite® 30B
has stronger attraction for PA molecules causing them to diffuse into galleries, and
more space for them to do so.
In another publication from the same laboratory an experimental organoclay
SCPX-2004 was used [Cho et al., 2000; Cho and Paul, 2001]. This new organoclay
is a close cousin of Cloisite® 30B – in SCPX-2004 the tallow is replaced with
rapeseed, which contains ca. 95% of C22 alkyl chain with single unsaturation at
C13 (erucyl). In both cases the same Na-MMT was used with CEC = 0.91 meq/g.
SCPX-2004 has been successfully used for exfoliation via direct melt compounding
of PA-6 (Mn = 29.3 kg/mol) with 0-20 wt% of the organoclay, using either a TSE
or a SSE at 240 °C. The extruded pellets were injection moulded into standard
test mould. For the SCPX organoclay, XRD gave the interlayer spacing
d001 = 1.8 nm. CPNC (with 5 wt% clay) was prepared either in a TSE or a SSE;
the former process engendered full exfoliation, while the latter only a partial
exfoliation, but large domains of unaltered organoclay remained. TEM confirmed
these observations. The individual layers were found aligned along the flow axis.
The average clay platelet thickness and length were determined as approximately
3 and 120 nm, respectively. At a clay content of 3.16 wt% it produced a respectable
modulus (3.7 GPa versus 2.7 GPa for neat PA-6 and 4.3 GPa for PA-6/C30B)
and excellent elongation at break (38% versus 40% for neat PA-6 and 10% for
PA-6/C30B).
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Exfoliation of Clays
235
Clay-Containing Polymeric Nanocomposites
modulus with clay content, a similar increase of the tensile strength and poorly
correlating decrease of the elongation at break. The authors also reported a
synergistic effect on tensile strength and modulus when the exfoliated
nanocomposite was used as the matrix for a glass fibre reinforced composite.
Work from the same laboratory by Fornes et al. [2001] indicated that during
melt intercalation two processes simultaneously take place: thermodynamically-
driven diffusion of macromolecules into the interlamellar galleries, and mechanical
peeling off of platelets or short stacks. If during the former process the diffusion-
controlled intercalation sufficiently reduced the solid-solid interactions between
the adjacent platelets, the latter process may lead to exfoliation. It is noteworthy
that the minimum interlayer thickness of the organoclay needed for the PA-6
macromolecules to diffuse into is relatively small, d001 = 1.8 nm. However, the
chemical character of the intercalated onium cation, hence miscibility with PA-6,
is important as the diffusion of PA-6 molecules expands the interlamellar gallery
height at least by a factor of two. The stress field present during the compounding
also seems essential for efficient exfoliation.
The next contribution from this group was analysis of the behaviour of a
series of CPNCs with PA-6 as the matrix and containing up to 4.5 wt% of
organoclay [Fornes et al., 2004]. Three types of organoclays with quaternary
ammonium ions were tested. These were MMT-type, intercalated with: tetramethyl
(4MA), trimethyl hydrogenated-tallow (3MHTA), or dimethyl di(hydrogenated-
tallow) (2M2HTA). The nanocomposites were prepared by melt compounding
in a TSE. XRD and TEM demonstrated that the degree of dispersion increased
from 4MA (the worst) to 3MHTA. The modulus and yield strength increased in
the same order, while the elongation at break showed the opposite trend. These
results indicate that for melt intercalation by PA-6, a minimum interlayer spacing
is required – the minimum being located between d001 = 1.36 and 1.80 nm,
measured for MMT-4MA and MMT-3MHTA, respectively. The second important
information concerns the interaction between the PA-6 macromolecules and the
organoclay – in spite of larger initial interlayer spacing (d001 = 2.42 nm) MMT-
2M2HT did not disperse as well as MMT-3MHTA. Evidently, a more thorough
covering of clay platelet in MMT-2M2HTA by immiscible (with PA-6) long alkyl
tails than that produced by MMT-3MHTA is to blame. Partial access of the clay
surface to PA-6 chain-ends provides compatibilisation, similar to that provided
by PO-MAH in CPNC with PO as the matrix.
Exfoliated CPNC was obtained by melt compounding PA-6 with doubly-
intercalated MMT [Liu et al., 2003]. Thus, MMT was first intercalated with
3MHDA, and then with the diglycidyl ether of bisphenol A. A high level of clay
dispersion was achieved up to 5.6 wt% of inorganic content. At this loading the
mechanical properties (with reference to neat PA-6) increased by: tensile modulus
112%, tensile strength at yield 71%, flexural modulus 89%, flexural strength
54%, impact strength 34%, etc. In parallel, the HDT of PA-6 of 62 °C increased
to 157 °C.
Hasegawa et al. [2003] described quite a revolutionary method for the
production of PA-based nanocomposites. Thus, PA-6 was compounded in a TSE
with an aqueous suspension of Na-MMT (2 wt% solids). During compounding
the water was removed by vacuum-aided devolatilisation. The PA-matrix was
not hydrolysed. According to OM and TEM the clay platelets were exfoliated
and dispersed homogeneously. The tensile and flexural moduli of the CPNC were
28 and 14% higher than those of neat PA-6, respectively. Similarly, the tensile
236
Exfoliation of Clays
and flexural strengths were higher by 28 and 12%, respectively. The Izod impact
strength of the new nanocomposites was 12% lower compared to PA-6 and HDT
increased from 75 °C for the neat resin to 102 °C. Gas permeability was 31%
lower than that of neat PA-6. In short, the properties of the new PA-6/MMT
nanocomposites were comparable to those of commercial CPNC from Ube (see
Table 62), prepared by compounding PA-6 with 2 wt% MMT-ADA organoclay.
CPNCs with PA-66 as a matrix were prepared in a high strain rate TSE [Nair
et al., 2002]. The final composition contained 1 to 15 wt% of unidentified
organoclay from SCP. While no details on the compounding protocol were given,
the strategy adopted by the group involves:
1. The use of organoclay suitable for melt compounding.
2. Preparation of a concentrate by compounding the organoclay with the matrix
resin in a TSE.
3. Using a continuous or batch mixer, dilute the concentrate to the final
composition and pelletise.
4. Adjust the MW of PA by solid-state polycondensation.
5. Form final object by injection moulding, extrusion, etc.
The processing conditions are not critical, but moderation is recommended – the
process must provide sufficient residence time at sufficient shear stress at a
temperature near to the Tm of the matrix resin. According to the authors, the
variables that mostly affect the dispersion are: screw design, rotational speed,
throughput rate and the feeding method.
The cited publication focused on the fracture mechanics study of PA-66
with different types of layered silicate having nanoscale (fully dispersed) or
multiscale (mixed nanoscale/microscale) structure. Independently of the structure
and concentration, the fracture toughness was proportional to the size of the
crack-tip plastic zone at fracture. At low clay concentration, the toughening
effects in CPNC increased with exfoliation and strong clay/matrix interactions.
However, at high clay concentrations, where the initiation toughness was low,
no significant effect of these microstructural factors was observed – the
composites with mixed nanoscale/microscale particulates exhibited the best
toughness. In the latter systems high initiation toughening from the nanoclay
was combined with high propagation resistance from the micron sized particles.
The organoclays seem to influence shear flow at the crack tip, thus playing an
important role in the toughening mechanism.
Incarnato et al. [2003] melt compounded a commercial ADS copolyamide with
up to 9 wt% Cloisite® 30B. The specimens showed mixed intercalated/exfoliated
clay dispersion with altered matrix crystalline morphology, e.g., high content of
the γ-crystalline phase, and reduced crystallisation temperature.
237
Clay-Containing Polymeric Nanocomposites
238
Exfoliation of Clays
239
Clay-Containing Polymeric Nanocomposites
240
Exfoliation of Clays
Since PA-6 has Tm ≅ 219 °C, I.30 with better thermal stability than C20A
was chosen for the preparation of CPNC with PP/PA-6 blend. The compounding
sequence was altered, first blending PP with PP-MA, and then adding I.30 at 100
rpm. PA-6 was incorporated using two procedures:
1. Two-step process where first PA-6, PP-MA, and I.30 were mixed, then PP
was added;
2. Three-step process, where first PP-MA was mixed with I.30, then with PA-6,
and finally with PP.
As summarised in Table 37 the compounding resulted in intercalation. The
presence of PA-6 did not increase the d001 value, but reduced the intensity of the
XRD diffraction peak, indicating a higher degree of exfoliation.
The molecular weight and MAH content of the compatibilising PP-MA strongly
affect the nanostructure and the properties of PP nanocomposites. PP-MA with a
lower molecular weight and a high MA content leads to better dispersion, but
reduces the mechanical performance. Similarly, addition of PA-6 increases the
interlayer spacing, but reduces the tensile strength. Addition of a high molecular
weight PP-MA with lower MAH content may improve both stiffness and
toughness, but improvements are limited viz. 14% for tensile strength, 49% in
241
Clay-Containing Polymeric Nanocomposites
tensile modulus and 30% in Izod impact strength. The best overall performance
was obtained from the system: PP + 15 wt% PP-MA (1.5 wt% MAH) + 5 wt%
Cloisite® 20A.
Following the successful direct melt exfoliation of Na-MMT in a PA-6 matrix
by Hasegawa et al. [2003] the method was extended to a Na-MMT/PP system
[Kato et al., 2003]. A TSE with D = 32 mm, and L/D = 77 was used at T = 200
to 220 °C and screw speed of 300 rpm, with residence time of ca. 6 min. The
barrel was divided into three functional sections: (1). mixing, (2). exfoliation,
and (3). devolatilisation. Into section (1), first PP and PP-MAH were fed from
the main hopper to be melt compounded with Na-MMT (fed a bit downstream).
Into section (2) ca. 10% of water was injected (at the processing temperatures
the saturated vapour pressure is 1.5 to 2.3 MPa) to expand the interlayer spacing
of Na-MMT, and facilitate reactions between MAH and the clay surface. In
section (3) a two-stage devolatilisation was carried out. As a result, the clay was
uniformly dispersed as either exfoliated platelets or intercalated short stacks.
The mechanical properties of these nanocomposites were nearly the same as those
of conventional CPNC prepared by compounding with organoclay, for example,
the flexural modulus of the new CPNC was 2.76 versus 2.88 GPa.
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Exfoliation of Clays
A partial explanation for the poor mechanical performance can be found in the
reduction of crystallinity. To compensate for it a higher clay loading is required.
Thus, CPNC with up to 10 wt% MMT were prepared with C4 and C5 organoclays
[Lepoittevin et al., 2002a,b]. The highest tensile modulus was obtained for 10 wt%
C5 (increase by a factor of 1.85), but the material became brittle (7% elongation
at break). A better balance of properties was obtained for a 5 wt% C5 loading,
viz. modulus increased by 45% and the elongation at break, εb = 560%. The
CPNC also showed improved thermal stability and flame resistance.
Lepoittevin et al. [2002b] also prepared CPNC with PCL as the matrix via in
situ intercalative ring-opening polymerisation of ε-caprolactone catalysed by
dibutyl-tin dimethoxide, Bu2Sn(MeO)2. For comparison, 1, 3, 5, and 10 wt % of
C1, C4 and C5 organoclays were incorporated. The C1 and C4 content had no
effect on the PCL molecular weight (Mn = 14 to 24 kg/mol), but as C5 content
increased, the Mn was found to decrease, probably due to chain transfer by the
intercalant’s –OH groups. The polymerisation resulted in a modest intercalation
of C1 (d001 increased from 1.2 to 1.63 nm for the 3 wt% in PCL matrix); in
intercalation of C4 (d001 increased from 1.86 to 2.68 nm); and in nearly full
exfoliation of C5, confirmed by TEM. TGA showed better thermal stability for
the exfoliated than for the intercalated CPNC, both exceeding the degradation
temperature of neat PCL.
Tortora et al. [2002] also used the polycondensation route, but starting with
MMT pre-intercalated with ω-amino dodecyl acid, 0 to 44 wt% of MMT-ADA.
According to XRD exfoliation was achieved for CPNC with up to 16 wt% clay.
243
Clay-Containing Polymeric Nanocomposites
244
Exfoliation of Clays
245
Clay-Containing Polymeric Nanocomposites
including primary and quaternary alkyl (C8, C12, C18, etc.) as well as primary
and tertiary amines with biphenyl groups, e.g., 4-cyano-(4´-biphenyl-oxy)-undecyl
ammonium salt, that showed good miscibility with LC. MMT intercalation was
conducted in aqueous medium at 50 °C stirring the suspension for 3 h, washing
the precipitate with ethanol and freeze-drying it. The interlayer spacing varied
with the intercalant from d001 = 1.37 to 3.28 nm. Next, the organoclay (0.2 to 2
wt% in the final composition) was dispersed in DMF or dimethyl acetamide
(DMAc) and the LC was added. The solution was spin-coated on slide glass,
DMF slowly evaporated at 50 °C, and then under vacuum. When the clay had
good affinity for LC, the system was homogeneous. The CPNC exhibited bistable
and reversible electrooptical effects between a light scattering and transparent
state that could be selected by changing the frequency and voltage of applied
electric fields. To activate transparency a 50 ms electrical field (60 Hz, 100 V)
application was required. To induce opacity a 50 ms high frequency field (1.5
kHz, 100 V) was needed. When the field was switched off the transparency (in
the first case) or opacity (in the second) remained. The memory effect is related
to the orientation of clay particles caused by application of the low frequency
field and randomisation by the high frequency one. This new CPNC is a potential
candidate for light controlling glasses, high information display devices (that do
not require active addressing devices), erasable optical storage devices, etc.
246
Exfoliation of Clays
247
Clay-Containing Polymeric Nanocomposites
248
Exfoliation of Clays
used. Melt compounding of PLA with 4 wt% of this organoclay was carried out
in a TSE at 210 °C. Compounding increased d001 from 2.1 to 3.1 nm, but it
reduced the PLA Mw from 177 to 150 kg/mol. The effect of the organoclay on
crystallinity was quite modest, viz. the degree of crystallinity increased by ca.
4%, Tg decreased by 4 °C, Tm was unchanged and Tc increased by 28 °C. However,
at the same time the improvement of the mechanical properties of PLA was
significant – flex modulus, storage modulus and flex strength at 25 °C all increased
by: 26, 25 and 9%, respectively. Surprisingly, incorporation of the organoclay
accelerated the rate of PLA biodegradability by ca. 60%.
In the fourth paper of this series [Ray et al., 2003], PLA was melt compounded
in a TSE at 210 °C with 4, 5 or 7 wt% of organoclay. The latter was MMT (CEC
= 0.9 meq/g; p ≈ 100), pre-intercalated with trimethyl octadecyl ammonium
(3MODA). Melt compounding only slightly reduced the Mw of the PLA matrix
(from 177 to 165 kg/mol), and virtually did not affect Tg and Tm. The strongest
increase of the PLA degree of crystallinity was for 4 wt% clay loading – an increase
from 36 to 65%. At the higher organoclay contents the crystallinity decreased to
56 and 54%, respectively.
Again, these nanocomposites were only intercalated. While the interlayer
spacing of organoclay was d001 = 1.93 nm, incorporation into PLA melt at the
level of 4, 5 and 7 wt% organoclay increased this value to 3.05, 2.7 and 2.8 nm,
respectively. The data also indicate that here the number of platelets in a short
stack was about 4. Nevertheless, the improvement of the mechanical properties
(see Figure 57) was quite impressive – note that the tensile strength and the
elongation at break go through a local maximum at about 4 wt%. On the other
hand, the Young’s modulus and the heat distortion temperature linearly increase
with the clay content in the whole range of compositions. In Figure 58 the relative
oxygen permeability is shown versus organoclay content. The experimental data
249
Clay-Containing Polymeric Nanocomposites
follow Equation 23 with the aspect ratio, p = 24. Since the average number of
platelets in the stack is about 4, and the interlayer spacing is about 3 nm, the
effective length of the stack is 288 nm – to be compared with the estimate by the
authors of approximate platelet diameter, D ≈ 200 nm.
As has been noted before, incorporation of MMT enhanced the
biodegradability of PLA. It is interesting that the enhancement is not observed
during an initial period (30 < ti < 50 days). Afterwards, without the organoclay
the biodegradation proceeds at a slow rate, whereas in its presence it is
dramatically increased – all specimens decomposed in 60 days. Since the
biodegradation proceeds by hydrolysis of the ester linkages, one may speculate
that the difference is related to the size of the PLA crystals, as well as the presence
of ≡Si-OH hydroxyl groups. The melt flow behaviour of these systems strongly
suggests that these groups react with PLA, causing end tethering. However, such
a non-catalysed reaction is slow and numerous ≡Si-OH groups are most likely
left behind.
Paper 5 of this series examines the influence of different organoclays on the
performance of PLA nanocomposites [Ray et al., 2003b]. At a constant loading
of 4 wt%, the best performance was obtained using synthetic fluoromica (FM)
pre-intercalated with methyl di-polyethylene glycol coco ammonium ion: the
flexural modulus increased by 26%, strength by 9%, HDT increase by 17 °C,
and O2 permeability was reduced by a factor of 2.8. Furthermore, biodegradability
of this system was twice as rapid as that of neat PLA. The final contribution in
this series [Ray and Okamoto, 2003] focused on the flow and foamability of
PLA containing up to 7 wt% of MMT-ODA. Non-linear viscoelastic behaviour
was observed in dynamic, steady state and extensional flow fields. High quality
foams with bubble size of 2.59 ± 0.55 μm were produced.
250
Exfoliation of Clays
Notes:
* Q = quenched, A = sample Q annealed at 120 °C, C = crystallized from melt
at 120 °C for 3 h
** D = spherulite diameter, Tg is the glass-transition temperature, T1 is the onset
temperature for cold crystallisation and Tm is the melting temperature
251
Clay-Containing Polymeric Nanocomposites
252
Exfoliation of Clays
50 °C [Biswas and Ray, 1998]. Both methods resulted in a similar conversion versus
time plot. The cationic polymerisation at 50 °C was catalysed by MMT. First, the
NVC was adsorbed by the MMT surface, forming a complex either with the
counterion or with metal oxide impurities in MMT (e.g., Fe2O3), which resulted in
electron transfer that initiated polymerisation. Up to 10 wt% of poly-N-vinyl carbazole
(same as poly-9-vinyl carbazole, PVK) was retained by MMT after extraction by
benzene, indicating the presence of end-tethered macromolecules. XRD showed that
as a result of polymerisation the characteristic MMT diffraction peak (d001 = 0.99 nm)
was significantly reduced in intensity and a new one (d001 = 1.46 nm) appeared. The
latter indicated intercalation, but judging by its low intensity, probably some
exfoliation took place. Considering the high concentration of MMT in these systems
(≤ 43 wt%) exfoliation was not to be expected. Incorporation of MMT significantly
improved the thermal stability; whereas PVK totally decomposes at 700 °C, the CPNC
lost only 12.2 wt% at 683 °C. However, the most astonishing result of the process
was the increase of DC conductivity by 10 orders of magnitude: from 10-16 to 10-6
S/cm, and doping may increase it even further.
In the subsequent paper the authors discussed polymerisation of NVC in the
presence of FeCl3-impregnated MMT [Ray and Biswas, 1999]. XRD displayed
only one d001 = 0.98 nm peak, thus the MMT-FeCl3 complex was not intercalated
during polymerisation. TEM showed the clay particles to be in the range 30-
40 nm. However, the DC conductivity of the CPNC was in the range 3.1 x 10-5 S/cm
at 5.9 wt% of FeCl3, dependent on the FeCl3 loading. In this context it may be
interesting to note that polymerisation on the surface of nanoparticles can be
used for the preparation of self-assembled monolayers. For example, brush-type
core-shell macromolecular structures were polymerised on the surface of Au
particles with diameter d = 2-5 nm by means of surface-initiated living cationic
polymerisation of 2-oxazolines [Jordan et al., 2001].
In 2002 Suh and Park prepared CPNC with MMT-ODA dispersed in a PVK
(Mw = 100 kg/mol) matrix. Three organoclays were prepared, containing 0, 50,
75 and 100% of intercalant per 100% of the clay’s CEC. Dissolving PVK in
chlorobenzene, and then adding a suspension of 1 wt% organoclay resulted in
CPNC. XRD of the organoclay indicated that the interlayer spacing increased
with ODA content from d001 = 1.25, 1.72, 1.77 and 1.89 nm, for 0, 50, 75 and
100% CEC, respectively. The spacing in dry, cast films of PVK/MMT-ODA also
depended on the ODA content. Evidently, for 0% (neat MMT) a non-intercalated,
simple, filled system was obtained. Intercalated CPNC were obtained for
compositions containing 75 and 100% CEC of ODA. However, the system
containing a low density of the intercalant in organoclay, PVK/MMT-50%ODA
was found exfoliated. This, seemingly surprising observation is in excellent
agreement with thermodynamic theories discussed in Section 3.15.
Yu et al. [2004] prepared a series of CPNCs by dispersing an organoclay in
NVC, and then UV-photoinitiating in situ polymerisation with triarylsulfonium
salt as the initiator. The organoclay was Na-MMT pre-intercalated with acidified
diallyl amine: (CH2=CH-CH2)2NH2+ Cl–. The final CPNC contained 0 to 1 wt%
of clay. Within this range of composition, Mn decreased from 2273 to 1438 g/mol,
while Tg increased from ca. 48 to 78 °C. This Tg increase is intriguing, considering
the low clay loading, poor exfoliation, and the low and decreasing (with clay
content) molecular weight of the matrix (note that Tg decreases with Mn as:
Tg = Tg∞ - A/Mn).
253
Clay-Containing Polymeric Nanocomposites
2.4.4.4 Polydiacetylene
An attempt was made to intercalate MMT, vermiculite or mica with diamine-
diacetylene (DADA), monoamine-diacetylene (MADA), or ω-aminoacid-diacetylene
(AADA), then polymerise these using 60Co irradiation [Srikhirin et al., 1998]. For
this purpose, 14-amino-10,12-tetradiynoic acid and 10,12-docosadiyndiamine
(diacetylenic diamine), were synthesised. The approach was to intercalate the clays
with a cationically terminated diacetylene monomer by cation exchange. The
intercalation was carried out by mixing the clay with diacetylene ammonium salt
solution in 10% EtOH/water for up to seven days at 70 °C. XRD and FTIR
confirmed the intercalation. The interlayer spacing of the intercalate decreased
with the number of washings, e.g., from d001 = 4.5 to 3.7 nm. The interlayer spacing
and polymerisability of the intercalated diacetylene were found to depend on the
molecular length, the CEC of the clay, the type of diacetylene molecule, and the
solvent treatment.
Polymerisation of a diacetylene may occur when the monomer has proper
packing in the solid state. The polymerisation results in a conjugated backbone,
providing π-electron delocalisation along the backbone which gives polydiacetylenes
their unique electrical and optical properties. The polymerisation of the intercalated
diacetylene should result in growth of the polydiacetylene chain along the interlayer
gallery. However, packing of the intercalated monomers controls the reactivity of
the diacetylene/clay complex. Since the intercalated DADA/MMT, AADA/MMT
and AADA/vermiculite lie flat on the clay surface they lack the proper geometry to
be polymerised. The intercalated MADA/vermiculite and MADA/MMT are tilted
with respect to the clay surface, but polymerisation was only observed in
MADA/vermiculite where the intercalated diacetylene has proper packing geometry
and monomer density (smaller area per intercalated molecule).
The conductivity of I2-doped polyaniline (PANI) approaches that of Cu, but
the polymer is brittle and sensitive to humidity and oxygen. Recently MMT was
intercalated with aniline hydrochloride, and then aniline was electropolymerised,
increasing the interlayer spacing to d 001 = 1.47 nm [Feng et al., 2001].
Unfortunately, the note did not report data on the stability and conductivity of
this potentially interesting material.
254
Exfoliation of Clays
255
Clay-Containing Polymeric Nanocomposites
256
Introduction
Part 3
Fundamental Aspects
Clay-Containing Polymeric Nanocomposites
Thermodynamics
3.1
Thermodynamics
Tg = Tgb ⎡1 − ( a / h) ⎤
δ
(30)
⎢⎣ ⎥⎦
where Tgb is the glass transition of the bulk phase, h is the film thickness,
and a and δ are empirical parameters which depend on the system, viz. for
PS a = 3.2 nm and δ = 1.8; for PMMA a = 0.35 nm and δ = 0.8. It was
reported that the behaviour was independent (or nearly so) of the substrate.
A mechanism that may explain such Tg behaviour is the presence of a thin
surface layer having high molecular mobility and higher free volume fraction
than that in the bulk [Forrest and Dalnoki-Veress, 2001]. The thermodynamic
analysis of the surface/interface energy indicated that there are two basic
mechanisms responsible for the minimisation of the surface energy: high
257
Clay-Containing Polymeric Nanocomposites
concentration of highly mobile chain ends and migration toward the surface
of low molecular weight components (low MW fractions and additives)
[Helfand and Tagami, 1971; 1972].
Recently, Monte-Carlo (MC) simulation was used to study the behaviour of
thin polymeric films. As shown in Figure 59, the computations gave results
closely resembling the experimental results. Furthermore, it was found that
the thin films have a fluid-like interfacial region where mobility is considerably
higher than in the bulk film [Jain and de Pablo, 2002]. The computed results
indicated that it is not an effect of different skin composition, but rather the
chain conformation. In agreement with Helfand and Tagami calculations,
near the surface MC simulations predicted high concentration of chain ends
and reduced density. In this region the linear macromolecules have non-
Gaussian coil configuration.
3. For type (3) the Tg depends on both film thickness and weight-average
molecular weight (Mw). The reduction of Tg is significantly more pronounced
than in type (2). For high Mw the following dependence was found to describe
the behaviour:
Tg − Tg* = b ln(Mw / Mw* ) × (h − h* ) (31)
where symbols with asterisk (*) are reference variables.
For PS: b = 0.70 ± 0.02 K/nm, Mw* = 69 ± 4 kg/mol, h* = 10.3 ± 0.1 nm, and
Tg* = 423 ± 2 K. The dependence is illustrated in Figure 60.
Chow [2002] proposed the glass transition theory for unsupported, nanoscale
polymeric films with thickness < 100 nm. The theory is based on the Gibbs and
DiMarzio time-independent theory that Tg is related to the loss of configurational
entropy of a liquid during the cooling experiment. The entropy in turn can be
related to the free volume fluctuations, which depend on the temperature and
film thickness. The Langevin equation was used to derive the following
dependence:
[ ⎧
]
2θ ⎫
[ ] ( )
ln Tg (h, N ) / Tg∞ = − k B N / 2 N o ΔC p ⋅ exp ⎨− (h / ho ) ⋅ N o / N ⎬
⎩ ⎭
(32)
where Tg and Tg∞ are the polymer glass transition temperature in the film and in
the bulk, respectively; h and ho are the film thickness and its critical value equal
to the radius of gyration; kB is the Boltzmann constant; N and No are the number
of statistical segments in a polymer and in a reference state; ΔCp is heat capacity.
The exponent θ = 0.7 was determined for polystyrene. The relation predicts that
the Tg of low molecular weight polymer thin films has higher value than that of
high molecular weight. This unexpected result is confirmed by experiments and
the empirical dependence is illustrated in Figure 60. The author also derived an
expression predicting variation of Tg with the strength of the polymer-substrate
interactions. For low (or absent) interactions the dependence for free film was
recovered; hence Tg(film) < Tg(bulk). For strongly interacting systems the Tg in
thin film was predicted to have a higher value than that observed for the bulk
polymer: Tg(film) > Tg(bulk).
Another type of nanosized particles with unexpected Tg behaviour was recently
described [Mi et al., 2002]. The authors prepared single-macromolecular coil
size globules of polyacrylamide (PAAM; Mw = 5,000 to 6,000 kg/mol) by
atomisation spraying of a dilute polymer solution, followed by drying. Thermal
analysis showed that the globules had a higher Tg than that of the same bulk
258
Thermodynamics
259
Clay-Containing Polymeric Nanocomposites
polymer, viz. 205 versus 193 °C, respectively. The explanation offered is based
on the configurational entropy of a single macromolecule in the bulk and in the
globular state. The analysis indicated that polymer chains in the latter state should
have Tg higher by a few percent (absolute T-scale), e.g., by ca. 10 °C, which
indeed was observed. However, this analysis neglects the surface energy difference
(which acts in the opposite direction), as well as the interaction of the globule
with the substrate (which tends to increase Tg).
In conclusion, three factors have been identified as affecting the glass transition:
molecular weight (MW), film thickness (h), and the interactions between film
and the substrate (χ). The theory predicts that high molecular weight polymer
diffusing into narrow interlamellar galleries will have high mobility under the
condition of poor interaction with the clay, but poor interactions means absence
of the driving force for diffusion. On the other hand, strong interactions means
good ‘motivation’ for the macromolecules to diffuse, bind with the clay substrate
and ‘solidify’ into a layer of adsorbed macromolecules with low segmental
mobility.
3.1.2 Nanothermodynamics
In the early 1960s Hill noted that the equilibrium thermodynamic properties of
sufficiently small systems differ from those predicted by the classical
thermodynamics of large systems [Hill, 1994]. More recently, the field was
renamed nanothermodynamics [Hill, 2001a; 2001b]. Originally, the treatment
considered homogeneous, small systems, such as individual macromolecules or
colloidal particles, each composed of n-elements. For n → ∞ the macroscopic
properties are recovered. However, when n is small there are at least two significant
contributions to the energetic state of such a system, the first depends on the
surface energies, and the second on the entropy related to the dynamic state of
the particles. For example, a single platelet of MMT, owing to its thickness
(0.96 nm) and large aspect ratio, has a specific surface area of ca. 800 m2/g, and
about 36% of its atoms are on the surface. Considering the high surface energy
of solids (e.g., surface energy of freshly cleaved mica is γ = 4,500 mN/m) the
surface effects are expected to dominate the thermodynamic state of nanoparticles.
Since in most systems the miscibility and phase equilibria are determined by a
fine balance of small energetic and configurational contributions, the surface
effects are expected to influence them, and thus to be critical for the performance
of CPNC.
For the principle of nanothermodynamics to apply to a macroscopic system,
it must be visualised as an ensemble of small subsystems (or aggregates)
independent of each other. The number of elements n in each aggregate does not
have to be the same. A good example is a semicrystalline substance having
numerous small crystals of various sizes that contain n molecules. The substance
may show size-related effects, e.g., of the melting point, width of the melting
transition, heat capacity, glass transition temperature, etc. Other examples are
provided in recent publications on statistical thermodynamics of metastable
droplets [Hill and Chamberlin, 1998], on ferromagnetism [Chamberlin, 2000]
or on phonon scattering by the boundary of nanocrystals [Shrivastava, 2002]. In
the latter paper it was shown that the specific heat of crystalline materials depends
on particle size.
One of Gibbs contributions to the equilibrium thermodynamics was addition
of the chemical potential to the basic energy-heat-work equation. This
260
Thermodynamics
de = − SdT + VdP − ∑ N dμ i i
i (34)
− S = (∂e / ∂T ) P, μ ; V = (∂e / ∂P)T, μ ; Ni = (∂e / ∂μ i )T, P, μ
i i j
261
Clay-Containing Polymeric Nanocomposites
2. Environmental Variables N, P, T:
From the partition function:
Δ( N , P, T ) = ∑ j, V
{ }
exp − E j ( N , V ) / kT exp{− PV / kT } (37)
ϒ ( μ , P, T) = ∑ j, N, V
{ }
exp − E j ( N , V ) / kT exp{Nμ / kT } exp{− PV / kT } (41)
− kT ln ϒ = E − TS + PV − μN = e
(42)
− d ( kT ln ϒ ) = − SdT + VdP − Ndμ = de
The latter case is particularly important since here the system is ‘completely open’
and all environmental variables are intensive. Note that the three variables: μ, P
and T cannot all be independent in a macroscopic system but they can in a small
system. In nanosystems these intensive variables determine the mean size N (an
extensive variable). This type of system is found in biology, in bulk magnetic
materials, a Gibbs surface excess resulting from an adsorbent molecule at the
end of a one-dimensional lattice gas, or metastable supersaturated gaseous states
near the gas-liquid transition point.
Recently, this treatment was extended to one-dimensional adsorption of gas
[Hill, 2001a; 2002b]. Consider a surface of B adsorbent, with molecules
independent of each other, from each of which a chain of M binding sites extends
vertically. B and M are both very large. The B molecules, at T and μ, go on and
off the sites. There is an interaction energy (w) between any two adsorbed
molecules on nearest-neighbour sites of a chain. Also, there is an interaction
energy w′ between an adsorbent molecule and an adsorbed molecule that occupies
the first site of the chain. The mean number of adsorbed molecules per chain is
denoted N ex and typically its magnitude is of the order of 1 to 10. For B surface
excesses (small system) free energy is:
E = TS + μN ex B + eB
(43)
(
dE = TdS + μd N ex B + edB )
So far, nanothermodynamics have not been applied to PNC.
262
Thermodynamics
3.1.3.1 Introduction
In his PhD thesis of 1995 Vaia used a lattice model to describe the thermodynamic
behaviour of CPNC comprising organically modified layered silicates, e.g., mica
or MMT (the work was published two years later [Vaia and Giannelis, 1997a;
1997b]). Initially, the interlayer galleries are occupied by hydrated alkali metal
cations, which during intercalation are exchanged for organic ones – most often
quaternary alkylammonium ones. Because of the negative charge on the silicate
surface and crowding of intercalant groups, the alkyl tail of the alkylammonium
molecule projects away from the surface. However, as the data in Figure 23
demonstrate, the expansion of the interlamellar gallery proceeds step-wise, at
lower efficiency than would be expected from fully stretched hydrocarbon chains.
At the processing temperature of CPNC, Tprocess ≥ 150 °C, the interlayer
structure is expected to be disordered with a density comparable to that of liquid
alkanes. Preparation of CPNC involves the formation of nanostructures where
the matrix molecules (monomers, macromers or cyclomers introduced during
the reactive process or macromolecules incorporated during melt compounding)
diffuse into the interlayer galleries, either as a result of static annealing, dynamic
mixing or both. Polymer diffusion into galleries expands the silicate layers.
Depending on the degree of penetration and resulting interlayer spacing, either
intercalated or exfoliated nanocomposites are obtained. Their structure depends
on the length, density and type of intercalant, on the type, molecular weight and
structure of the polymer, on the concentration of the pre-intercalated clay, as
well as the polymer-clay and polymer-intercalant interactions.
Vaia modelled CPNC as two parallel platelets pre-intercalated with short
chains tethered to the clay surface, and then dispersed in an infinite sea of molten
polymer (infinitely diluted system). During the second stage of the intercalation
the macromolecules diffuse into the interlamellar galleries. Within these galleries
the polymer forms a dilute solution with intercalant molecules. The basic
assumptions are that the system is incompressible, has constant polymer density,
and the intercalant is end-tethered. Furthermore, it was assumed that the
interactions that account for the miscibility/immiscibility of polymer/organoclay
systems are polymer-intercalant and polymer-clay type – the clay-clay interactions
and their variation with the gallery height were neglected. The final state of the
intercalation is given by the equilibrium thermodynamics. The author assumed
that the interlamellar gallery height does not exceed the full extension of the
intercalant chains on both gallery surfaces, thus the model accounts only for the
initial intercalation of organoclay by molten polymer. A thermodynamic
description takes into account the entropy-related configurations of the
constituents and the interactions between them. The external forces (e.g., shearing)
are not considered.
Derivation starts with the assumption that the macroscopic thermodynamic
description of the system is obtained considering a single sandwich of the organoclay
clay (having infinite breadth and width and the initial separation h0) embedded in
molten polymer. As the macromolecules diffuse into the gallery, the interlamellar
spacing increases to h. The Helmholtz free energy change, ΔF, associated with the
interlayer expansion from ho to h, is given by the internal energy change (associated
263
Clay-Containing Polymeric Nanocomposites
264
Thermodynamics
where νi, mi, and ϕi are the molar volume per segment, the number of segments per
chain, and the interlayer volume fraction, respectively. The statistical surface
fractions of interlayer sites near the surface that are occupied by the tethered chains
are expressed as: ψs ≡ ψs (h); ψso ≡ ψsh0 ≥ ψs h ≥ h0). The statistical surface factor, c,
accounts for the inaccessibility of sites on the far side of the surface (c = 0.75 for z
= 4, decreasing to 0.5 for z → ∞, where z is the lattice coordination number).
Finally, a2 is the intercalant segment length of the tethered chain and R is the gas
constant. Since ln c < 0, Equation 47 predicts that the entropic contribution of
the intercalant is positive, thus favourable for intercalation.
The parameters of the configurational entropy that originates from the
polymer, intercalant and their sum are listed in Table 40; the computed
dependencies are presented in Figure 61. Evidently, the loss of polymer entropy
during its diffusion into a gallery is partially compensated by the configurational
gains of the intercalant molecules. While initially there is a possibility of a small
increase of the interlayer spacing (by 0 < h - ho < 0.8 nm sufficient to accommodate
1 to 2 macromolecules) any larger expansion is forbidden by a rapid decrease of
the total entropic change. Thus, in the absence of favourable energetic interactions
any further polymer diffusion into the interlamellar galleries is not possible.
As it will be evident from the experimental data presented in Section 4, many
CPNC prepared by the melt or reactive intercalation method (e.g., in PS or PO
matrix), show increased interlayer spacing, Δd001, by about 0.35 to 0.75 nm,
which corresponds to single or two macromolecular layers inside the interlamellar
gallery. On the basis of Vaia’s entropic calculation one may postulate that in
these systems the energetic contribution to the thermodynamics is negligibly small.
265
Clay-Containing Polymeric Nanocomposites
3.1.3.3 Interactions
Vaia assumed that the energetic contributions originate in interactions between
the three components of the system: the silicate, s, the tethered intercalant, a,
and the polymer, p. Furthermore, the total change of the internal energy is taken
as a sum of the energy change associated with each pairwise interaction, εjk, with
the number of contacts expressed by the contact area. The pairwise interaction
energy per contact was expressed in terms of the cohesive or interfacial energy
per lattice site. Thus, the internal energy change of the system upon polymer
intercalation is:
(
ΔE = Aspf ε sp + Aapf ε ap + Asaf − Asai ε sa)
where A jkf and A ijk is
the total area of contact between components j-k for the final
(f) and the initial (i) system, respectively. The dependence was simplified assuming
that initially all the lattice sites within the interlayer gallery are occupied by
tethered intercalant chain segments, thus
Asp = Asaf − Asai
The next step in the derivation was a bit arbitrary, using van Opstal et al. [1991]
expression for the internal energy change per interlayer volume that takes place
during intercalation:
Δeν = ϕˆ 1ϕˆ 2 Δε =
(
2ϕˆ 1ϕˆ 2 ε sp, sa / ho + ε ap / r2 ) (48)
[
1 − ϕˆ 2 1 − (r1 / r2 ) − (r1 / ho ) ]
266
Thermodynamics
where Δε is the effective interaction energy per interlayer volume and ri is the
radius of the interaction surface, related to the molar volume and segment length
by the simple dependence: ri2 = ν i / πN A ai (where NA is Avogadro’s number). The
change in interactions at the interlayer surface was written as εsp, sa = εsp – εsa. To
encourage intercalation by diffusion of macromolecules the energetic contribution,
Δev, thus the numerator in Equation 48, should be negative. Evidently, this can
be expected when the interaction energies of polymer: εap < 0 and/or εsp < εsa –
when polymer ‘likes’ to cohabit the gallery, interacting with intercalant chains
and/or the clay surfaces.
The total free energy change associated with polymer diffusion into
interlamellar galleries and increased interlamellar spacing may be calculated from
Equations 44-48. In Figure 62 the total free energy change during polymer
diffusion into the gallery space is presented for εap ≅ 0 (van der Waals interactions
between intercalant chains and macromolecules) and for four values of the
interaction parameter, εsp, sa. Other parameters were taken from Table 40.
As the author noted, the values for the interaction parameters, εij, are not
readily available. Thus, he proposed that these might be replaced by interfacial
energies between interacting species i-j, viz. εap ~ vap and εsp, sa ~ vsp – vsa. However,
since the interfacial energies are also inaccessible, Vaia adopted the procedure
proposed by van Oss [1994] of calculating the interfacial energy from the surface
energies of the interacting species. The procedure considers that the interactions
are composed of polar/associative ( ν ip ) and dispersive/dipolar ( ν id ) forces:
ν ij = ν ijp + ν ijd
ν ijp = 2⎛ ν i+ − ν i− − ν −j ⎞ (49)
⎝ ⎠
2
ν ijd = ⎛ ν id − ν dj ⎞
⎝ ⎠
where ν i+ and ν i− are respectively, the electron acceptor and donor contributions.
Luciani et al. [1996; 1997; 1998] showed that the interfacial properties are
dominated by the polar and hydrogen bonding interactions, whereas the bulk
properties are dominated by the dispersive forces. In consequence, another method
for calculating the interfacial energy has been proposed. The method involves
computation of the interfacial tension coefficient from the difference between
the dipolar, polar and hydrogen bonding components of the two interacting species
i-j, viz.:
n
( ) ( ) ( )
ν ij = k1 (T )⎧⎨Θ δ i, d − δ j, d + δ i, p − δ j, p + δ i, h − δ j, h ⎫⎬
2 2 2
(50)
⎩ ⎭
where k1(T) and n are equation parameters and Θ ≅ 0.4 is the relative measure of
the importance of the dispersive contribution (its value for bulk interactions is
4). Since the solubility parameter can be calculated from the group contribution
method [Hansen, 1967; 1994; 1995; 2000], Equation 50 is general.
267
Clay-Containing Polymeric Nanocomposites
and it ‘dissolves’ into polymer diffusing into the interlamellar gallery. However,
reduction of entropy by such a ‘melting’ process is relatively small. Thus, the
theory predicts that the entropic effects are small and mainly detrimental to
intercalation by diffusion of macromolecules; hence the only method for achieving
intercalation is by ascertaining favourable energetic contributions.
Adopting the derivation by van Opstal et al. [1991], Vaia simplified the energetic
contribution given by Equation 48. The magnitude and sign of the effective
interaction parameters is related to pairwise interactions between the three
constituents, the accessibility of interaction sites, the interlayer packing density,
and the size of the intercalant chain. In most organoclays the intercalants have
apolar, paraffinic moieties, thus van der Waals dispersion forces dominate polymer-
intercalant interactions. In most cases, these interactions are characterised by a
small positive value of εap. By contrast, the clay surface is polar, thus if the diffusing
polymer has groups able to form polar or hydrogen bonds, the polymer-surface
interactions may be more favourable to exfoliation, thus εsp,sa < 0. In the case of
polar polymers, the favourable interactions may also be engendered by suitably
modifying the intercalant molecules. However, such a modification must be
carefully designed, as too strong interactions during an early stage of intercalation
may form a tightly packed polymer layer around the clay particles, slowing down
further polymer diffusion into the galleries.
The enthalpic contributions in Equation 48, εsp,sa and εap, are scaled with ho
and r2, respectively. Since, as discussed above, the former may be negative and
the latter positive, contrary to the expectations, better chances for exfoliation
may be found starting with organoclay having small (but adequate to polymer
268
Thermodynamics
diffusion) value of the interlayer spacing, d001 ≅ h0 + 0.96. On the other hand, for
reducing the small, parasitic contribution of εap the value of r2 should be maximised
by selecting intercalant with large molar volume moieties. Thus, not only the
magnitude of the energetic interactions, but the intercalant structure is important.
When the interaction parameter, εsp, sa = εsp – εsa < 0 an intercalation, then at
higher values, an exfoliation is possible. According to the adopted mechanism, it
is not a binary interaction parameter, but the relative magnitude of two binary
interaction parameters that counts. If exfoliation is to take place: εsp < εsa, i.e.,
clay must interact more strongly with the macromolecules than with the intercalant
chains. Accordingly, the role of the latter seems to be to sufficiently open the
interlamellar galleries facilitating the diffusion of macromolecules. Thus, again
the thermodynamic argument favours organoclays with small, but sufficient
interlayer spacing.
Serious difficulties are expected, and indeed found, when trying to exfoliate
organoclay with nonpolar olefinic macromolecules, e.g., PP. For these systems a
compatibiliser strategy has been used. Thus, polar groups are introduced (e.g.,
by maleation) into macromolecules having the same molecular configuration as
the nonpolar polymer. The key strategy is for these compatibilising
macromolecules to engender strong polymer-clay interactions. The nonpolar part
of these modified macromolecules must remain miscible with the nonpolar
polymer, ascertaining a single-phase structure of the matrix. Since the magnitude
of the Helmholtz free energy depends on the fine balance between small entropic
and enthalpic contributions, these ‘compatibilising’ strategies may be suitable
for the polymer-induced exfoliation.
In summary, the mean-field statistical lattice model is a first approximation
of the polymer melt intercalation. It is a simplified equilibrium thermodynamics
model, which considers only diffusion of molten polymer into a single gallery
formed by two organoclay platelets immersed in an infinite sea of polymer melt.
Of the three components: clay (s), polymer (p) and intercalant (a), the binary s-s
interactions have not been considered. Under normal circumstances these
interactions are about 100 times stronger than those between organic segments,
i.e., a-a or p-p. The s-s interactions are responsible for the difficulties in breaking
the clay particles into short stacks, doublets and finally into individual exfoliated
platelets. The model does not incorporate the ‘small system’ contributions
introduced by Hill. One must also ponder whether for the nanoscale system the
assumption of random mixing (e.g., absence of molecular adsorption on the
surface of crystalline solid) is valid. Furthermore, the model assumes absence of
external forces during melt exfoliation.
In spite of the simplifications and omissions the model helps in understanding
the mechanisms responsible for polymer intercalation. The insight gained leads
to recommended procedures for enhanced intercalation hence improved CPNC
performance. The recommendations are based on considerations of the entropic
and enthalpic contributions to equilibrium thermodynamics. The free energy of
the process is a fine balance of these two. The entropic penalty of macromolecular
confinement within the interlamellar galleries may be, at least partially,
compensated by the increased conformational freedom of the intercalant chain
as the gallery expands. The model indicates that to be successful in forming
exfoliated CPNC strong energetic interactions between the diffusing polymer
and clay are required. Vaia is less enthusiastic about inducing interactions between
intercalant and polymer, expecting hindered kinetics of polymer diffusion.
269
Clay-Containing Polymeric Nanocomposites
270
Thermodynamics
Figure 63 Empirical correlation between the PS matrix molecular weight and the
time required for reaching equilibrium intercalation under static melt annealing at
160 °C. Data [Vaia and Giannelis, 1997b].
with the clay, εsp,sa < 0 and the polar contribution to the interfacial
energy, ν ijp < 0; and ν ijp > ν ijd . According to Equation 48, the internal energy is
zero when:
ε sp, sa / ε ap = − h / r2 or when ε sp, sa / ε ap = ξc (51)
where εjk are the interaction parameters (the subscripts indicate: the silicate, s,
the tethered intercalant, a, and the polymer, p), h is the gallery height, r2 is radius
of the interacting species 2, ξc is a characteristic parameter of the system.
Substituting the corresponding surface energy contributions into this relation a
‘product map’ was constructed. The map (see Figure 64) defines the area where
the favourable (negative) values of the energetic contribution are expected.
271
Clay-Containing Polymeric Nanocomposites
Figure 64 A ‘product map’ showing that favourable energetic interactions (Δev < 0)
are expected for polymers with dominating acid or base character. After [Vaia and
Giannelis, 1997b], see text.
lattice (e.g., diamond or cubic) model limits the possible molecular configurations.
It works well for low segment density, but it is difficult to use when the density is
high, as for example in planes with end-tethered linear macromolecules. The
simulations show that as the grafting density increases the macromolecules, to
avoid overcrowding, stretch in the vertical or z-direction. In the absence of a
solvent (‘dry brush’) the incompressibility of the polymer chain is responsible for
the stretching.
The off-lattice continuum models, MC or MD, perform better at high segment
density. Here the bond angle and/or length are allowed to vary, i.e., in the ‘pearl-
necklace’ model bond length is fixed while in the ‘bead-and-spring’ model it is
not. MD solves equations of motions for each statistical segment, i:
( )
m d 2 ri / dt 2 = −∇Ui − mΓ ( dri / dt ) + Wi (t ) (52)
where Ui is the total potential for segment i, Γ is the bead friction and Wi is a
random force acting on each bead. The interactions are assumed to follow the
Lennard-Jones potential within specified radial distances for the repulsion and
attraction.
The numerical method that is important in describing the configuration of
polymeric brushes is based on the self-consistent mean-field approach.
272
Thermodynamics
273
Clay-Containing Polymeric Nanocomposites
from the initial value ho to h. The free energy change during intercalation is
computed as: ΔF = F(h) – F(ho).
It is noteworthy that in these computations the interactions between the clay
platelet and either intercalant or polymer were assumed neutral, non-perturbing.
The only type of interaction of interest was the one between intercalant and
polymer. This focused interest contrasts with the opinion expressed by Vaia. Balazs
et al., admit that the intercalant-polymer interactions may unfavourably affect
the kinetics of polymer diffusion into the galleries. However, there is nothing in
the SCF methodology that would preclude systematic studies of the property
changes when varying other interaction parameters.
For the case of a non-intercalated clay sandwich immersed in a molten polymer
(see Figure 65) computations of the free energy per unit area as a function of the
interlamellar gallery height, ΔF/A = f(h), show that even for χsp = 0 the free
energy is positive, and thus intercalation is unfavourable. The effect is entropic –
the macromolecules in contact with the surface have reduced conformational
probability. When to start with the clay is intercalated and the macromolecules
are able to interact with the intercalant chains the enthalpic contribution may
compensate for the confinement effects. The computations for χap = -0.01 to
0.02 show a systematic increase of the free energy, ΔF/A = f(h). For polymer with
Np = 100 statistical segments, intercalant with Ni = 25 and the intercalant grafting
density ρ = 0.04, the polymeric intercalation was predicted only for χap ≤ 0.005.
However, when Np = 300 was assumed, no intercalation was predicted for χap = 0.
In other words, the miscibility between intercalant and macromolecules is reduced
with increased polymer molecular weight. To compensate for this effect one may
want to increase the Ni value from 25 to 50 or 100 – indeed, the computations
show that for χap = 0, this strategy leads to exfoliation, for χap = 0.01 it allows for
the polymer to intercalate, but for χap = 0.02 it makes the matter worse. These
observations based on the free energy changes are supported by the computed
segmental density profiles φ = φ(z).
While some results of the numerical calculations could be reasoned out from
the thermodynamic principles of polymeric systems, the effects of changes on the
clay platelets’ grafting density, ρ = 1/s (where s is the surface area per one
intercalant molecule), would be difficult to predict. Note that this parameter is
related to the intercalant concentration in the system, intercalant structure and
to the CEC of the clay (e.g., for MMT with CEC = 1 the surface area per one
ionic group is 1.244 nm2). The CEC varies (see Section 2.2) from 0.02 (kaolin) to
1 (MMT) to 2.5 (hectorite). SCF computations for ρ = 0.04 to 0.12 show that for
the latter value ΔF is high, thus as the packing density within the gallery increases
it becomes harder for the macromolecules to diffuse into it and mix with
intercalant chains. In short, on the one hand it is hard for macromolecules to
diffuse in between non-intercalated clay platelets, but on the other diffusion is
difficult when the intercalation density is high, i.e., there is an optimum in grafting
density for forming polymer/clay nanocomposites.
According to these computations the optimum value of CEC (or ρ) depends
on the interaction between the polymers and the intercalant, χap. In practice, the
intercalant ions may be primary, secondary, tertiary or quaternary ammonium
or phosphonium; they may have shorter or longer hydrocarbon chains, and (in
the case of the most popular quaternary type) they may have one to four long
chain groups. In the latter case, the results of SCF computations predict that the
intercalant with a single long tail should be better than the one with two or
274
Thermodynamics
Figure 65 Free energy per unit area as a function of surface separation, h, for five
different values of the polymer-intercalant interaction parameter, χap. Other
parameters are: N = 100; Ni = 25 and χsa = χsp = 0. The grafting density ρ = 0.04
and 0.12 for Figure (a) and Figure (b), respectively. The cartoons (c), left and right
show, respectively, the initial and final state, where the surfaces are separated by
macromolecules [Balazs et al., 1998].
Reprinted with permission from [Balazs et al., 1998]. Copyright 1998 American
Chemical Society.
275
Clay-Containing Polymeric Nanocomposites
three. This may explain the behaviour observed for the melt exfoliation of PA-6
[Dennis et al., 2000; 2001]. The authors melt blended PA-6 with 5 wt% of either
Cloisite® 15A or Cloisite® 30B. TSE compounding with the former organoclay
resulted in intercalation, whereas that with the latter in exfoliation. Both are
based on montmorillonite intercalated with quaternary ammonium ions: dimethyl
dihydrogenated tallow quaternary ammonium chloride and methyl tallow
bis-2-hydroxy ethyl quaternary ammonium chloride (MMT-2M2HTA and
MMT-MT2EtOH, respectively). Thus a higher packing density is expected for
Cloisite® 15A than for Cloisite® 30B. Evidently, the ability of macromolecules to
diffuse into interlamellar galleries of pre-intercalated clay depends not only on
the type of radicals (e.g., aliphatic versus aromatic) but also on the intercalant
structure, viz. the number of long aliphatic chains attached to onium ion. Vaia
[1995] observed that the kinetics of intercalation for FH clay intercalated with
2M2ODA is slower than that with either ODA or 3MODA.
The SCF numerical computations were also carried out for CPNC systems
with a compatibiliser. Two methods of compatibilisation were explored: (1) by
addition of compatibiliser between the intercalant chains and the polymer, and
(2) by addition of a compatibiliser, which is miscible with the polymer and able
to bind directly to the clay surface.
1. To examine the efficiency of the first approach, the computations were carried
out for the system with Na = 25, Np = 100, and χap = 0.01. Different amounts
of a polymeric compatibiliser (subscript c; Nc = 100) were added. The
interactions of compatibiliser with intercalant (subscript a) and polymer
(subscript p) were assumed to be: χac = χpc < χap. The simulation showed, as
expected, that addition of a compatibiliser improves the ability of polymer
to intercalate. However, the process was found inefficient, requiring at least
10% of the compatibiliser that forms an interphase between the tethered
intercalant layer and molten polymer. Evidently, the need for a large amount
of compatibiliser would have a negative effect on CPNC cost and performance.
Furthermore, enhanced interaction between the intercalant and polymer may
hinder the intercalation/exfoliation process not only for kinetics reasons,
but also owing to the loss of the conformational entropy.
2. To examine the efficiency of the second approach, computations were carried
out for the system where bare clay platelets are dispersed in a mixture of a
polymer with its homologue containing reactive group (called a ‘sticker’) at
one chain end. Aside from the sticker, the functionalised chains were
chemically identical to the matrix polymer. For the computations, the polymer
and compatibiliser chain lengths were assumed to be: Np = 100 and Nf = 75,
respectively. Strong interactions between the clay and the sticker group were
assumed (χsf = -75), while the other interaction parameters were set equal to
0. Figure 66 indicates that this approach is highly promising. There is a
substantial effect upon addition of 5% of the functionalised polymer, but
little further gain upon addition of up to 70%. The dependence shows that
the method leads to exfoliation, creating stable polymer/clay dispersions.
Evidently, in practice one may start with pre-intercalated clay, but one having
low grafting density, ρ.
The key to the second approach is the presence of the ‘sticker’ groups at the chain
ends able to strongly interact with the clay surface. In principle, such a functionalised
compatibiliser could be either a homopolymer with a strong polar group or an AB
276
Thermodynamics
Figure 66 Free energy per surface area versus gallery height for clay-polymer-
compatibiliser (functionalised polymer) system. The latter polymer content (0 to
70 wt%) is indicated.
277
Clay-Containing Polymeric Nanocomposites
(
ΔF = ΔFbrush − na + n f μ − ) ∑n μ i i
i (55)
ΔFbrush = ΔFstretch + ΔFmix + ΔEa
where μ is the chemical potential of the end-functionalised chain, μi is that of the
non-functionalised, polydispersed polymer, ΔFstretch accounts for the stretching
of the attached macromolecules, ΔFmix accounts for the free energy of mixing of
functionalised and non-functionalised chains, and ΔEa is the energy of attaching
the functional group to the surface. By substituting the appropriate terms the
following expression for the total free energy of the system was derived:
(ΔFtotal / RT )( N / Ntotal ) =
⎡ h ⎤
(
Nk 2 h2 / 3 − hmax
2
)
+ φ ⎢1 − exp − Nk 2 hmax
⎢⎣
2
{ }∫ {
exp − Nk 2 x 2 dx / h ⎥
⎥⎦
} (56)
0
⎡ h ⎤
∑
+ N (φi / Pi )⎢1 − exp − Pk
i ⎢⎣
i
2 2
hmax{ exp − Pki }∫ {
x dx / h⎥
2 2
⎥⎦
}
0
reactive group.
Note that for h > hmax, a layer of bulk polymer appears between the outer
edges of the two brushes. This however does not change the free energy of the
278
Thermodynamics
{
Θ (h) = h − φ exp − Nk 2 hmax
2
}∫ exp{− Nk x }dx
2 2
0
h
(58)
−N ∑ φ exp{
i
i − Pk
i
2 2
hmax }∫ exp{− Pk x }dx
i
2 2
279
Clay-Containing Polymeric Nanocomposites
It was found that the derived analytical expressions agreed well with the
numerical predictions by SCF. For example, the dependencies shown in Figures 66
and 67 could be generated by either of these two models. Similarly, the numerical
SCF data on the thickness of the unperturbed brush, hmax, also show satisfactory
agreement with the analytical prediction.
Recently, SCF was used to determine a range of independent variables that
guarantee thermodynamic miscibility in a realistic model system, which comprises
four components: solid clay platelets, low molecular weight intercalant, polymeric
matrix, and an end-functionalised compatibiliser [Kim et al., 2004]. In the
simulation, realistic values of the binary interaction parameters were used. The
results showed that intercalation and exfoliation is expected within limited ranges
of independent variables. Furthermore, it was found that the presence of bare
clay surface (e.g., generated by thermal decomposition of intercalant) strongly
hinders the clay dispersion. The 2D simulation successfully identified the most
influential factors (e.g., compatibiliser type and concentration) and established
their optimum ranges.
[( ) ]
σ n = 2 ln −2ν d π −1 / 2 / b ln(1 − φd ) − 1
(60)
ρn ≡ ( 4 / π) sin γ = −2(ν d / b) / ln(1 − φd )
where γ is the angle between two disks. The analysis for disks with an aspect
ratio p ≡ D/L = 30 predicts the existence of a phase diagram with three regions:
immiscible, isotropic and nematic. The region of miscibility decreases with
increasing N and χ. Furthermore; increasing p promotes nematic ordering and
reduces the isotropic phase.
280
Thermodynamics
This initial investigation was significantly expanded during the following years
[Ginzburg and Balazs 1999; 2000; Ginzburg et al., 2000; 2001]. The new model
predicts phase diagrams that include: isotropic, nematic, smectic, columnar, plastic
(or house-of-cards), and crystalline structures. For these calculations, the authors
combined the SCF model with the Somoza-Tarazona formalism of the density
functional theory (DFT). The resulting free energy functional was minimised
with respect to both the orientational and positional single-particle distribution
function, potentially determining all phases and the coexistence regions.
The free energy of a system
r r was
r written
r as a functional of a single-particle
r r
distribution function, γ (r , n ) = ρ(r ) f (n ) , where
r r and n are the coordinate rand
the nematic director, respectively, while ρ(r ) is disk number density, and f (n ) is
the Onsager orientational distribution function. The fluid was assumed
incompressible; i.e., the sum of the volume fractions of polymer, φp, of intercalant,
φi, and clay, φc, equals 1: thus φp + φi + φc = 1.
The free energy consisted of three terms, Fid, Fster and Fint:
1. Fid – the free energy of an ‘ideal gas’ of polymer
This term can be written as a sum of the translational and orientational
contributions coming from the clay particles, and that originating from the
polymer, Fid = Fc + Fp, respectively, the latter calculated from the Huggins-Flory
theory:
r r r r r r r r
( )
Fid / kT = ρ(r ) ln ρ (r )dr + ρ (r ) f (n ) ln 4πf (n ) dndr + (ν / Nν m )φp ln φp (61)
∫ ∫ ( )
r
where N is the chain length of the polymer, ρ(r ) is the positional (or local) density
of clay platelets, n is the total volume of the system, vm is the monomer volume
and φp is the volume fraction of the polymer. For the intercalated organoclay
platelets the effective thickness is: Leff = L + 2ρNi, and the effective volume of
such a particle: Veff = (π/6)D2Leff.
2. Fster – the contribution due to the excluded-volume effects for clay platelets
A semi-empirical steric interaction expression was used:
r r r
[ ] (
Fster / kT = ρ(r ) Vexcl ( f ) / Vphe Ψhs Φ (r ) dr
∫ )
(62)
where Ψhs is the Carnahan-Starling function that describes the excess freer energy
density for hard spheres as a function of their packing fraction; Φ (r ) is the
smoothed, local volume fraction of clay; Vexcl(f) is the average excluded volume
per particle for a given orientational distribution; and Vphe is the excluded volume
per particle for perfectly aligned ellipsoids.
The sum of the free energy terms, Fid + Fster, describes an athermal dispersion
of hard ellipsoids in a polymer matrix, capable of forming liquid crystalline
(nematic) or crystalline phases. To generate smectic or columnar phases, strong
anisotropic long-range interactions are required. These are provided by the Fint
contribution.
3. Fint – the enthalpic interactions between clay platelets
This term was derived from the pair correlation function for the particles, g(1,2);
hence it is mostly determined by the excluded-volume effects:
r r r r r r r r r r r r
Fint / kT = (1 / 2) ρ (r1 ) f (n1 )ρ (r2 ) f (n2 ) × δ (1 − n1 n2 )g(1, 2)V (r1 − r2 )dr1 dr2 dn1 dn2 (63)
∫
281
Clay-Containing Polymeric Nanocomposites
[ {(
U1 ( z ) = Eo 1 − exp − z − Leff )}] (65)
where Eo is the interaction energy between clay platelets and Leff is an effective
thickness of clay platelet. The second component, U2(z), was computed using the
SCF method. The shape of this potential depends on N, Ni, ρ and the binary
interaction parameters, χ.
The equilibrium morphology was computed for the mixtures of a polymer
(N = 300) with intercalated clay platelets, modelled as oblate disks having D = 30,
L = 1, thus p = 30. Two values for the clay-clay interaction strength were used,
E0 = 0 (no long-range attraction), and E0 = 0.1 kBT/a2 (strong attraction). All the
binary interactions, except that between polymer and intercalant were assumed
= 0; the latter χap = χ varied from –0.05 to +0.05. As far as the intercalation was
concerned, the following systems were considered: (a) ρ = 0.2, Ni = 5, (b) ρ = 0.04,
Ni = 25, (c) ρ = 0.02, Ni = 50, (d) ρ = 0.04, Ni = 50, and (e) ρ = 0.02, Ni = 100.
Note that the total amount of intercalant in systems (a)-(e) was: θ = ρNi = 1, 1, 1,
2, and 2, respectively.
The calculations of the phase diagram were carried out in two steps:
1. Using SCF the free energy profile U2(z) was computed for the five systems,
varying the binary interaction parameter within the indicated range, first for
E0 = 0, then for E0 = 0.1 kBT/a2.
2. The phase diagram was constructed as a map: χ versus φ (see Figure 68). The
total volume fraction of the intercalated clay: φc ≤ 0.601. Schematic
representation of the phases is shown in Figure 69.
The phase diagrams for the considered systems are complex. For χ > 0, the systems
are immiscible, showing coexistence between the polymer-rich isotropic phase
and the clay-rich crystalline phase. For χ close to 0, the two-phase region becomes
narrower and splits into isotropic-nematic and nematic-crystal phases. The triple
point (I-N-Cr) and the width of the nematic phase depend on the system. The
computed smectic phases were always metastable. For χ < 0, the isotropic-nematic
and nematic-crystal coexistence regions become narrower and shift toward higher
values of φ. When χ is strongly negative, the new ‘plastic solid’ (or house-of-
cards) and columnar phases appear. Evidently, at low clay loadings, the strong
repulsion between neighbouring disks forces them to adopt more energetically
favourable ‘edge-to-face’ or ‘house-of-cards’ configurations. This leads to either
gelation or crystallisation. At higher clay volume fractions, the steric excluded
volume effects dominate the long range disk-disk repulsion, forcing the formation
of columnar and crystal phases.
282
Thermodynamics
283
Clay-Containing Polymeric Nanocomposites
284
Thermodynamics
The phase maps in Figure 68 show similarity for the same total intercalant
loading, θ = 1 and θ = 2, viz. systems (a)-(c) and (d)-(e), respectively. However,
for platelets intercalated with short densely grafted chains (system a), the
immiscibility between the clay disks and polymer dominates the phase behaviour
of the system. This observation confirms the previous SCF computations, which
suggested that the present strategy of intercalation leads to an unfavourable
thermodynamic environment. Instead of high saturation of clay surfaces with
C12 to C18 alkyls an intercalation with fewer, strongly bound to the surface, long
chain molecules should be carried out. Note that increasing Ni from 25 (system
b) to 50 (system d) moves the isotropic-nematic-crystal triple point upward,
extends the stability region of the nematic phase to higher χ values and narrows
the two-phase isotropic-nematic region, indicating thermodynamically stable
exfoliated composites. Comparing systems c and e leads to similar conclusions.
One may object to the above computations on the ground that assumption of
E0 = 0 for the clay particles is not realistic. It is known that the surface energy of
a crystalline solid is high and that there is a strong van der Waals interaction
between the clay platelets. Thus, it is interesting to see how the results are affected
by the imposition of the strong clay-clay attraction, viz. E0 = 0.1 kBT/a2.
For systems with θ = 1, the clay-clay attractions dominate the entropic
contribution of the surfactant molecules. The phase diagrams show the
immiscibility between polymer and clay within the full range of χ. For systems
with θ = 2 (see Figure 70) the miscibility is significantly diminished in comparison
to the corresponding E0 = 0 cases (compare with systems (d) and (e) in Figure 68).
The isotropic-nematic-crystal triple point is shifted downward, the areas occupied
by isotropic and nematic phases is reduced, and the nematic-crystal transition
occurs at lower values of φ.
285
Clay-Containing Polymeric Nanocomposites
gained from compatibilisation of the polymeric matrix with the intercalant chains
– a large quantity of the compatibiliser would be required. By contrast, direct
compatibilisation of the clay/polymer shows greater potential. For this purpose,
the end-terminated macromolecular chains with single strongly bonding group
(a ‘sticker’) are preferred. Their chain length should be smaller, but of the same
order of magnitude as that of the matrix polymer. Evidently, for the practical
reasons (kinetics) one would start with pre-intercalated clay, and use the functional
compatibiliser with molecular weight just above the critical value for
entanglement.
More recently complex phase diagrams were computed. This was accomplished
by combining the SCF-generated free energy profiles with the Somoza-Tarazona
free energy functional. The computations demonstrated how variations of the
principal parameters affect the formation of isotropic, nematic, smectic, columnar,
crystal, and plastic solid (house-of-cards) phases. The calculated phase diagrams
286
Thermodynamics
are in qualitative agreement with the predictions of the SCF model. As the length
of the grafted chains and/or their density increases, the miscibility between the
clay sheets and the polymer is improved, and the resulting mixture can exhibit
exfoliated (isotropic or nematic) structures for a range of clay volume fractions.
For short intercalant chains, the polymer is unable to penetrate the galleries and
the system becomes immiscible. The computations demonstrated that the phase
equilibrium of CPNC is sensitive to the specific features of clay-clay, clay-polymer,
intercalant-polymer and clay-compatibiliser interactions. For quantitative
prediction of the phase behaviour, one must correctly describe all these
interactions, e.g., by using molecular simulation.
There is a large difference between the idealised mathematical model of CPNC
and the physical reality. For obvious reasons the ingredients used in the simulation
are homogeneous, monodispersed in size and molecular properties. Furthermore,
the simulation is based on equilibrium thermodynamics – the forces responsible
for the evolution of idealised CPNC structures are exclusively thermodynamic
and the final morphology is at thermodynamic equilibrium in the molten state.
The reality is quite different as the ingredients are far from homogeneous, there
are numerous process additives in each commercial resin, the clays are mineral
products with a host of compositional and structural defaults, the system is
mechanically dispersed which may either disturb the shape of clay platelets
(attrition or bending) and/or induce platelet orientation, then usually cooled down
to room temperature which induces vitrification or crystallisation that cause
internal stresses, etc. These are some of the reasons that make direct comparison
between the model and reality problematic. The model can and does serve as a
guide – with future developments the guide will become progressively more
realistic, able to account for the numerous contributions mentioned in the
preceding sentences. However, considering the complexity of the CPNC systems,
molecular modelling is the only method to examine the contributions of each
element, the only way to understand the mechanisms involved, and the only
logical approach to maximise nanocomposite performance.
287
Clay-Containing Polymeric Nanocomposites
that reduced the clay-clay interactions to zero. The melt was a mixture of telechelic
flexible N-polymers (their volume fraction = φ) and non-functionalised P-polymer
(volume fraction = 1-φ). These polymers had P ≥ N >> 1 statistical segments,
each of diameter a. The N-polymer had two ‘sticker’ terminal groups, one at
each end of the chain. The groups could interact with the clay surface with the
energy per sticker-clay contact of ε.
Thus, the gallery between the platelets was filled by N- and P-polymers. A fraction
of the N-chains was anchored to the platelets with the rest (as well as P-chains) being
free (subscript f). The anchored chains could be attached to the surface by one
(subscript t for ‘tails’) or two ends (subscripts l or b for ‘loops’ or ‘bridges’,
respectively). The following values of the Huggins-Flory interaction parameters
were assumed: χNN = χPP = 0, and χ = χNP. The free energy of the chains within the
gallery was expressed as a sum of the individual contributions:
F = Fads + Fint + Fcomp + Fel + Fent + Fdem (66)
where Fads is the sticker-surface adsorption energy for N-chains, Fint is the
interaction energy between the N and P chains, Fcomp is the compression energy
for chains at relatively low interlamellar gallery height, h, and Fel is the elongation
energy for loops, tails, and bridges, Fent is the entropic energy for mixing the
different types of chain configurations within the brush layers, and Fdem is the
demixing energy associated with extracting N and P chains from the surrounding
melt and localising these chains in the confined layers.
The free energy of the system, F, was written deriving the six components of
Equation 66 and casting them in terms of the reduced gallery height: a = h/Na,
αp= h/Pa, αtot = htot/Na and αl = hl /Na, where htot stands for the total height of the
brush, htot ≤ h/2 (with h being the gallery height), and hl is the average distance
that a loop molecule reaches from the clay surface. Its value depends on the
energy per contact between the clay platelet and a functionalised chain end (ε/T),
the volume fraction of functionalised chains in the bulk melt, N and P, the numbers
of segments in each functionalised and non-functionalised chain, respectively,
and the Huggins-Flory interaction energy parameter, χNP. Next, F was numerically
differentiated to obtain the conditions for local minima in respect to individual
volume fractions: φP, φl, φt, φb, and φf, calculated from the respective number of
statistical segments:
φl, t, b, f = nl, t, b, f Na3 / Ah ; φ p = n p Pa3 / Ah ; ∑φ = 1
i
i (67)
The free energy, F, was computed in its reduced form (in respect to temperature
and surface area) as a function of the reduced gallery height:
( )
Fa2 / AT = α Na3 / Ah ( F / T ) versus α ≡ h / Na (68)
The initial computations were carried out for the dispersion of intercalated clay
in a telechelic, bi-functionalised melt (φ = 1). The results are presented in Figure 71
as the reduced free energy and volume fractions of different conformations versus
the reduced gallery height, α. Four regions are indicated:
(I) The chains t, l, and b are highly compressed. The reduced free energy rapidly
decreases with α to negative values (miscibility).
(II) A shallow, local minimum of free energy, which originates in weak stretching
of all the chains within the brushes. The number of bridges decreases and
tends to zero on the border of this region.
288
Thermodynamics
Figure 71 The reduced free energy for different conformations versus the reduced
gallery height, α. Four regions of behaviour are indicated. After [Kuznetsov and
Balazs, 2000a]. See text.
(III) This is the ‘relaxation’ region, where the free chains appear. The free energy
is further reduced with α.
(IV)Separate brush layers are formed with unperturbed Gaussian free chains filling
the space between them, thus exfoliation.
The minimum in region (II) is thermodynamically metastable hence there is no
optimal spacing (intercalation) other than exfoliation. This is surprising as it
could be expected that the bridging chains give rise to a thermodynamic barrier
to separating clay platelets beyond the point where the bridges are disrupted.
Evidently, this energy cost is compensated by that gained by adsorption of free
chains, which can penetrate the gap at larger α. The results imply that clay sheets
can be exfoliated in a melt of telechelic chains. However, the metastable minimum
in region (II) can lead to a kinetically trapped degree of dispersion.
Additional computations show that the magnitude of the local minimum can
be controlled by the sticker adsorption energy, ε/T, and the molecular weight of
the N-chain. Evidently, increasing the former and decreasing the latter forces the
reduced free energy deeper into the negative values, increasing the miscibility.
However, for practical reasons this may not be the best solution. For sufficiently
small values of the barrier height, an imposed stress or increased temperature can
help overcoming the kinetic barrier and lead to exfoliated CPNC.
In a system comprising intercalated clay dispersed in a mixture of
functionalised (N) and non-functionalised (P) polymers the plots of the free energy
per area (F/T)(a2/A) versus the reduced gallery height, α, are similar to that shown
in Figure 71. However, at low volume fraction of N-chains, φ < 0.05, and high
e/T-values, the minimum in region (II) is a global one, forcing the system into a
289
Clay-Containing Polymeric Nanocomposites
290
Thermodynamics
291
Clay-Containing Polymeric Nanocomposites
adsorbed foreign substance (ni = 0) the surface tension coefficient, ν1, is given by
the ratio of surface energy to surface area; hence it may also be called the specific
surface energy.
The specific surface energy of solids, ν1, is difficult to measure as these are
often subjected to 3D residual stresses, surface roughness all the way to nanoscale,
readily adsorb environmental gas, vapour or liquid molecules and may be
contaminated by compounds that are difficult to remove. The highest measured
surface energy is for diamond: ν1(C-diamond) = 9820 mN/m. A high value was
also determined for orthoclase, KAlSi3O8, viz. ν1 = 7770 mN/m [Brace and Walsh,
1962]. The specific surface energy of a metal in equilibrium with its own vapour
is also high, viz. ν1(Cu) = 1,430, ν1(Au) = 1,510 mN/m, similarly for crystalline
oxides, viz. ν1(CaO) = 1,310, ν1(MgO) = 1,090 mN/m. By contrast, amorphous
bodies have significantly lower ν1 than crystalline. For example SiO 2 :
ν1(amorphous) = 260, ν1(hydrated, amorphous) = 130, while ν1(quartz) = 1030
and ν1(hydrated quartz) = 422 mN/m [Condon and Odishaw, 1967; Stokes and
Evans, 1997].
These values for crystalline solids should be compared with those of organic
compounds. For example, the polymer surface tension coefficients at 20 °C range
from 10 to 49 mN/m (for fluorinated acrylic to polyesters or polyamides,
respectively) [Brandrup et al., 1999]. Similar values have been measured for
organic liquids – the highest is ν1(glycerol) = 63 mN/m, with –OH groups on the
surface. In short, the surface energy of a crystalline solid is about two orders of
magnitude greater than that of organic liquids.
Owing to morphological nanorugosity the surface of crystalline solids is usually
highly complex. This is particularly true for mineral silicates where the surface
may be defined only in statistical terms. The clays, due to variation of composition,
show great variation of the surface heterogeneity [Papirer and Barard, 1998].
The latter also varies with the type of adsorbed compound. Evidently, adsorption
affects the surface energy of crystalline solids. For example, the specific surface
energy of freshly cleaved mica in vacuum is ν1 = 4,500 mN/m whereas that
measured in air is 375 mN/m.
One of the consequences of the surface energy contribution to the energetics
of a body is the dependence of the transition temperature on the degree of
dispersion. For example, the melting temperature of bulk PE is Tm ≅ 400 K, but
PE-particles with diameter varying from 13 to 5 nm have Tm = 266 to 218 K.
Another consequence of the high surface energy is the aggregation of solid
powders. According to Johnson et al. [1971], the force between two interacting
spheres (of radii R1 and R2) is given by:
ε = ν11πR1R2/(R1 + R2) (70)
For R1 = R2 the relation simplifies to read ε = ν11πR/2. Equation 70 is general and
independent of the elastic modulus. The attraction force is then proportional to
the radius – the smaller the particle, the smaller is the force of individual contact.
However, dividing the same mass of crystalline powder into the number of particles
requires that NiRi3 = NjRj3, thus a change of the total aggregation energy, E = Nε,
i.e.:
Niεi/Njεj ≡ Ei/Ej = (Rj/Ri)2 (71)
For example, to disperse the same volume of CaCO3 particles of about 10 nm diameter
would require 62,500-fold more energy than that needed for a standard filler powder
292
Thermodynamics
with diameter of about 2.5 μm. Furthermore, since the dispersing force during
compounding is given by the product of radius and stress, Rσij, to achieve the same
efficiency the stress should be increased by a factor of 200.
[ (
φ ex / φ b = A B + χ s − χ sc∞ )] (72)
where A ≅ 5/6 and B ≅ 1/5 are constants, χs is the Silberberg adsorption parameter,
and χ sc∞ is the critical adsorption energy for infinite chain lengths. With decreasing
chain length the adsorption/depletion transition shifts to lower χs values. This
effect is strongly enhanced if the end segments of the chain adsorb preferentially.
Cosgrove et al. [1987; 1991] used neutron scattering to study polymer
adsorption from dilute solutions on solids (mica or PS latex particles). The results
presented in Figure 74 indicated that homopolymer concentration exponentially
declines from the surface in the z-direction, while the copolymer concentration
profile follows a parabolic dependence. The thickness of the adsorbed layer varied
from one system to the next, but within a relatively narrow range of values. The
root-mean-square (rms) thickness was slightly larger than the unperturbed radius
of gyration, viz. 3.6 versus 4.8 nm for copolymer and 6.8 versus 9.0 nm for PS,
respectively. After evaporation of solvent the thickness of the adsorbed layer was
reduced by about 50% (viz. to 3.3 and 4.4 nm, respectively) indicating high
293
Clay-Containing Polymeric Nanocomposites
packing density in the original layer adsorbed from dilute solution. The rms
thickness of the adsorbed layer is one measure of the phenomenon, another being
the distance in the z-direction, zmax, over which the polymer concentration is
measurably higher than the bulk concentration, φ > φb. For the systems studied
by Cosgrove et al., zmax = 24 nm was reported. As shown in Figure 74, all other
parameters being the same, the magnitude of zmax very much depends on the
polymer molecular weight.
Israelachvili et al. [1984] reported that when two saturated layers of PS on
mica approach each other, starting at a characteristic distance, zc, they attract
each other. The experiment was conducted in a cyclohexane solution of PS, near
the Θ-condition using the surface force analyser (SFA; see Figure 75(a)) designed
and originally built by Israelachvili in 1978. The distance zc = 60 to 120 nm
depended on the PS molecular weight and the thermodynamic miscibility. The
results were well reproduced in two different laboratories.
294
Thermodynamics
Figure 75(b) The SFA was used to measure the viscosity of adsorbed PS-X from a
toluene solution. The results indicate a solid-like behaviour for the first adsorbed
layer: 2z < 220 ± 10 nm [Klein et al., 1993]. See text.
(b) Reprinted with permission from [Klein et al., 1993].
Copyright 1993 American Chemical Society.
295
Clay-Containing Polymeric Nanocomposites
Confirming the earlier observations, Klein et al. [1993] reported that non-
functionalised anionic PS poorly adsorbs from dilute toluene solution onto a
mica surface. The measurements gave the correct magnitude of the solution
viscosity within a few nanometres from the surface. The situation was dramatically
different when the PS chains were terminated with the zwitterionic group,
-(CH3)2N+-(CH2)3SO3–, giving ammonium-terminated PS-X. The molecular weight
of PS-X was Mw = 375 kg/mol, Mw/Mn = 1.03 and the radius of gyration in
toluene, Rg = 57.5 nm. Figure 75(b) also shows variation of the ‘effective mobility’
parameter, G, in the z-direction, thus orthogonal to the mica surface. The ‘effective
mobility’ parameter was defined as:
( Ao / A) − 1 = 2( z − z H ) / ηo
2
G ≡ 6πR2 ω / K (73)
where R is the mean radius of curvature of the mica sheets, K is the spring constant,
ω is the frequency, A and Ao are amplitudes of oscillation, z is the distance from
the mica surface and zH is its value (known as the hydrodynamic thickness) at
which the extrapolated value G = 0, and ηo is the zero-shear viscosity of the bulk
liquid.
With the low grafting density (mean spacing between attached chains of s =
14.5 ± 1.5 nm) the hydrodynamic thickness nearly doubles the radius of gyration.
Furthermore, within the first layer from the mica surface (110 nm or so thick)
the segmental mobility of PS macromolecules is practically zero, indicating a
solid-like behaviour of the adsorbed chains.
More recently, the surface force apparatus was redesigned and the
nanorheological measurements were carried out on undiluted polybutadiene (PBD;
Mw = 6.95 kg/mol; the entanglement molecular weight, Me = 1.85) [Luengo et
al., 1997]. The initial measurements of the normal forces at very slow approach
(2-3 min per point) indicated the presence of two regions: (1) a steeply repulsive
force with an incompressible ‘hard wall’ at zhw ≅ 5 nm of solid-like PBD adsorbed
on the mica surface, and a roughly exponential decay at larger distances. The
exponentially decaying region had a decay length of about 3.5 nm, which is close
to the unperturbed radius of gyration, Rg = 3 nm. These repulsive forces indicate
strong binding of polymer to the surface, at least over the time scales of the force
runs (1-2 h), and an immobilised layer of thickness of about 1.5 Rg per surface.
The chain conformations in such confined surface layers may be in the glassy or
rubbery state.
Next, the dynamic oscillatory measurements were carried out at strains γ < 30%,
frequency, ν (Hz) = 0.03 to 80 and with the separation distance, 2z = 10 to
250 nm. As the distance between two mica sheets decreased, three regions of the
dynamic behaviour could be distinguished: (1) bulk, (2) intermediate, and (3)
tribological. Figure 76 and Figure 77 present results of these measurements.
(1) Bulk: For 2z > 200 nm the phase angle (between strain and stress signals) δ ≈ π/2,
and the measured storage and loss shear moduli (G´ and G´´, respectively)
followed the bulk behaviour.
(2) Intermediate: At smaller z-gaps, δ < π/2 while the values of the shear moduli
were higher, showing an ‘elastomeric-like’ plateau indicating a 3D structure.
(3) Tribological: At the smallest gaps, 2z ≤ 12 nm, δ = 0, or a Hookean-type
response of an elastic body was obtained. On the flow curve (log viscosity
versus log deformation rate) the data followed a straight line with the slope
= –1, i.e., η ∝ 1 / γ˙ ; or : G ′ ∝ ν 2 and G ′′ ∝ ν where ν is the radial frequency.
296
Thermodynamics
Figure 76 Effect of surface separation (distance D = 2z) on the storage (G´) and
loss (G´´) moduli of PBD at T = 25 °C and frequency n = 13 Hz. Data [Luengo et
al., 1997].
297
Clay-Containing Polymeric Nanocomposites
The authors also reported the presence of normal stresses during the steady-
state shearing. Caused by them, initially the gap between mica sheets would
increase toward an equilibrium separation, to return to the original separation in
about one minute after stopping. The effect depended on the initial separation
and the shear rate. Since a similar behaviour has been observed for ‘brush’ layers
of zwitterion-terminated PS end-grafted to mica in toluene, the inference is that
PBD coils are effectively bound to the surfaces not by ionic but van der Waals
forces.
It should be stressed that such behaviour is not limited to macromolecules.
Low molecular weight organic solvents having either spherical or short-chain
molecules (e.g., alkanes, octamethyl-cyclotetrasiloxane, oligomers, etc.) behaved
similarly under confinement [Gee and Israelachvili, 1990; Granick, 1991; Hu
and Granick, 1992]. For example, when dodecane was confined to a diminishing
gap from ca. 5 to 2.8 nm it underwent an abrupt transition (similar to
crystallisation) to a solid-like state. Virtually all confined liquids solidified on the
mica surface. Since the process is rate-dependent (time scale ranges from minutes
to hours), the thickness of the solidified layer varied from two molecular layers
up. In some cases, with increasing confinement some liquids showed a smooth
increase of viscosity by up to 7 orders of magnitude. For either of these two types
of low molecular weight liquids the layer thickness within which the viscosity
was above that in the bulk was quite large.
298
Thermodynamics
299
Clay-Containing Polymeric Nanocomposites
The dynamics of the organic phase were studied using NMR surface-sensitive
cross polarisation and bulk-sensitive spin-echo experiments. Synthetic, Fe3+-free
fluorohectorite (FH) was intercalated with ODA, and then melt-annealed with
PS under static conditions [Zax et al., 2000]. Within the gallery the polymer
constituted 68 wt% (ODA the rest). The molecular dynamics simulation suggested
the presence of a symmetrical five-layer structure of the organic phase. Thus,
near the surface there was a preponderance of phenyl groups, next the backbone
carbons intermixed with the alkyl groups. The highest probability of finding the
intercalant carbon was within the central layer. The NMR results showed that
the chain segments (both phenyl and -CH2- groups) that interacted with the surface
were dynamically inhibited. By contrast, within the central layers the segments
were more mobile than in the bulk at comparable temperature. The transition
from the glassy to molten state took place over a wide temperature range – starting
at lower T and ending higher than for the bulk PS. Furthermore, by contrast
with the bulk behaviour, the PS inside the interlamellar gallery space did not
show the customary, isotropic molten phase behaviour.
Anastasiadis et al. [2000] used dielectric spectroscopy to study the segmental
dynamics of 1.5 to 2.0 nm thick polymer film confined between clay platelets in
a nanocomposite. For the study hectorite and MMT were intercalated with
dimethyl-dioctadecyl-ammonium bromide (2M2ODA). Mixing the dry
organosilicate with up to 30 wt% of poly(methyl-phenyl siloxane) (PMPS,
Mw = 2.6 kg/mol, Mw/Mn = 1.2) resulted in formation of h = 1.5 to 2 nm thick
polymeric films inbetween the organically modified silicates. The PMPS segmental
motion is dielectrically active. Three processes were detected: (1) slow, resembling
the one for bulk-PMPS; (2) intermediate, possibly related to orientational motions
of the intercalant; and (3) fast due to the confined PMPS.
300
Thermodynamics
301
Clay-Containing Polymeric Nanocomposites
ions having more than one type of substituent groups. However, the overall image
that emerges from these models is expected to remain intact: reduced segmental
mobility near the high-energy clay surface, increasing towards the characteristic
bulk melt mobility at a distance of ca. 100 nm.
Manias and Kuppa [2002] provided a short topical review, focusing on the
simulation of structure and dynamics of PS macromolecules in slits. The MD results
were compared to experimental results for CPNC containing onium-modified
fluorohectorite dispersed in a PS matrix. Reasonable agreement was found.
302
Thermodynamics
macromolecules strongly interact with clay, i.e., χsp << 0. The tails of these
compatibilising macromolecules should not favourably interact with intercalant
chains, i.e., χap ≥ 0, but be miscible with the matrix polymer. The kinetics of
intercalation for this case depend on the system (magnitude of interacting energies,
intercalant density and structure) as well as on the molecular weight of the
diffusing macromolecules [Balazs et al., 1998].
Diffusion is defined as a change of the centre-of-mass position of a
macromolecule (rCM) over time that is significantly longer than that required for
the configurational rearrangements. The simplest case is entropy-driven diffusion
of a molecule in a background of identical molecules – self-diffusion, Ds. When
the background molecules are not identical the process is called tracer diffusion,
D*. When the diffusion takes place in a mixture of two species, the mutual
diffusion coefficient is given by Fick’s law, as a ratio of the flux (J) to the
concentration gradient (∇c): DM = –J / ∇c. In the entangled melts the diffusion is
slow, with Ds = 10-10 to 10-16 m2/s, thus 1 h diffusion results in the displacement:
ΔrCM = 6tDs = 1.5 mm to 1.5 μm, respectively [Kausch and Tirrell, 1989].
The MW-dependence of the diffusion coefficient can be calculated from the
Rouse beads-and-springs model of polymeric chains as DRouse = (kBT/ζ)/N, where
ζ is the friction coefficient and N is the number of beads (proportional to MW),
and the longest relaxation time, τRouse ∝ N2. The Rouse model is adequate for Ds
and D* of low molecular weight species. For high molecular weight melts Doi-
Edwards reptation model still uses Rouse kinetics within the confining tube, but
to escape from the tube it must move over its primitive path:
⎧ D ∝ 1 / M for M ≤ Me
Dreptation = (4 / 15)( Me / M ) DRouse ⎨ s (74)
⎩ Ds ∝ 1 / M for M > Me
2
303
Clay-Containing Polymeric Nanocomposites
this region there is a strong dependence of DM on P-a, with a = 2.5 or 3.0, dependent
on the assumption. At a still lower range of non-entangled matrix, P << Pe, a = 1.
The derived relationships are based on the mean-field approach, where each
statistical element within either the diffusing or surrounding chain has the same,
average character. In consequence, these relationships are well applicable to
intercalation where the polymeric chain diffusing into the gallery is composed of
statistical segments favourably interacting with either the intercalant segments
or the clay. Diffusion of the end-functionalised compatibiliser macromolecules
will require further considerations.
where ρj, μ T* and Kij are, respectively, density, mass absorption coefficient and a
constant. The time-dependent quantity ζ(t) is a fraction of the melt-intercalated
organoclay. The kinetic curves, ζ(t) versus t, depend on composition (organoclay,
polymer, its Mw), temperature (T), pressure (P), etc. The kinetic of intercalation
curves were fitted to the relation derived by Breen et al., [1987] for vapour sorption
of MMT:
∞
ζ(t ) = 1 − ∑ (4 / α ) exp{− Da
m =1
2
m
−2
α m2 t } (77)
The latter authors modelled MMT as a cylinder of stacked circular disks, each of
the radius α. The diffusion was assumed Fickian, with the diffusivity constant,
D. Integration of the diffusion equation yields the above relation, where am is the
m-th positive root of the zero order Bassel function. The predicted dependence is
shown in Figure 78.
Fitting the kinetic data to Equations 76 and 77 Vaia et al., were able to determine
the effective diffusion rate parameter, D/a2. For the PS30/FH-ODA system the
temperature dependence was of the Fulcher-type: log(D/a2) = ao – a1/(T – T∞),
where a1 = 604 ± 40 K and T∞ = 322 K. For the series of narrow molecular
weight distribution (MWD) PS the data followed Equation 74. In Figure 79 the
self-diffusion data extracted from these measurements (FH-ODA with
monodispersed PS resins) as well as for PS fractions [Fleischer, 1987; Antonietti
304
Thermodynamics
305
Clay-Containing Polymeric Nanocomposites
and Sillescu, 1985] are plotted versus Mw. The solid lines are drawn with the
theoretical slope of –2, predicted by the reptation theory. The coefficient governing
the kinetic diffusion into galleries, Da-2, is ten decades larger than Ds for PS.
Assuming that the diffusion into the galleries is the same as in the case of self-
diffusion, one obtains for the apparent radius of the FH platelets a = 214 nm.
This seems to be the right order of magnitude. The reasonableness of this quantity
implies that diffusion into a gallery with, h = 1.2 to 2.2 nm, is not particularly
affected by the narrow slit geometry. This is striking, since the unperturbed radius
1 /2
of gyration of the PS samples used was rΘ2 = 5 to 15 nm (for Mw = 30 to
300 kg/mol) hence significantly larger than h. Thus PS macromolecules do not
diffuse as a Gaussian coil but as extended macromolecules with chain diameter
controlled by the segmental motion. According to Flory, the average diameter of
a paraffinic chain is equal to about 3.5 -CH2- units, thus having the diameter of
ca. 0.45 nm, for PS this magnitude is about twice as large, ca. 0.90 to 0.95 nm.
In another publication [Vaia et al., 1996] melt intercalation was carried out
on synthetic FH pre-intercalated with either dodecyl (DDA) or octadecyl (ODA)
ammonium ion. Two narrow molecular weight PS resins, with Mw = 30 and
400 kg/mol, and one poly-3-bromo-styrene (PS3Br) PS with Mw = 55 and Mw/Mn = 2
were used. XRD studies showed that in contrast with intercalated PS30/FH-DDA,
the PS3Br/FH-DDA system was exfoliated. Clearly, the polar Br-group in the
para position increased the polymer-silicate interactions to the extent that
exfoliation was possible. The exfoliation was partially confirmed by TEM.
Stacking of 5 to 20 layers with interlayer spacings of between 2 and 4 nm and the
presence of the original crystallites or the primary particle were discernible.
Individual silicate layers were observed near the edge whereas small coherent
layer packets separated by polymer-filled gaps are prevalent toward the interior
of the primary particle. The larger expansion of the gallery height and disordered
structure were apparently responsible for the disappearance of the XRD peak.
The heterogeneity of the CPNC structure, stacking in the primary particle
implies that the process is more complex than simple sequential separation of
individual layers starting from the surface of the primary particle. Long-range
forces (e.g., stresses associated with gallery expansion and layer bending) will
maintain stacking of an optimal size. Layer-by-layer delamination may take place
near the edge of the primary particle but it is unlikely in the central part. The
increased polarity of PS3Br (with respect to PS) will interact more with the polar
FH surface. As a result, the frictional coefficient, associated with polymer diffusion
into the gallery, should increase slowing the melt intercalation kinetics.
Qualitatively, these effects were observed.
Chen et al. [2003] followed the procedure used by Vaia et al. However, in this
case poly(styrene-b-isoprene) block copolymers (PS-b-PI) diffused into
interlamellar galleries of synthetic fluorohectorite, pre-intercalated with ODA.
Intercalation at T = 100 to 170 °C was followed by XRD for up to 70 h. The
copolymer diffused similarly on either side of the order/disorder transition
temperature. The intercalation rate decreased as the PS block increased.
306
Thermodynamics
∂μ ⎡ Do c( x ) Bo ⎤ ⎛ ∂μ ⎞ ⎛ Do ⎞ ⎡ c( x )h2 k B T ⎤
Dtrans = ⎢ + ⎥ ⎜ ⎟⎜ ⎟ ⎢1 + ⎥ (79)
∂ ln c( x ) ⎣ k B T η ⎦ ⎝ ∂ ln c( x ) ⎠ ⎝ k B T ⎠ ⎢⎣ 12Doη ⎥⎦
For the non-entangled melts, the Stokes equation holds, hence Doη/kBT = 1/3πa
(where a is segmental diameter). Thus, the diffusional component dominates for
small slit height, h, and the viscous one when the gap is wide.
The kinetics of melt intercalation by polymer diffusing into a clay slit under
stationary (no mixing) conditions was modelled using MD [Lee et al., 1998a;
1999; 2000; Baljon, 1999]. The simulation model was a face centred cubic lattice
oriented with planes parallel to the xy plane of the clay platelet. On each side of
the lattice stack there was a reservoir of molten polymer, equilibrated at constant
T and P. To start the process, two central lattice layers were removed to form a
rectangular slit into which the polymer could diffuse. The size of the slit was
fixed, non-expanding by the diffusion process. The system was strictly binary,
without a low molecular weight intercalant. The polymer molecules were
represented by anharmonic bead-spring chains. Polymer beads, separated by a
distance r, interacted with the interaction energy ε according to the truncated,
repulsive Lennard-Jones potential for r ≤ rc ≡ σ21/6. The finite extendable non-
linear elastic (FENE) model was used to express the bonding potential between
nearest-neighbour beads along the chain, separated by distance r. The bead-lattice
potential with the interaction energy εbl was given by truncated, attractive Lennard-
Jones potential at rc = 2.2σ. Thus, the bead-bead interactions were either zero or
repulsive at short distance, while the bead lattice was attractive. The simulations
were performed at constant T* =kBT/ε = 1, assuming that the ratio of the
interaction parameters, ε/εbl = 1, 2 or 3 (in latter publications the ratio went up
to 10), and the random force in y and z directions obeys the Gaussian statistics.
An analytical model for diffusion of polymer into a slit gallery of length L in
the x-direction was derived in the form of Laplace transforms:
sinh Ψ
ζˆ (s) =
[
sΨ cosh Ψ + (din / Dout )1 / 2 sinh Ψ ] (80)
Ψ ≡ sL / 4 Din
2
where Din and Dout are diffusion coefficients inside and outside the slit. Since the
Laplace transform is a function of sL2 divided by s, the intercalation kinetics,
307
Clay-Containing Polymeric Nanocomposites
ζ(t), depend on tL-2. The superposability of the kinetic curves computed for
different values of L would provide evidence that melt intercalation is a diffusion-
controlled process.
The computations were performed for L = 43σ to 341σ. The results ζ(t) versus
t/L2 indeed superposed onto a single curve. Assuming that Dout = ∞ the effective
diffusion coefficient, Din = Deff was calculated from Equation 80 by fitting the
dependence to the simulated kinetic curve. Excellent agreement between the
simulated data and the analytical prediction with the fitted value of Deff was
obtained.
It is important to note that as the interaction ratio, ε/εbl, increases the computed
kinetics slow down and the diffusion coefficient decreases. Since the diffusion
driving force is proportional to this ratio, crowding at the entry to the slit is
evidently slowing down the intercalation – the macromolecules want immediately
to interact with the slit walls instead of diffusing further into the gallery in a
more civil way. Crowding at the gap by macromolecules eager to interact with
slit surfaces also slows the intercalation process. As a result, the polymer
concentration decreases linearly in the x-direction and shows two local maxima
in the z-direction. While the x-gradient is a measure of the non-equilibrium aspect
of the process, the enhanced concentration of the interacting polymer segments
near the silicate wall is not.
Simulation was also carried out to determine the centre of mass diffusion of
polymeric chain within the reservoir. The computations determined that the
equilibrium, bulk self-diffusion coefficient, Ds = 0.006σ2/τ, but the effective
diffusion coefficient governing the intercalation Deff = 3σ2/τ, hence 500 times
larger. The authors argued that once the slit is open the process is no longer
governed by the equilibrium properties. Computations of the centre of mass
displacement of the 1st chain to enter the slit show that its diffusion coefficient is
comparable to Deff, while the macromolecules that follow diffuse more slowly.
Simulation of diffusion inside the gallery, in the y-direction gave very small values
– about 1/10 of the equilibrium Ds.
The amphiphilic intercalant may enhance the intercalation kinetics (relative
to the case of homopolymer intercalants) and form novel structures. Thus, in the
last publication of this series melt intercalation with symmetrical diblock
copolymer was simulated [Lee et al., 2000]. The model slit surfaces were assumed
grafted with low molecular weight intercalant. The system was maintained at
constant pressure to permit the slit to open as polymer intercalates. The kinetics
of intercalation were simulated for different values of surface-block-A and surface-
block-B interaction parameters. It was concluded that suitable diblock copolymers
might be used to intercalate clay.
Starting with the Landau and Lifshitz one-dimensional equation of motion,
Ginzburg et al. [2001] derived a simple relation that describes the dynamics of
melt intercalation. The derivation is based on a model, which assumes the presence
of ‘kinks’ – a sudden, local expansion of the interlayer spacing between two clay
platelets. Accordingly, intercalation is a process of localised excitations that move
the kink, opening the interlamellar space. The model stipulates that the kinks
originate in the interplay between the double-well potential for the clay-clay
long-range interaction, bending elasticity of the platelets, and sufficiently strong
external shear force.
308
Thermodynamics
( P + a / V )(V − b) = T / R
2
( )( )
or P˜ + 3 / V˜ 2 3V˜ − 1 = 8T˜
V˜ = V / V*; T˜ = T / T*; P˜ = P / P * (81)
V* = 3b = Vc ; T* = 8a / 27 Rb = Tc ; P* = a / 27b2 = Pc
Pc Vc / RTc = 3 / 8
Of interest to van der Waals were low molecular weight liquids with a well-
defined critical point – the coordinates of this point, Pc, Vc and Tc, were used as
the reducing parameters. For T = 0 the hard-core volume, Vo = b. van der Waals
considered that molecules move in ‘cells’ made by the surrounding molecules
with uniform potential. The volume, within which the centre of a molecule can
freely move, is what defines the free volume. The free volume fraction is usually
defined as: f = Vf /V = V – Vo/V, where Vf = V – Vo. Detailed methods of
computation of Vo from the chemical structure have been developed, viz. [Bondi,
1968; van Krevelen, 1993; Porter, 1995].
Several comprehensive reviews of the eos’s used for polymeric liquids have
been published. For example, Rodgers [1993] collected PVT data for 56 polymers
at P ≤ 200 MPa and melting T-range from 50 to 170 °C. The review presents
fundamentals of the theories and it evaluates fit to experimental data. Five
prominent eos were examined. These are listed in chronological order.
1. Flory-Orwoll-Vrij (FOV) [1964]:
˜ ˜ / T˜ = (1 − V˜ −1 / 3 ) −1 − 1 / VT
PV ˜˜
˜ ˜ ˜
V = V / V*; T = T / T*; P = P / P * (82)
V* = ρ ; T* = s*η* /(c* k B ); P* = c* k B T * / V *
*
3
where: ρ*, s*, η*, c* are respectively: the ‘hard-sphere’ radius, number of
contacts per segment, the segment-segment interaction energy, and the
coordination number (kB is the Boltzmann constant).
2. Simha-Somcynsky [1969] (S-S) – will be discussed in the next section.
3. Sanchez-Lacombe [1978] (S-L):
309
Clay-Containing Polymeric Nanocomposites
[ ]
˜ ˜ / T˜ = −V˜ ln(1 − ρ˜ ) + (1 − 1 / r )ρ˜ − 1 / TV
PV ˜˜
ρ˜ = 1 / V˜ = V * / V ; T˜ = T / T*; P˜ = P / P * (83)
where r = M w P * / RT * ρ*; T* = ε * / k B
where M w is the weight-average molecular weight, while ρ* is the
characteristic density parameter. The parameter r represents the number of
lattice sites occupied by the r-mer. Evidently, its presence in the eos negates
the principles of corresponding states – it can be recovered only for r → ∞.
4. Hartmann and Haque [1985] (H-H):
˜ ˜ 5 = T˜ 3 / 2 − ln V˜
PV
(84)
V˜ = V / V0 ; T˜ = T / T0 ; P˜ = P / B0
The characteristic pressure reducing parameter, B0, has been identified as the
isothermal bulk modulus extrapolated to T = 0 and P = 0.
5. Dee and Walsh [1988] (D-W):
( ) − (2 / T˜ )(1.2045V˜ )
−1
˜ ˜ / T˜ = 1 − 0.8909qV˜ −1 / 3
PV −2
− 1.011V˜ −4
(85)
q ≅ 1.07 ; V˜ = V / V*; T˜ = T / T*; P˜ = P / P *
Within the low-pressure region Rodgers found that all these five eos are adequate
– the worst performance was of S-L and the best of S-S theories. However, as the
pressure increased, FOV and S-L dependencies started to perform poorly, while
S-S and D-W continued to provide good description. Rodgers cited the following
deviations: for FOV ΔV × 104 = ± 22 (7), for S-L ΔV × 104 = ± 33 (10), for H-H
ΔV × 104 = ± 9 (6), for D-W ΔV × 104 = ± 6 (5), and for S-S ΔV × 104 = ± 7 (4).
These differences were computed for the full pressure range; the values in
parentheses are for the low pressure range, P ≤ 50 MPa.
310
Thermodynamics
define a universal, reduced P˜ − T˜ − V˜ surface for all liquids. In other words, they
generate master isotherms and isobars. Provided the theory is quantitatively
successful, a superposition of experimental and theoretical lines will yield the
scaling parameters and thus the material characteristic interaction parameters,
ε* and v*.
To derive the eos, S-S first calculated the partition function, Z, for all possible
numbers of arrangements of occupied sites and empty holes in a lattice with z
coordination number. The Helmholtz free energy is directly given as: F = -RT
lnZ. In reduced variables the obtained free energy function F̃ has the
form: F˜ = F˜ [V˜ , T˜ , h(V˜ , T˜ )] . Thus, in addition to the usual volume and temperature
dependence, F̃ contains the hole fraction h, which in turn must vary as: h = h(V˜ , T˜ ) .
This variation is obtained by minimising the free energy at a specified volume
and temperature, i.e.:
(∂F˜ / ∂V )V˜ , T˜ = 0 (87)
From the Helmholtz free energy the pressure is obtained as:
P˜ = −(∂F˜ / ∂V˜ )T˜ (88)
From the above relations the S-S eos is derived in the form of coupled equations:
˜ ˜ / T˜ = (1 − η)−1 + 2yQ2 (1.011Q2 − 1.2045) / T˜
PV (89)
3c[(η − 1 / 3) /(1 − η) − yQ (3.033Q − 2.409) / 6T˜ ] + (1 − s) − sln[(1 − y) / y] = 0 (90)
2 2
with Q = 1 /(yV˜ ) and η = 2-1/6yQ1/3. The two equations not only predict how the
specific volume varies with pressure and temperature, but at the same time how
the free volume parameter, h, changes with these. Of all the eos, only the one
derived by S-S explicitly gives the hole fraction, h = 1 – y, which is directly related
to the free volume fraction, f. Equations 89 and 90 provide a corresponding
states description of the PVT behaviour of any liquid. Once the four characteristic
311
Clay-Containing Polymeric Nanocomposites
parameters: P*, V*, T*, and 3c/s are known, the specific volume and all its
derivatives are known in the full range of P and T. For linear molecules the external
degrees of freedom are proportional to the number of segments: 3c = s +3. Thus,
for linear polymers, where s >> 3, the external degree of freedom: 3c/s ≅ 1; hence
for polymers, only three parameters: P*, V*, and T*, are required.
The S-S theory also provides a simple expression for the reduced cohesive
energy density (CED):
[
˜ = U˜ / V˜ = −( y / 2V˜ )( yV˜ )−2 2.409 − 1.001( yV˜ )−2
CED ] (91)
where U is the internal energy of the system – one of the intensive thermodynamic
quantities. From CED the solubility parameter can be calculated as
δ = CED = CED ˜ × P * . Accordingly, δ is also an intensive function of
independent variables: δ = δ(T, P), independent of other variables, viz. the type
of solvent used to dissolve a given polymer. Recent analysis of δ for 38 different
molten polymers shows that, in accord with van der Waals prediction, the product
˜ ˜ )1 / 2 is approximately constant, thus δ is proportional to polymer density,
δV ∝ (UV
ρ = 1/V, which in turn depends on T and P [Utracki and Simha, 2004; Utracki,
2004]. Comparison with the values listed in handbooks for δ indicate that these
are significantly lower than computed from the polymer melt properties. The
origin of this discrepancy has been traced to the free volume contribution – since
the experimental values for δ are determined in solution, the macromolecular
environment there (i.e., free volume) is equivalent to that found in molten polymer
at high temperature, viz. T ≅ Tg + 300. Considering that different polymers have
different compressibility and thermal expansion coefficients, the difference
between the solubility parameters of two liquids (supposedly related to their
miscibility) will change with T and P. Users beware!
The full range of the reduced independent variables of polymer melts was
calculated as [Utracki and Simha, 2001a]:
1.6 < 100 × T˜ < 7.1 and 0 < 100 × P˜ < 35 (92)
Owing to the overlapping properties of polymers, the range of variables in these
inequalities is much wider than that experienced by a single resin. Within these
limits the coupled eos in Equations 89 and 90 can be approximated by
polynomials. The goodness of fit was judged by considering the values of the
standard deviation (σ), the correlation coefficient squared (r2) and the coefficient
of determination (Cd). The reduced specific volume follows the dependence:
[ ( ) ]
ln V˜ = ao + a1 T˜ 3 / 2 + P˜ a2 + a3 + a4 P˜ + a5 P˜ 2 T˜ 2 (93)
The values of ai parameters and the statistics of fit are listed in Table 42.
Considering the value of the standard deviation (σ = ± 0.18%) the fit is considered
satisfactory.
The following expression well approximates the hole fraction:
( )
h V˜ , T˜ = ao + a1 / V˜ + a2 T˜ 3 / 2 + a3 / V˜ 2 + a4 T˜ 3 (94)
Again, the goodness of the fit can be judged by the parameter values listed in
Table 42. However, even with only three parameters (i.e., assuming that a3 = a4 = 0)
the standard deviation of σ = 0.55% was computed.
312
Thermodynamics
a5 -1329.9 ± 52.8 —
_ 0.00183 0.00253
r2 0.99973 0.99965
Cd 0.99967 0.99899
( )
δ˜ = ao + a1 P˜ / T˜ + a2 + a3 P˜ + a4 P˜ 2 T˜ (96)
The numerical values of the fitting parameters for equations 95 and 96 are listed
in Table 43. Evidently, the polynomial expressions well approximate the eos
prediction, even with three parameters.
There are several practical advantages of these polynomial relationships. In
spite of their simple form they provide good approximation of thermodynamic
properties in the molten state within the full range of P and T. Their derivatives,
e.g., the thermal expansion coefficient and the compressibility factor:
α ≡ (∂ ln V / ∂T ) P−const and β ≡ (∂ ln V / ∂P)T =const
respectively, can easily be calculated for any temperature and pressure.
Furthermore, fitting Equation 93 to experimental data results in rapid
determination of the reducing parameters, P*, V* and T*. When highly accurate
values of these parameters is required (viz. for determining the binary interaction
parameters, ε* and v*), the latter values may be used as the initial estimates for
the iterative fitting of the data to the coupled Equations 89 and 90. This approach
greatly shortens the iteration process and provides highly reliable solutions.
313
Clay-Containing Polymeric Nanocomposites
It is evident that the reducing parameters of the S-S eos, P*, V* and T* (or the
interaction parameters incorporated there) must depend on the polymer molecular
characteristics (its conformation, configuration, molecular weight, etc.) as well
as on the additives, present in all commercial polymers [Utracki, 2002b].
As an example Table 44 lists the values of the reducing parameters for several
PS resins. The molecular weight of resins marked Z (for Zoller) is Mw = 110 to
0.9 kg/mol. Nova PS1301 (Mw = 270 kg/mol) is a ‘crystal’ (transparent) PS for
extrusion, thus probably relatively free of additives. Dow 667 is an injection
moulding grade containing 2.5 wt% mineral oil. The other commercial resins,
BASF 1424 and Monsanto HH105, have unknown additives. The indicated
authors computed the last four sets of parameters from the same set of
experimental data (measured by Quach and Simha in 1971), but using different
procedures. Evidently, the characteristic parameters depend not only on polymer
MW and diverse additives, but also on the routine used to compute them, viz.
sequential or simultaneous, the criteria used for minimisation of deviations, etc.
In many cases, only a relative change of polymer specific volume is of interest
and the use of listed in the literature values of P*, V* and T* is acceptable. In
this case it is possible to compute the PVT surface and obtain all the derivative
properties (viz. thermal expansion coefficient, compressibility, etc.) using tabulated
parameters. When more fundamental information is required, repetitive tests of
a given resin must be conducted with precision ΔV < 0.2%.
314
Thermodynamics
Note: The first 8 sets of parameters in this table were computed by the author
(LAU)
315
Clay-Containing Polymeric Nanocomposites
Jain and Simha [1980; 1984] demonstrated that for such binary mixtures the
S-S theory is directly applicable provided that the reducing and interaction
parameters are treated as averages. Thus, fitting Equations 89 and 90 to
experimental data yields the composition-dependent averages indicated by the
angular brackets, viz. X . Extension of the S-S theory has to account for the
presence of component-1 (mole fraction x1) and component-2 (x2 = 1 – x1):
( )
P * = qz ε * / s ν * ; T * = qz ε * / R c ; V * = ν * / Mo
P * V * / R T * = c / s 1 / Mo ( )( ) (97)
c = c1 x1 + c2 x2 ; s = s1 x1 + s2 x2
Mo = ( Mo1 s1 x1 + M02 s2 x2 ) / ( s1 x1 + s2 x2 )
where: zqi = si(z – 2) + 2 with z = 12. Then the averages <ε*> and <v*> are
related to the individual interactions as follows:
p
ε* ν* = X12 ε11ν11 + 2 X1 X2 ε12
* *p
ν12 + X22 ε 22
* *p *p
; p = 2, 4 (99)
The two values of p reflect the assumed Lennard-Jones 6-12 pair potential. The
two relations in Equation 99 have six parameters, four of which are accessible
from the PVT measurements of the neat components (i.e., polymer-1 and polymer-2),
thus the two cross-interaction parameters, ε12
*
and ν12
*
can be determined. Their
value may indicate attractive or repulsive cross-interactions, but as experience
with liquid mixtures showed, the strong attractive energetic interactions usually
lead to a smaller value of the volumetric interaction parameter. To facilitate
computations, Equation 99 can be transformed into:
2 Ξ4 Ξ2
ν* = × ν11
*2
; and ε * = 2 × ε11
*
Ξ2 Ξ4
⎛ ν * ⎞ ⎛ ε* ⎞
2
316
Thermodynamics
( )
1 /2
ε12
*
= δ e ε11
*
× ε 22
*
3 (101)
( )
⎡ * 1 /2
( )
1 /3 ⎤
ν12
*
= δ ν ⎢ ν11 + ν 22
*
⎥⎦/ 8
⎣
In these dependencies the two adjustable parameters are close to unity, δe, δv ~ 1
(maximum departure from unity was reported by Simha and Moulinié [2000] to
be ca. 13%). Note that the Berthelot’s geometric mean rule with δe = 1 has been
shown to be valid in many applications.
The next step is extension of this binary treatment to suspensions.
317
Clay-Containing Polymeric Nanocomposites
from the matrix macromolecules by size and the interaction parameters. Both
components, the matrix and the solid particles, are placed on a lattice, assuming
that hard-core specific volumes of the components are about equal: ν11 *
~ ν 22
*
.
For the flexible polymeric chain the external degree of freedom, 3c, is assumed to
be proportional to the number of statistical segments, s, and for macromolecules
3c1/s1 → 1. By contrast, for solid particles this parameter tends to zero, 3c2/s2 → 0.
Furthermore, since now the PVT behaviour of component 2 (solid particles!) is
not accessible, additional assumptions are needed to solve Equation 99.
The validity of these assumptions was demonstrated by Simha et al. [1984;
1986] and by Papazoglou et al. [1989]. The aim of these studies was to examine
the suitability of the S-S eos theory for describing the observed changes in the
system modulus, thermal expansion coefficient and the compressibility engendered
by the addition of solid particles. The authors computed these functions for specific
ratios of the interaction parameters, viz.:
3
⎧⎡
( ) ⎫
1 /3 ⎤
ν 22
*
/ ν11
*
= 1 : 1; ν12
*
/ ν11
*
= ⎨⎢1 + ν 22
*
/ ν11
*
⎥⎦ / 2⎬ = 1.0492
⎩⎣ ⎭ (102)
ε *
22 /ε
*
11 = 5; ε
*
12 /ε
*
11 = 1.2 − 10
It has been shown that the extended S-S theory was able to account for different
experimental sets of data and demonstrated that for an optimised ‘adhesion ratio’,
∗ ∗
ε12 /ε11 , good agreement between the S-S eos and several continuum-based theories
of the system modulus was achieved.
It is noteworthy that the relationships in the first line of Equation 102 are
consistent with the fundamental assumption of the lattice theories that the cell
size for any component in the system should not differ by more than 10% from
the average. The Berthelot’s geometric mean rule was also assumed valid, thus:
ε12
*
/ ε11
*
= ε 22
*
/ ε11
*
≅ 2.24 .
318
Thermodynamics
319
Clay-Containing Polymeric Nanocomposites
320
Thermodynamics
The deviations from the theoretical dependence at ambient P and the highest T
are caused by thermal decomposition and degassing.
The reducing parameters (P*, V*, T*) were obtained by the simultaneous least
squares fit of all data points to the S-S eos (Equations 89 and 90). Their values, the
statistics of fit, and interaction parameters computed from Equation 86 are listed
in Table 45. To directly compare the specific volume variations, V = V(P, T), for
PA and PANC the predicted dependencies were computed by substituting the
reducing parameters from Table 45 into Equations 89 and 90. To avoid crowding
the figure, only five pressures are shown. Computations simultaneously provided
h = h(P, T). The results are presented in Figure 83.
In Figure 84 the ratios V(PA)/V(PANC) and h(PA)/h(PANC) at the same T
and P are shown. While the addition of organoclay to PA reduced the specific
volume by about 1% (insensitive to P and T) the effect on the hole fraction is
more pronounced (by ca. 15%) and more dependent on the independent variables.
Up to this point the treatment of the PVT data for PA and PANC were identical
– for the former it resulted in the material-characteristic reducing and interaction
parameters, whereas for the latter only average values were obtained. To calculate
the individual binary interaction parameters of Equation 99, the site fractions,
Xi, must be calculated from a CPNC model.
The CPNC from Ube is known to be exfoliated, free of interfering low
molecular weight intercalant and the clay concentration is low. Thus, the first
proposed model is that of randomly dispersed clay platelets in a molten PA matrix.
Accordingly, the clay platelets may be approximated by disks of diameter
d = 200 nm and thickness t = 1 nm, density, ρ = 2.5 g/ml, with ‘molecular’ mass,
M = NAρπd2h/4 = 47,296 kg/mol and ‘molecular’ volume Vp = M/ρ = 18.92 × 106
ml/mol. This volume is assumed to occupy s2 lattice sites. In the lattice model of
a mixture, the hard-core volumes of the constituents should not differ too much.
For the assumed 6-12 potential the factor 21/6 relates the positions of potential
Table 45 Eos fit to PVT data for PA-6 and PANC from Ube. Data
[Simah et al., 2001]
Parameter PA-6 PANC
321
Clay-Containing Polymeric Nanocomposites
Figure 83 Specific volume (a) and hole fraction (b) for PA-6 and PANC versus
temperature at five pressures: ambient, 50, 110, 150 and 190 MPa. Note that a
small difference in density translates to a substantial loss of the free volume
parameter, h.
Reprinted with permission from [Utracki et al., 2003]. Copyright 2003 American
Chemical Society.
322
Thermodynamics
Figure 84 The V and h data from the preceding figure are plotted as ratios at the
same T and P (for each point). Note the reverse P-dependence – while the ratios of
h increase with P, those of V decrease.
Reprinted with permission from [Utracki et al., 2003]. Copyright 2003 American
Chemical Society.
323
Clay-Containing Polymeric Nanocomposites
Besides the unexplained large value of the volume repulsion parameter, ν12*
,
the disproportionately large reduction of the matrix free volume by addition of
0.64 vol% of clay is inconsistent with the model – the model simply does not
offer any mechanism that could justify these results. The assumption of naked
clay platelets randomly floating in molten PA-6 contradicts the high energy of
crystalline solids discussed in Section 3.1.7.1, the results computed from MD
adsorption of organic molecules on the clay surface, and the direct measurements
of solidification of macromolecules (by means of surface force apparatus and
neutron scattering) on the high-energy solid surface (see Section 3.1.7.2). Thus,
the simple, additive model had to be modified.
324
Thermodynamics
(1) The reduction of molecular mobility near the crystalline surface computed
from MD and measured experimentally. This has been discussed in Section
3.1.7. Several researchers reported an increase of viscosity as the distance
from the clay platelet decreased toward the last 4 to 6 nm – at that stage the
viscosity reached an immeasurably high value, taken as an indication of
solidification. For example, the dynamic oscillatory measurements identified
three regions: bulk behaviour for z > 100 nm, intermediate, and solid-like
for z > 6 nm where Hookean-type stress-strain behaviour was observed
[Luengo et al., 1997].
(2) The molecular structure of Ube PANC. According to an early patent, the
preparation of exfoliated PNC involved three steps [Deguchi et al., 1992]:
(a) intercalation of MMT with ω-dodecanoic acid ammonium chloride (ADA),
(b) mixing the intercalated clay with ε-caprolactam and water, and (c)
compounding the adduct in a TSE with ca. 70% of PA-6. Chain-ends titration
indicated that about 1/3 of the macromolecules were end-tethered to the
clay surface.
(3) The observed PVT behaviour of PA, PANC and their 1:1 mixture. The PVT
data were collected with painstaking care, investigating all possible influences,
sources of error and ad nauseam verifying the reproducibility. The new sets
of data for PA and PANC confirmed the accuracy of the preliminary findings,
and lead to similar values of the interaction parameters. However, calculation
of the binary interaction parameters using different pairs of the three polymeric
compositions (PA, PNC and their 1:1 mixture) resulted in different values of
the binary interaction parameters. The assumption of random mixing is
probably not correct for the CPNC system studied, and a different model
must be proposed.
The new model considers that in these diluted and exfoliated PNC:
1. Clay platelets are exfoliated and at the concentration of 0.64 vol% (hence φ
= 0.0064) they are randomly distributed in the PA-6 matrix.
2. 1/3 of clay cations are used for end-tethering the PA-6 macromolecules.
3. Contrary to the previous assumptions, the clay platelets are not bare, but
rather they are enrobed in two PA-6 layers of different structure and
properties.
4. Directly on a clay platelet there is the first or inner layer of solidified PA-6,
zsw ca.6 nm thick. As the distance from the clay platelet surface exceeds this
limit, an intermediate layer starts. This layer, where PA-6 chain mobility
progressively increases, extends from ca. 6 to ca. 100 nm from the platelet
surface, thus 6 ≤ zin (nm) ≤ 100. At still larger distance, z > 100 nm, the
segmental mobility of this exterior layer is the same as that in the bulk
polymeric matrix.
This model of ‘hairy clay platelets’ (HCP) [Utracki and Lyngaae-Jørgensen, 2002]
implies that only at φ < 0.005, where the clay platelets are more than 200 nm apart
(the assumed diameter of the model disk is 200 nm), are the values of the interaction
parameters expected to be constant. At higher concentrations, φ > 0.005 or w > 1.2
wt%, the HCPs overlap, PA-6 macromolecules with bulk properties are absent,
and the interactions depend on composition. Thus, the adopted model considers
individual clay platelets to be covered by solidified polymer and dispersed in a
matrix composed of PA macromolecules of the intermediate and exterior layers. It
325
Clay-Containing Polymeric Nanocomposites
is important to note that in this new model the random placement of binary
component has been assured by virtue of redefining the dispersed particles as HCP.
In the calculations it was assumed that the ‘12’ parameters characterising the
hetero-contacts are approximated by averages – the repulsive volume by the
algebraic average of the radii, the attractive interactions by Berthelot’s geometric
mean rule, i.e., that in Equation 101: δe, δv = 1. Applying the model to Equation
99 resulted in the sets of binary interaction parameters listed in Table 47. The
model considers the clay platelets to be covered by two layers of PA-6 with the
segmental mobility increasing with the distance z from the platelet surface. In
consequence it is expected that the interaction parameters will be similar
ε11
*
≈ ε12
*
≈ ε *22 . This is indeed shown by data listed in Table 47.
Thus, for the simplest diluted and exfoliated CPNC systems, the PVT
measurements provide well-defined functions of V = V(P, T) and h = h(P, T).
Furthermore, from the reducing parameters the average values of the energetic
and volumetric parameters can be unambiguously calculated. However, the
calculations of the individual interaction parameters ‘11’, ‘12’, and ‘22’ very
much depend on the adopted model – on the definition of what physically are the
interacting species ‘1’ and ‘2’. Thus, when ‘1’ is taken as an average statistical
segment of the PA macromolecule and ‘2’ an inorganic ‘bare’ clay platelet the
energetic interactions: ε 22 *
≅ 95ε11
*
are found. On the other hand, when the model
specifies that species ‘1’ are statistical segments of PA in the melt and ‘2’ are
inorganic clay platelets embedded in layers of PA with reduced chain mobility,
the energetic interactions change dramatically to ε 22 *
≅ ε11
*
.
On face value both approaches are correct and the relative magnitudes of the
energetic interactions have physical sense. However, while the former model was
unable to explain the significant reduction of free volume, the latter model provides
a direct and unequivocal response: it is precisely the strong interaction between
the clay surface and PA-6 segments that causes the reduction of segmental mobility
and the reduction of free volume. The latter model also agrees with the well-
documented adsorption of organic molecules of inorganic, high surface energy
substances. It is consistent with our understanding of this type of CPNC.
Notes: In the PA/PANC mixture and in PANC the variations of v*ij are as
postulated in the text. Values of ε*ij in parentheses were computed for matrices of
different mobility hence they are fitting averages. The experimental error for ε*ij
and v*ij is ± 1.5 and ± 1.0%, respectively.
326
Thermodynamics
Figure 85 Hole fraction as a function of temperature and pressure for neat PS 1301.
327
328
Table 48 Statistics of fitting the Simha-Somcynsky eos to experimental data and the computed parameters for PS,
and PNC containing 1.4 to 17.1 wt% Cloisite‚ 10A [Tanoue et al., 2003a; 2004]
Parameter PS1301 HS16A HS17 HS18 HS19 HS20
104 × V* (ml/g) 9525.9 ± 4.7 9583.7 ± 9.6 9567.8 ± 5.9 9458.8 ± 9.8 9259.6 ± 15.1 9011.2 ± 14.6
<εij> (kJ/mol) 32.49 ± 0.06 33.08 ± 0.14 33.28 ± 0.08 33.19 ± 0.13 32.80 ± 0.20 32.45 ± 0.20
<vij> (ml/mol) 43.69 ± 0.23 44.16 ± 0.48 44.53 ± 0.30 43.92 ± 0.50 43.90 ± 0.77 43.05 ± 0.78
Thermodynamics
The most interesting question was how the addition of different amounts of
organoclay affected the free volume fraction, i.e., the h-function. A plot of the
relative hole fraction, h(PNC)/h(PS) at constant pressure P = 1 MPa and three
temperatures, T = 360, 460 and 560 K, is shown in Figure 86. A similar plot of
the relative specific volume, V(PNC)/V(PS), versus w linearly decreased in the
full range of composition, consistently with the constant ratio of densities in the
molten state: ρ(organoclay)/ρ(PS) = 1.49.
The free volume in PANC with 2 wt% organoclay dispersed in PA-6 at
T = 300-590 K and P = 0.1 to 200 MPa was lower by 12 to 17% than that of the
matrix (see Figure 84). Since during the reactive exfoliation the intercalant
(ω-amino dodecyl acid (ADA)) became the first mer that end-tethered PA-6
macromolecules to the clay surface, there was nothing in these nanocomposites
to prevent adsorption of PA-chains on the high surface energy clay platelets. The
adsorption and resulting reduction of chain mobility caused such a large loss of
free volume. The dependencies displayed in Figure 86 are most interesting since
in these PS-based CPNC the degree of intercalation/exfoliation is incomparably
lower than that in PA-6/MMT. Furthermore, here the 2MBHTA intercalant is in
stoichiometric excess (over MMT CEC), thus it forms an intermediate layer
between the inorganic, high-energy clay surface and PS matrix. As a consequence,
one would not expect PS macromolecules to be adsorbed and loose mobility.
Apparently, in spite of these obstacles, the clay is able to reduce PS segmental
mobility. Furthermore, the data show that initially the relative loss of free volume
is proportional to the clay content – more clay, less free volume. Figure 86 indicates
that h(PNC) < h(PS) for organoclay content from 0 to ca. 16 wt%. However, the
dependence reaches a local minimum at ca. 4 wt% organoclay (4 to 6% loss of
the free volume) then starts to increase with the organoclay loading. The latter
effect is related to progressively poorer dispersion of clay platelets.
329
Clay-Containing Polymeric Nanocomposites
Figure 87 Relative hole fraction of PS1301 with 0 to 17.1 wt% of Cloisite® 10A at
T = 360, 460 and 560 K as a function of the average energetic interaction
parameter, ε * . In the upper part the linear regression results are shown; in the
lower part the organoclay concentration for each data point is given. Data
[Tanoue et al., 2003a; 2004].
330
Thermodynamics
331
Clay-Containing Polymeric Nanocomposites
332
Thermal Stability
3.2
Thermal Stability
333
Clay-Containing Polymeric Nanocomposites
334
Thermal Stability
The authors did not observe any significant changes to the thermal decomposition
of organoclay treated with t-butyl dimethyl chlorosilane. In air, the decomposition
started with a small TGA peak at about 150 °C and a major one centred at
250 °C. Under nitrogen the decomposition started at ca. 180 °C and proceeded
in three steps with peaks at 254, 320 and 438 °C.
In their patent of 1998, Christiani and Maxfield noted that a MMT-ammonium
complex with secondary amine was more thermally stable (onset of decomposition
at T = 275 °C) than that with either tertiary or quaternary ones. Thus, for melt
exfoliation in a PA matrix, they preferred MMT pre-intercalated with dipentyl
ammonium chloride.
Gilman et al. [2000a; 2000b] reported that during extrusion compounding
of PS with MMT-2M2ODA (dimethyl dioctadecyl ammonium chloride) at 185 °C
the intercalant was thermally degraded. The authors pointed out two factors
causing this unwanted effect: increased temperatures and the presence of air. The
oxidative degradation also affected the matrix PS, broadening its polydispersity,
Mw/Mn from 1.8 to 2.40. The degradation was found detrimental to the flame
retardancy of CPNC, as the re-aggregated clay offered less protection to the
polymer. Since extrusion of PS with inorganic NaMMT, under the same processing
conditions, did not affect the PS, it was concluded that the free radicals formed
during the intercalant degradation were to blame. The authors proposed the
mechanism, where the byproducts of the Hofmann elimination mechanism
[Hofmann, 1851] of quaternary ammonium reacted with oxygen to give peroxy
radicals, which in turn attacked the PS macromolecules.
Tanoue et al. [2004a; 2004b] reported similar observations for CPNC prepared
by melt compounding PS with MMT-2MBHTA (Cloisite® 10A; C10A) at 200 °C.
FTIR transmission spectra were measured on a Thermo Nicolet spectrometer at
a resolution of 4 cm-1 and with an accumulation of 128 scans. To enhance
detectability of the chemical changes, difference spectra were calculated for the
extruded samples by subtracting out the spectrum of neat PS and comparing the
results with the spectrum of C10A. The analysis identified characteristic peaks
of the dimethyl benzyl amine (2MBA) - a byproduct of the Hofmann
decomposition [Aldrich Co., 1997; Bellamy, 1975]. In addition to these peaks,
there are strong carbonyl peaks at 1705 and 1736 cm-1 in most of the extruded
samples containing organoclay, which corresponds to =C=O groups formed by
oxidation of the double bond in the long-chain olefin - another byproduct of the
Hofmann decomposition. Finally, there is evidence of a ketone carbonyl group
present in PS. The rheological measurements of the re-extruded CPNC showed
that the zero-shear viscosity, ηo, was reduced by about 30% each time. This is
particularly noteworthy since increasing the residence time in a TSE by a factor
of up to 10 did not further reduce the CPNC matrix viscosity. Similarly, extrusion
of neat PS had only a small (ca. 2%) effect on ηo. Thus, the combination of
oxygen, temperature and organoclay was responsible for the degradation of PS.
CPNC of PP (Mw = 278, Mn = 72 kg/mol), PP-MA (Mn = 23 kg/mol; 2 wt%
MAH) and an organoclay (Cloisite® 20A or 30B; C20A = MMT-2M2HTA or
C30B = MMT-MT2EtOH) were prepared by melt blending to have about 5 wt%
of clay [Bellamy, 1975]. These dry blends were compounded at 210 °C for 10 min
in an internal mixer at 50 rpm. During the process both organoclays lost a
proportional amount (to the initial) of the constituent elements (e.g., lost of about
10% of C), which indicates that thermal decomposition took place even under
these relatively mild conditions. This confirmed the suspicions that thermal
335
Clay-Containing Polymeric Nanocomposites
336
Thermal Stability
Total 26 32 35
337
Clay-Containing Polymeric Nanocomposites
PO-MA graft copolymer was incorporated. The results from cone calorimetry
suggest that nanocomposite formation has occurred, since there is a significant
reduction (by 30 to 40%) in the peak heat release rate (for more information on
flame retardancy see Section 5.2). However, these data do not differentiate between
the stability of the clay-intercalant complex and that of the matrix.
Delozier et al. [2002] performed the TGA analysis of their organoclay (MMT
with a quaternary ammonium containing tallow group) in air and nitrogen. The
organoclay started to degrade in air at 150 °C, lost approximately 1% weight at
200 °C, 5.5% at 250 °C, and 12% at 300 °C. Under nitrogen the organoclay was
more thermally stable, viz. at 250 °C the weight loss was 4% and at 300 °C it
was 9%. The effects were specifically blamed on the degradation of the long
hydrocarbon tails. The process is known to begin near 200 °C and it accelerates
as the temperature increase [Xie, et al., 2000].
Degradability of CPNC, comprising PA-6 and 5 wt% of MMT pre-intercalated
with ω-amino dodecyl acid (ADA) was studied [Davis et al., 2003]. Compounded
and dried specimens of neat PA-6 and CPNC were injection moulded at 300 °C.
Under identical conditions, CPNC degraded (Mn decreased by ca. 40%), while
PA-6 did not. ε-Caprolactam and terminal vinyl groups were detected in the
product.
The Hofmann elimination mechanism was used to explain the discoloration,
molecular weight decrease, and reduction of mechanical performance of CPNC
with PA-6 as the matrix [Fornes et al., 2003; 2004]. The authors compounded
the CPNC in a TSE at 240 °C and then injection moulded at 260 °C. The relative
(to extruded PA-6) colour index decreased (i.e., colour intensity increased) with
organoclay loading. However, the value for CPNC (proportional to that of neat
organoclay) decreased with the reduction of matrix molecular weight. Intercalants
with more unsaturation, -C=C-, and/or hydroxyl-ethyl groups, -C2H4-OH,
developed stronger discoloration. The authors concluded that more thermally
stable intercalants are needed. Similar observations were reported for CPNC
with PC as the matrix [Yoon et al.; 2003].
Evidently, thermal degradation of the organic cation poses a serious problem
when preparing and processing CPNC. The experience shows that when
blanketing by nitrogen is not used, the degradation mainly depends on the number
of reprocessing steps and to a minor extent on the total residence time at higher
temperature. The organoclays containing quaternary ammonium intercalants are
thermally unstable at temperatures above 150 to 165 °C. However, the onset of
degradation can be pushed up to above 200 °C by ascertaining the absence of O2
and controlling the composition, the method of treatment (e.g., extent of shearing)
and time of heating. Furthermore, the decomposition of intercalant in case of
highly polar macromolecules that may directly interact with clay surface, e.g.,
PA, is not as critical as that in the case of hydrophobic polymers with low polarity,
such as PO or styrenics.
The use by Inoue et al. [2002] of melamine as an intercalant is an important
development. This the first time a compound known as a flame retardant has
been used as intercalant, replacing the notoriously unstable quaternary
ammonium. This promising route is very much worth pursuing.
From the chemical point of view, the least stable are the quaternary ammonium
ions with a structure: Ri4N+, where Ri is a straight paraffinic chain. Reduction of
the degree of substitution is expected to improve the thermal stability, i.e.,
RiH3N+ > Ri2H2N+ > Ri3HN+ > Ri4N+ (but at the same time the ionic strength
338
Thermal Stability
may decrease). Another method for improving the thermal stability involves double
alkylation of the β-carbon(s), e.g., replacing straight paraffinic chain, viz.
RCH2CH2-N+ by RC(CH3)2CH2-N+ [Starnes, 2002]. The enhancement of MMT-
ammonium stability by the use of ammonium-Ni complexes has been reported;
the decomposition temperature was 50 to 150 °C higher than that without the
Ni-complex. Another method of enhancing thermal stability is by the use of the
‘sizing agents’, e.g., silanes or titanates [Maxfield, 1996].
Much less information is available on the stability of phosphonium systems.
Stability up to 370 °C was claimed by Ellsworth [1999], but more recent work by
Zhu et al. [2001a] indicates a more modest effect, viz. stability of MMT-phosphonium
higher by ca. 30 to 50 °C than that of MMT-ammonium. One possible source for
such discrepancy is the method used for defining the onset of decomposition.
When the degradation products have low vapour pressure and high solubility in
the degrading specimen the TGA analysis may be misleading - degradation may
have taken place, but the byproducts did not evaporate. For this reason, XRD/FTIR
followed by evaluation of the key properties after heating is essential.
During the last 10 years or so, the search for more thermally stable organoclays
has intensified (see Sections 2.3.2 to 2.3.7). The research on inorganic intercalants
was a significant step in this direction, but owing to the complexity and associated
costs so far this approach has not gained industrial approval. Observations that
clay readily interact with complex, aromatic salts resulted in repeated attempts
to incorporate these, more thermally stable molecules as intercalants. Thus,
replacing ammonium salt by that of a cyclic tertiary amidine leads to greater
thermal stability and more efficient intercalation of clay [Zilg et al., 1999]. Since
complex, aromatic molecules are often either functional or coloured (conjugated
double bonds), Eastman and TNO patented the use of dyes as intercalants [Barbee
et al., 2000c; Fischer et al., 2001]. For similar purposes, Imai et al. [2002]
developed intercalant (dimethyl isophthalate substituted with a triphenyl-
phosphonium group) able to react with PET, bind to clay and be stable up to at
least 275 °C.
Evidently, other stable organic compounds may be used for this purpose -
limitations are only imposed by availability and costs.
339
Clay-Containing Polymeric Nanocomposites
The TGA results are usually presented in the form of three parameters: T10
(°C), T50 (°C), and char content (wt%); the first two indicating the temperature
at which 10 or 50% weight loss was recorded, and the last represents the fraction
of material which remains at 600 °C. It is evident that even the initial 10%
weight loss takes place at much higher temperatures than the thermal degradation
of organoclay (see Section 3.2.1). Recently, MMT was intercalated with oligomeric
molecules, bringing the organic content in the organoclay to 65-73 wt% [Su et
al., 2004]. In this case, both flammability, and T10 decreased with organoclay
loading.
340
Rheology
3.3
Rheology
3.3.1 Introduction
Before discussing the flow behaviour of CPNC it is worth summarising
information on the flow of clay suspensions.
• The early application of clay suspensions was for increasing the viscosity of
aqueous or organic liquids, to ‘give body’ and facilitate application, e.g., in
paints or greases. This has been efficiently accomplished by the ability of
clay to form face-edge interactions that leads to ‘house-of-cards’ 3D (gelled)
structures. The suspensions showed strong thixotropic effects, rapidly
increasing with concentration up to full gelation of the system at about
5 vol%.
• The computational and experimental data show that molecules form layered
structures on the face of crystalline solids. The first 2-3 layers show solid-
like behaviour and the solid surface effect stretches a long distance in the
z-direction. The z-distance where the viscosity is equivalent to that of neat
liquid depends on the molecular mobility; on average it stretches to 10-
12 layers, but in the case of macromolecules the distance may be as large as
100 to 120 nm.
341
Clay-Containing Polymeric Nanocomposites
342
Rheology
Viscosity at lim η(γ˙ ) = lim η ′(ω ) = lim η E (ε˙ ) / 3 lim η(γ˙ ) ≠ lim η ′(ω ) ≠ lim η E (ε˙ ) / 3
vanishing γ˙ →0 ω →0 ε˙ →0 γ˙ →0 ω →0 ε˙ →0
deformation rate
343
Clay-Containing Polymeric Nanocomposites
344
Rheology
where a = 0.025 ± 0.004 and b = 1.47 ± 0.03 with the correlation coefficient
squared, r2 = 0.9998 and standard deviation, σ = 0.622. Brodnyan [1959] adopted
Mooney’s relation between relative viscosity and volume fraction of hard spheres
and proposed an experimentally modified formula for prolate ellipsoids. At infinite
dilution this formula has the same form as the relation between [η] and p given
in Equation 107 for discs, but with a = 0.399 and b = 1.48.
For freely rotating prolate ellipsoids (rods) with p > 20 the following
dependence was derived [Simha, 1940; Simha, 1952; Frisch and Simha, 1956]:
2 ⎡ ⎤
[η] = 14 +
15 5
p
⎢
1
+
1
⎥
⎢⎣ 3 ln( 2 p) − 4.5 ln( 2 p) − 0.5 ⎥⎦
(108)
while for the oblate ellipsoids (discs) with p >> 1 Simha [1940] derived:
[η] = (16 / 15)( p / arctan p) (109)
Figure 89 shows that [η] very much depends on the shape and the aspect ratio of
anisometric particles. As is to be expected, the strongest enhancement of [η] with
p is observed for rods (prolate ellipsoids or fibres). Oblate ellipsoids (disks) show
intermediate behaviour between that of prolate ellipsoids and hard spheres. For
disks the prediction by Simha virtually superimposes on that by Kuhn and Kuhn
[1945] – they both form the upper bound for [η]. Goldsmith and Mason [1967]
proposed a relation that gives a lower bound, while the experimental values are
located in-between. The [η] is sensitive to polydispersity as well as to the regularity
of shape.
Figure 89 Intrinsic viscosity for rods and discs versus aspect ratio. In the latter
case the theoretical, (time-averaged) and the experimental dependencies are shown.
The Einstein value for monodispersed hard spheres, 2.5 for p = 1 is illustrated by
the horizontal line.
345
Clay-Containing Polymeric Nanocomposites
The plotted dependencies are averages – when initially the particles are all
aligned (e.g., in an electric field) and upon imposition of flow they start to rotate,
the rheological response (e.g., shear viscosity or [η]) will vary with the period
given by Equation 105. Ivanov et al. [1982] reported on the periodic oscillatory
nature of suspension viscosity in shear flow.
The above relations are valid within the high dilution region where the free
rotation of anisometric particles is feasible. Detailed analysis of flow within this
region is available [Goldsmith and Mason, 1967; van de Ven, 1989]. As the
concentration increases the particle-particle interaction becomes stronger and
the higher terms in Equation 104 have to be included. The relation breaks down
once the concentration of particles exceeds the limit of possible free rotation.
This limit, φ > φmax, can be calculated assuming that the discs are circular and the
volume they require for free rotation is that of the encompassed sphere. For the
monodispersed hard spheres and oblate ellipsoids the (experimental) maximum
packing volume fraction is φm ≅ 0.62 and φmax = 0.62/p. Empirically, for p < 50 a
weaker dependence was found:
φmax = (1.55 + 0.0598 p)
−1
(110)
As shown in Figure 90, the empirical dependence for φmax predicts higher values.
The most probable reason for the disparity is the tendency of discs to align parallel
to each other, even at low concentration (the same reason why, in suspensions,
the spheres readily make doublets), thus prematurely forming the structures
expected within the φ > φmax region, where the discs must adopt locally parallel
orientation with the spacing dependent on concentration, d001 = a0 + a1/φ (see
Figure 44 in Section 2.4).
These simple relations are valid for suspensions without strong interactions.
Dispersion of clays in aqueous media is complicated by the presence of electrostatic
Figure 90 Maximum packing volume fraction for freely rotating discs versus
aspect ratio. Lower solid line – theoretical, assuming monodispersed particles,
upper broken line – empirical, Equation 1.
346
Rheology
Figure 91 Three regions of flow of nematic LCP. The viscosity versus shear rate
dependence as generalised by Onogi and Asada [1980].
347
Clay-Containing Polymeric Nanocomposites
348
Rheology
parallel rheological and WAXS studies of stress growth, interrupted stress growth,
stress growth after flow reversal and stress relaxation. In spite of large rheological
effects, WAXS provided strong evidence that orientation effects were absent during
the shear flow. The extensional flow produced orientation, but its changes occurred
on a different timescale to those in the stress field. Thus, the disruption of the
interactive domain structure was proposed as the stress overshoot mechanism.
Pitches are notoriously complex comprising at least 461 identified chemical
components, with molecular weights ranging up to 2 kg/mol [McNeil, 1983].
Owing to unsaturation, some of the molecules have a rigid rod structure, while
some others (formed by fusing 4 to 10 aromatic rings) are discotic, hence their
structure may be considered intermediate between the rod-like LCP and CPNC.
The presence of these anisometric molecules is responsible for the nematic pitch
behaviour. The anisometric compound content may be adjusted by extraction or
by addition of synthetic compounds.
Fleurot and Edie [1998] studied the rheology of three mesophase pitches used
for production of carbon fibres. The steady shear data placed them within regions
I and II of the Onogi and Asada classification. The transient shear response was
determined by pre-shearing the samples at γ˙ = 0.5 s-1 for 2 min then letting the
sample rest for 8 to 4000 s, and then restarting the flow. The results are shown in
Figure 92. For all three samples the stress growth depended on composition. The
normalised peak height increased with the rest time after pre-shearing, but for
different pitches the form of the dependence was different and a master curve
could not be generated. The determined domain size was large, decreasing with
shear rate ( γ˙ = 0.5 to 10 s-1) from a = 16 to 6 μm. The authors applied the
domain theory of LCP with a qualitative success.
Figure 92 Normalised stress growth peak for three mesophase pitches versus rest
time before re-shearing at the rate of shear of 0.5 s-1. After [Fleurot and Edie,
1998].
349
Clay-Containing Polymeric Nanocomposites
Marrucci [1984] formulated the domain flow theory assuming a balance between
the alignment tendency of the velocity field and the elastic resistance to deformation
of the director field. The Eriksen distortion stress, σE, was taken as proportional to
the elastic constant, K, and inversely proportional to the domain size. Noting the
domain size within the polydomain region I as ao and during the flow as a, the
stress associated with the recoverable (elastic) energy was calculated as:
(
σ E ~ K a −2 − ao−2 ) (111)
While the average stress is given by this dependence, the flow depends on the
local orientation – high velocity is expected in the region where the orientation
director and velocity vector are parallel to each other, and low velocity for the
opposite case. As a result, the rheological relation between the shear stress and
the deformation rate was scaled down to read:
σ = ηequilγ˙ao / ( ao − a) (112)
Equating these two equations gives the relation between the reduced viscosity,
( )
η/ηequil, and the reduced deformation rate, γ˙ redu = γ˙ ao2 ηequil / K (see Figure 93a).
Figure 93b shows the complementary dependence of the relative domain size
reduction versus the relative deformation rate. The derived relation has two
asymptotic limits. At low deformation rates the initial slope is predicted to be –1/2
(in contrast to the value of –1 predicted for the yield stress). This slower decrease
of the reduced viscosity with shear rate is in good agreement with many
observations of LCP flow. The second asymptote is obtained at higher rates,
where the plateau value of region II is recovered. Thus, as simple as the derivation
is, it provides sound explanations for the shape of the flow curves of LCPs. Since
the basic assumption was the presence of large domains with aligned particles,
this treatment may be useful for interpreting the flow behaviour of CPNC systems.
350
Rheology
Figure 93 Predicted by the Marrucci’s domain flow theory (a) apparent reduced
viscosity and (b) relative domain size versus shear rate. See text.
351
Clay-Containing Polymeric Nanocomposites
352
Rheology
initial slope of G´ and G´´ was found to decrease with increasing concentration
of organoclay. Thus for 0, 2 and 5 wt% loading:
g´´ ≡ (d log G´´/d log ω)ω < 10 = 0.93, 0.80 and 0.70, respectively.
These values should be compared to the expectations: for neat polymer g´ = 2
and g′′ = 1, for the LCP domain flow g´´ = 1/2, while for systems with yield stress
g´´ = 0. Thus, these CPNC behaved like a solution of LCP in a molten polymer,
and not like filled melts with yield stress. At high strains the platelets may be
aligned, which would greatly reduce the rheological response. In short, these
end-tethered systems behaved differently than could be expected from diluted
suspensions (see also: Section 3.2.7).
A slightly different approach was used by Wagener and Reisinger [2003].
Instead of using the initial slope of G´ and G´´ the authors calculated the ‘shear
thinning exponent’ from the initial slope of the complex viscosity versus frequency
dependence: n ≡ d logη*/d log ω. Evidently, the parameter is a reflection of the
3D structure. There are many mechanisms responsible for such effects (e.g.,
compatibilisation of immiscible mixture of polymers [Utracki, 2002a]), but in
CPNC, when other factors are constant, the exponent n may reflect the degree of
platelet dispersion. Indeed, for PBT with 4 wt% organoclay, empirically n
correlated with Young’s modulus: Y(GPa) ≅ 2.5 – 1.2n.
It is to be expected that the rheological behaviour of the end-tethered systems
will differ from that where such direct bonding is missing [Hoffmann et al.,
2000a]. The authors prepared two types of CPNC based on PS. In the first, the
clay was intercalated with phenyl-ethyl amine, and then dispersed in PS, while in
the second the clay was exfoliated with amine-terminated PS. A plot of the storage
shear modulus, G´ versus reduced frequency ωaT for the neat PS and PS with
intercalated clay nearly superimposed one on top of the other – addition of
organoclay did not change the basic flow properties of the PS matrix. By contrast,
the exfoliated, end-tethered CPNC (with amine-terminated PS) showed large
increases of G´ at low ω, indicating a network formation.
In the next publication, the melt flow behaviour of two exfoliated CPNCs
was studied. Two types of clay: synthetic fluoromica, FM, and mineral MMT,
were used [Hoffmann et al., 2000b]. First, the clays were intercalated using either
protonated ω-amino dodecanoic acid (ADA) or water, then dispersed in ADA,
which in turn was polymerised into PA-12. The use of ADA-intercalated clay
resulted in the formation of end-tethered CPNC with platelets chemically bonded
to the matrix, but with surprisingly small interlayer spacing, d001 ≤ 2 nm. The use
of water as a swelling agent resulted in exfoliated nanocomposites, but without
the chemical bonds between clay and the polymer chains.
A stress-controlled rheometer was used in the parallel plate geometry at
ω = 1 to 25 rad/s assuring linear viscoelastic behaviour. Comparison of the neat
PA-12 matrix flow with those for the two CPNC showed significant differences.
The presence of a superstructure was deduced from the low frequency behaviour.
The slopes of G´´ in the terminal region were: g´´ = 0.4 to 0.6 for the end-tethered
and 0.9 for the not-tethered CPNC, thus lower than those of PA-12 with similar
molecular characteristics. Furthermore, flow of CPNC with exfoliated but non-
tethered clay platelets, was dominated (at least up to 4 wt% organoclay loading)
by the matrix behaviour, with only a minor contribution from clay. Tethering
dramatically enhanced the storage and loss shear moduli, by one and by one-half
decade, respectively. This observation is particularly important since XRD showed
353
Clay-Containing Polymeric Nanocomposites
Figure 96 Stress relaxation, G(t), for PSIR and its CPNC. The solid lines were
computed from dynamic moduli, G´ and G´´.
Reprinted with permission from [Ren et al., 2000]. Copyright 2000 American
Chemical Society.
354
Rheology
MMT and the aromatic rings of PS. As discussed above, the non-tethered clay
platelets in the PS matrix showed limited influence on the CPNC flow. The
dramatic modification of the rheological behaviour shown in Figure 96 suggests
that in the copolymer clay is preferentially dispersed in PS-block domains, phase
separated from those of IR-blocks.
The data in Figure 96 also illustrate that the simple relation developed by
Ferry [1980] for a single component melt is also valid in these rheologically
complex systems:
G(t ) t =1 / ω = G ′(ω ) − 0.4G ′′(0.4ω ) + 0.014G ′′(10ω ) (113)
Sometimes, the end-tethering may be replaced by strong interactions between polar
groups and the clay surface. Schmidt et al. [2000, 2002a] measured birefringence
and small angle neutron scattering (SANS) during Couette shear flow of clay
suspensions in aqueous polymer solution. Thus, 3 wt% of synthetic hectorite (FH;
platelets with diameter d = 30 nm and thickness h ≅ 1 nm) was dispersed in an
aqueous solution of 2 wt% polyethylene glycol (PEG, Mw = 103 kg/mol) at pH = 10
and a NaCl concentration of 1 mmol/L. The birefringence indicated mechanical
coupling between clay platelets and PEG. At low rates of shear, γ˙ < γ˙ critical ~ 30 s −1 ,
birefringence was dominated by the clay platelets, but at high by the polymer
chains stretched in the flow direction. SANS data indicated that at γ˙ > γ˙ critical the
flow was strong enough to induce chain orientation. The clay platelets (within
aggregates with diameter d = 32-233 nm) were oriented in the flow direction with
the surface normal in the neutral (not radial) direction. In a later publication the
authors used SANS to study the effects of shear on clay platelet orientation [Schmidt
et al., 2002b]. As the rate of shear increased the clay platelets progressively oriented.
At the highest flow rates the macromolecules became stretched in the flow direction.
Lim and Park [2000; 2001] prepared CPNC by dispersing up to 10 wt% of
MMT (intercalated with 2M2HT; Cloisite® 6A) in either PS or in PS-co-MA
(containing 7 wt% MAH). Compounding in an internal mixer increased d001
from 2.94 nm (Cloisite) to 3.45 and 3.37 nm for PS and PS-co-MA, respectively.
In spite of the small difference of the interlayer spacing the low frequency dynamic
moduli showed large differences, viz. G´(10% clay, ω = 0.02) ≅ 0.1 and 6 kPa,
with the corresponding differences in the initial slope of g´ = 0.59 and 0.24,
respectively. Shearing these highly loaded samples at γ = 120%, ω = 1 rad/s for
30 min reduced the effects of association, but did not eliminate them entirely.
The cited examples demonstrate that instead of a sharp distinction between
the classical, filler-like influence of organoclays and the effects assigned to the
end-tethered CPNCs, there is a continuous spectrum of rheological behaviour.
The rheological response is associated with the ability of dispersed particles or
aggregates to interact with each other. In the presence of electrostatic interactions
in aqueous media the platelets readily form edge-face ‘house-of-cards’ structures,
even at low loading of ca. 5 wt%. However, in organic media there is a double
layer of semi-solid organic molecules that shields the silicate surfaces. Here, the
formation of 3D structures is possible by two mechanisms – crowding, as in
classical composites, or by entanglements. In the latter case the strongest effects
are to be expected when the terminal groups directly bond macromolecules to
the clay surface. However, entanglements may also be promoted by the use of
block copolymers or by forming associations between the clay surface and polar
groups of the polymer chain. Further examples of the effects of tethering will be
found in the following parts.
355
Clay-Containing Polymeric Nanocomposites
[ { }]
R3 (ω ) = R 1 − exp −( γ − γ L ) / k ; γ > γ L (117)
⎡ ⎤
1
R3 (ω ) = R ⎢1 − ⎥; γ > γ L (118)
⎢ 1 + ( Bγ )C ⎥
⎣ ⎦
In these relations R is a measure of the maximum intensity, γ is the applied strain,
γL is the maximum strain for the linear viscoelastic response, while k, B and C
are parameters characterising the relative intensity change of the 3rd harmonic
peak. The former relation, Equation 117, has been used to determine the limit of
the viscoelastic linearity, whereas the latter provides a better fit to data within
the full range of strains.
356
Rheology
Thus, the molecular weight of a MMT unit cell is Mu = 734 + water. The cation
exchange capacity of the idealised MMT is CEC = 0.915 meq/g, with Na+ spaced
ca. 1.2 nm apart.
Assuming that every clay plate and every cation on its surface is available for
the exchange reaction of Na+ for ADA and that each lauric acid group starts the
polycondensation, leads to the conclusion that near the clay platelets the end-
tethered PA-6 chains are densely packed. Since the molecular weight of PA-6 is
Mn = 22 kg/mol, the resulting clay content of the fully grafted hairy clay platelets
(HCP) should be 4.74 wt%. As the clay platelets are 0.96 nm thick and their
aspect ratio is p = 287 (see below), each platelet would have about 140,000 end-
tethered macromolecules, i.e., Mn ≅ 3×106 kg/mol of a single HCP. Thus,
polycondensation that involves every Na+ on the Na-MMT surface results in
formation of an entity that resembles a star-branched or dendritic macromolecule
357
Clay-Containing Polymeric Nanocomposites
of a very high molecular weight. Near the clay surface the macromolecules are
crowded and immobilised.
Polycondensation results in CPNC containing exfoliated clay particles with
PA-6 macromolecules tethered to their surface. For the reason of dyeability these
CPNC need to be diluted with about twice the amount of neat PA-6. Alternatively,
the grafting efficiency of the clay platelets may be reduced and HCP with Mn ≅ 1
to 3×106 kg/mol are produced. To form these materials, standard processing
methods, e.g., extrusion or injection moulding, may be used. The improvement
of the rigidity, tensile and flexural strength, heat distortion temperature and gas
barrier properties over neat PA-6 have been rationalised on the basis of the surface
effects, change in crystallinity as well as by the orientation effects imposed by the
processing flow field.
Kojima et al. [1994] studied the orientation and crystallinity of extruded PA-6
CPNC calendered films containing 0.18, 0.46 and 0.74 vol% of clay. XRD, TEM
and DSC measurements were carried out. It was found that clay platelets as well
as the γ-crystals of PA-6 had planar orientation. The orientation direction was
independent of the clay content, but the degree of orientation increased with it.
It seems that during the flow through a T-die followed by subsequent stretching
between chilled rolls the clay platelets became in-plane oriented, then the matrix
polymer crystallised with the chain axes parallel to the clay surface. The γ-form
of PA-6 has four monomeric units in the monoclinic unit cell with hydrogen
bonding between parallel chains. This form is often associated with the formation
of extended chain crystals during processing involving elongational flow.
In the following paper the authors reported on the orientation engendered by
injection moulding of CPNC into an end-gated, 3 mm thick mould cavity [Kojima
et al., 1995]. Here the MMT content was 2.2 vol%. XRD and TEM measurements
were carried out. In Figure 97 the 002-reflection peak intensity of γ-PA-6 versus
injected bar thickness, z, is shown. Three regions of orientations are evident:
skin with in-plane orientation for the PA-6 macromolecules as well as for the
clay platelets, intermediate with chains perpendicularly oriented to the clay
platelets and the flow direction, and the centre layer where the macromolecular
chain orientation is perpendicular to the clay surface, and clay platelets are
primarily oriented perpendicular to the flow direction.
It is interesting that during the flow through rolls that engenders film stretching
or during fountain flow in the mould cavity the macromolecular chains of PA-6
get oriented in-plane and crystallise with the chain axis parallel to the clay surface.
However, at lower stresses the lamellae are oriented along the clay surface with
chains oriented perpendicular to it. Kojima et al. speculated that this is the natural
behaviour of PA-6 chains, highly crowded near the clay surface caused by the
high grafting density.
More recently, Medellin-Rodriguez et al. [2001] studied SAXS/WAXS
orientation of the same Ube CPNC during steady-state shearing between parallel
plates at γ˙ = 60 s-1, and T = 240 °C for up to 20 min. Compression moulded film
specimens, 0.25 mm thick and containing 0, 2, and 5 wt% of MMT were used.
At this relatively low shear rate and at a temperature near the melting point there
was a gradual change of clay platelet alignment (see Figure 98). Owing to the
vorticity component in the shear stress matrix, the end-tethered clay platelets are
expected to tumble with the period given by Equation 105. The increasing
scattering intensity (in the direction perpendicular to the shear field) indicates
358
Rheology
Figure 97 XRD peak intensity of γ-PA-6 versus injected bar thickness, z. Three
regions of lamellar orientation are shown: skin with in-plane orientation,
intermediate with perpendicular orientation and central (see text).
Data [Kojima et al., 1995].
359
Clay-Containing Polymeric Nanocomposites
progressive orientation in the shear vector. Evidently, at φ < φmax the tumbling
motion of the clay platelets continues, but since the motion is periodic with long
residence time in the preferred direction the overall platelet orientation is in the
flow direction (e.g., see Goldsmith and Mason [1967]). The authors also reported
that randomisation of the clay orientation after cessation of shear is slow,
substantially slower than the relaxation of polymer chains. Thus, at T = 240 °C
it takes at least 12 min to randomise the platelets, whereas the PA-6 relaxation
time is about 0.4 s. In consequence, crystallisation during normal processing
conditions is bound to preserve the flow-induced clay orientation in the product.
Figure 99 Complex shear modulus as a measure of the PA-6 drying time under
vacuum at 80 °C. Data [Utracki and Lyngaae-Jørgensen, 2002]. The line follows
the exponential dependence: log G* = ao – a1 exp{-a2/t} with ao = 2.87 ± 0.01;
a1 = 0.43 ± 0.01; a2 = 1.4 ± 0.1 and the standard deviation σ = 0.02; r2 = 0.99995.
360
Table 52 Polynomial fit parameters for the time sweeps. The first five samples were re-extruded or compounded,
the last two 'as received'. Data [Utracki and Lyngaae-Jørgensen, 2002]
PANC wt% G′′0 G′′1 G′′2 rG′′ G′′′′0 G′′′′1 G′′′′2 rG′′
100 (PANC) 321.3 0.09600 -4.2305e-06 0.99971 3133.3 0.37305 -2.2062e-05 0.99859
100 (PANC) 559.7 0.1774 -1.0141e-05 0.99962 3773.2 0.54600 -2.8488e-05 0.99888
361
Rheology
Clay-Containing Polymeric Nanocomposites
In spite of the fact that before loading into a rheometer the specimens were well-dried,
during the 1 h in the rheometer the shear moduli, G´ and G´´, increased by a factor of
2 to 5 and 1.4 to 1.8, respectively. From these changes the rates of G´ and G´´ increase,
R´ and R´´, were calculated (see Equation 119, Table 52 and Figure 100).
As shown in Figure 100, the rates R´ and R´´ are both positive hence the two
moduli increase with time, but increasing the organoclay content caused an increase
of R´ and a decrease of R´´. In other words, addition of organoclay accelerates the
time-induced increase of G´, but it slows down that of G´´. This dual effect is
indicative of two parallel mechanisms: (1) polycondensation and (2) interaction
between the hairy clay platelets (HCP). Owing to the presence of the residual low
molecular weight amines (introduced during the intercalation and/or polymerisation
steps) an addition of organoclay slows down polycondensation. As the concentration
of clay in CPNC increases, the interactions between the HCPs increase as well.
Since these time effects were independent of the test conditions, it was concluded
that the explored variables had negligible effects on orientation – the effects were
chemical and thermodynamic in nature. As a consequence, the parameters listed in
Table 52 were used to recalculate all the subsequent rheological data to the initial
time. In consequence, the strain sweep, frequency sweep and other data reported
below are freed of these time effects.
362
Rheology
[ ]
G ′′(γ ) = Go′′ / 1 + G1′′γ 2f − G2′′γ 3f ; strain fraction : γ f + γ / 100 (120)
Knowing the parameters of this relation permits calculation of the strain
dependence of G´ and G″ for any composition (at ω = 6.28 rad/s). Evidently, the
largest strain effects are expected for the sample with the highest concentration
of clay, i.e., for PANC. However, even here at γ = 50% the reduction of G´ and
G″ is relatively small: 15 and 7.5%, respectively.
Figure 101 Time-temperature superposition for Ube PANC at the four indicated
temperatures
363
Clay-Containing Polymeric Nanocomposites
⎡ 1 1 ⎤
log aT = B⎢ − 2 ⎥
˜ ˜
⎢⎣ −0.0921 + 4.89T + 12.56T
2 ˜ ˜
−0.0921 + 4.89To + 12.56To ⎥⎦ (123)
(
or log aT = ao + a1 / 1 + a2 T + a3 T 2 )
It is noteworthy that for a2T >> 1 (i.e., well above the glass transition temperature),
the dependence leads to the Arrhenius equation.
Substituting numerical values into the Equation 123 (B = 0.3817 was used)
gives the prediction shown as a dotted curve in Figure 102. Both dependencies
(the experimental and calculated) seem to follow the Arrhenius dependence with
the activation energy of flow:
ΔHη = R[d log aT/d (1/T)] = 18 kJ/mol.
Figure 102 Temperature dependence of the frequency shift factor for PANC (see
Figure 101). Comparison between the experimental and computed (from Equation
123) dependencies.
364
Rheology
The highest value of log aT corresponds to T = 230 °C, i.e., about 10 °C above
Tm(PA-6) = 220 °C, thus some pre-crystallisation and/or stress-induced structural
change is to be expected.
The frequency dependence of the dynamic viscosity (η´ = G´´/ω) is shown in
Figure 103. The frequency sweeps were conducted at T = 240 °C, strains γ = 40%,
from ω = 0.1 to 100 or from 100 to 0.1 rad/s. For PA and the mixture containing
25 wt% PANC, the shear moduli did not depend on the scan directions. Thus,
scanning by either increasing or decreasing frequency, or scanning in the same
direction but starting from different frequency, produced different rheological
responses and the observed differences increased with clay loading. These shear
history effects were well reproduced within ± 2% by two operators who used
two rheometers and a variety of specimens. A Newtonian plateau was observed
only for PA and the mixture containing 25% PANC – the higher is the clay
concentration the higher is the negative slope at ω < ωc. However, even for neat
PANC the slope is small, ca. –0.1, smaller than what could be expected for the
domain flow. Evidently there are interactions between HCP in this region, but at
a clay loading of 0.64 vol% their strength and/or intensity are relatively low.
To analyse the frequency dependence of G´´ the data at γ = 10% scanned in
both directions and these at 40% scanned from 100 to 0.1 rad/s were fitted to the
Krieger-Daugherty type dependence, rewritten for dynamic flow [Utracki, 1988]:
− m2
[ ] ( )
′ / ω 2 = ψ o ⎡⎢1 + G ′′ / Gψ ⎤⎥
− m1 2
η ′ ≡ Gcorr
′′ / ω = ηo 1 + G ′′ / Gη ; ψ ≡ Gcorr (124)
⎣ ⎦
The dependence was derived for linear viscoelastic, pseudoplastic systems; hence
it is unable to describe the yield stress. The least-squares fit of Equation 124 to
data is shown in Figure 103. Excepting PA all compositions showed some ‘solid-
like’ behaviour at ω < ωc ≅ 1.4 ± 0.2 rad/s. Thus, only data above ωc could be
used to determine the parameters of Equation 124 (see Table 53).
Figure 103 Frequency scans for extruded PANC/PA mixtures at 240 °C at γ = 40%
from 100 to 0.1 and from 10 to 0.1 rad/s (different specimens); points –
experimental, lines – Equation 124 [Utracki and Lyngaae-Jørgensen, 2002].
Reproduced with permission, copyright Springer 2002.
365
366
Table 53 Frequency effects for PA-6/PANC mixtures at T = 240 °C and γ = 40%.
Data [Utracki and Lyngaae-Jørgensen, 2002]
Parameter PA-6 25% PANC 50% PANC 75% PANC 100% PANC
ω
η′ = G′ ′ /ω
1. η′
2
2. ψ = G′′/ω
The presence of the critical frequency, ωc, at which the HCP associations
vanish, is worth commenting. The transition is independent of the clay content.
Thus, it is related to the relaxation time of the aggregates, or by analogy to the
LCP-type flow, to the domain size. The effect is associated with the formation of
a structure that, at the selected level of T and γ, breaks at ω = ωc. This corresponds
to the relaxation time of τaggr = 4.5 s, i.e., significantly longer than that for PA-6:
τPA = 0.2 s. Identifying ωc with the transition from Region I to Region II of the
LCP-type behaviour and using the Marrucci [1984] relation:
γ˙ ≅ K / ao2 ηequil (125)
with the elastic constant K ≅ 10 (N), leads to the estimated value of the domain
-11
size for the three compositions (PANC, 75 and 50%) of ao = 310 nm. This may
be a coincidental agreement, but as will be shown below the aspect ratio, p =
296, was calculated from the barrier properties and suspension viscosity – the
value gives the bare platelet diameter d = 275 ± 9 nm, quite close to the domain
size in CPNC flow.
It can be shown that for incompressible, linear viscoelastic liquids there is an
interrelation between G´ and G´´ through the relaxation spectrum, H(λ):
∞
λH (λ )dλ ∞
H (λ )dλ
G′ / ω 2 = ∫ 1 + (ωλ )
0
2
; G ′′ / ω = ∫ 1 + (ωλ )
0
2
(126)
Since these functions are valid in the whole range of relaxation times, they are
also valid within narrow ranges inside this interval, say from λ = t to (t + Δ), thus:
()ξH ξ
(G ′ / ω ) = Δ 1 + ωξ
2
= ξ (G ′′ / ω ); t ≤ ξ ≤ t + Δ (127)
( )
2
The mean value theorem only requires that the integrals be continuous and the
interval Δ small, hence the proportionality between the two moduli should be
valid in the full range of the relaxation time and frequency. For Maxwell fluids
this means that:
(G ′ / ω ) = λ(G ′′ / ω )
2
or ψ (ω ) = λη ′(ω ) (128)
where λ is the main relaxation time. Thus, the simple Maxwell model represents
the flow behaviour for fluids in which the ratio of parameters in Equation 124:
m2/m1 = 2. A similar prediction can be obtained using other fluid models proposed
by, e.g., Oldroyd, Spriggs, Bird-Carreau, Bogue, Meister, and others. However,
as the data in Table 53 show, this condition is approximately observed only for
PA-6 and the 25% PANC mixture – for the other systems m2/m1 ≅ 5.5, hence
these systems are rheologically complex.
The deviation from linear viscoelastic behaviour at ω < ωc ≅ 1.4 ± 0.2 rad/s is
dramatically evident in Figure 104, where the ratio: G´/G´´ is plotted as function
of G´´. The plot is suggested by the Doi and Edwards [1978] theory predicting
that the log G´/G´´ versus log G´´ dependence for ‘well behaving’ liquids should
follow a straight line with the slope of 1:
367
Clay-Containing Polymeric Nanocomposites
Figure 104 Inverse loss tangent versus G´´ for PA/PANC mixtures at T = 240 °C
and ω = 0.1 to 100 rad/s. Solid symbols for γ = 10%, open symbols for g = 40%.
The predicted slope = 1 is also shown. [Utracki and Lyngaae-Jørgensen, 2002].
Reproduced with permission, copyright Springer 2002.
Figure 104 displays the log G´/G´´ versus log G´´ relations for all PA/PANC
compositions, frequencies and strains. The predicted dependence is close to the
observed only for neat PA-6. For the clay-containing samples the deviation from
the expected linearity increases with the nanoparticle content, hence it most likely
originates from the interparticle interactions that more strongly affect the storage
than the loss modulus. In simple words, addition of tethered clay particles to a
PA-6 matrix results in higher values for the stored energy than expected from a
second order fluid.
[ {
σ y (ω ) = σ yo 1 − exp −τ yω }]
u
(130)
This model may be also applied to CPNC. For end-tethered CPNC the interacting
entity is the HCP. Here the polydispersity of size is related to polydispersity of
the aspect ratio, which for CPNC is narrower than that found in polymer blends
hence u ≅ 1 may be postulated.
368
Rheology
The yield stress function at ω < ωc is presented in Figure 105. The data are
well represented by Equation 130 with σ yo = σy(φ), τy = 0.59 ± 0.03 and u ≅ 1.
The solid-like structure formation starts at about 20 wt% PANC reaching a
maximum value of σ yo = 23 Pa for neat PANC. It is noteworthy that the onset of
the yield stress takes place at a MMT concentration of about 2.5 times lower
than that calculated for the platelet maximum packing fraction. Thus, the 3D
structure formation originates from the presence of the end-tethered
macromolecules – it is of the chain entanglement type.
Figure 105 Frequency dependence of the yield stress function Y ≡ η’exp/η’lin = G´´exp/G´´lin
for PA/PANC mixtures at T = 240 °C. Lines computed from Equation 130.
[Utracki and Lyngaae-Jørgensen, 2002], copyright Springer 2002.
369
Clay-Containing Polymeric Nanocomposites
370
Rheology
Figure 107 TEM of PANC from Ube shows ‘in plane’ orientation of MMT
platelets. Orientation in not sheared specimens was random, with many bent clay
platelets [Perrin, 2002].
rates (Figure 108 (b)) the signal goes through a local minimum followed by the
polycondensation effect.
As was the case for LCP, interrupted stress growth studies have also been
carried out on these CPNC systems. The work is usually performed in three
stages: (1) pre-shearing; (2) allowing the system to rest for a specific time; (3)
shearing either in the same or the opposite direction. The most interesting results
are obtained within the Onogi-Asada plateau Region II.
Figure 109 shows the stress growth functions for two PANC specimens. Both
were identically pre-sheared for 300 s at γ˙ = 0.1 s-1. Next, the shearing stopped
for either 600 s (specimen (1)) or 1200 s (specimen (2)), and then they were
sheared for 300 s, at γ˙ = 0.1 s-1, but in the opposite direction. The data were
fitted to a distribution curve:
η = ηequil + ao t b ( a1 )
t
(132)
The parameter b provides a measure of the breath of distribution: tw/tn = 1 + 1/b
or tz/tn = 1 + 2/b, etc. The parameter ao is a measure of the orientation effect,
while a1 is a measure of the rate with which the overshoot dissipates, i.e., the
platelets re-align with the field. The dependence very well described the observed
curves – it is difficult to distinguish the experimental points from the computed
lines. The maximum values from the stress overshoot experiments are plotted
versus the rest time in Figure 110. The quality of fit as well as the fitting parameters
are listed in Table 54.
Differentiating Equation 132 provides the conditions for the local extremum
of the function at tmax, from which a simple relation for the incremental increase
of shear viscosity is obtained:
( )
ln Δη ≡ ln η − ηequil = ln ao + b(ln tmax − 1); tmax = − b / ln a1 (133)
Thus, for rest times of trest = 0, 600 and 1200 s, values of Δη = 0, 124 and 171
were obtained. As shown in Figure 110, the data follow a single exponential
dependence. As the peak height increases it becomes narrower, thus the value of
b increases and the dispersion parameter, tw/tn decreases.
371
Clay-Containing Polymeric Nanocomposites
Figure 108 Stress growth function of PANC at T = 240 °C and at γ˙ = 0.01 (a) or
0.1 (b). In the first case shearing in the cone-and-plate tooling was for 10 s only, in
the second for t = 1000 s.
372
Rheology
Figure 109 Two PANC specimens pre-sheared at γ˙ = 0.1 s-1 for 300 s: (1) relaxed
for 600 s then sheared for 300 s, at the same rate, but in the opposite direction; (2)
had the rest time twice as long. The curves computed from Equation 132 are
virtually indistinguishable from the experimental dependence.
Figure 110 The incremental increase of shear viscosity for PANC versus the rest
time after pre-shearing. As shown, the increase follows a single exponential.
373
Clay-Containing Polymeric Nanocomposites
immediately started to decrease toward the plateau then power law regions.
However, it is important to note that in these two cases the plateau levels were
different by about 10%. Apparently, the initial shearing of the specimen in the
first experiment for 1975 s more than in the second one was responsible for the
development of larger domains yielding a higher plateau value. This effect was
additional to that of the time-dependent polycondensation.
Next, the flow curves were determined starting at the same γ˙ = 0.01 s-1, but
changing the wait time between data points, Δt from 0 to 540 s (see Figure 111).
The flow behaviour systematically varied with Δt. The slower was the sweep
time, the better defined and the higher was the Region II plateau. As the figure
illustrates, similarly well-defined plateaux were found by plotting N1/ γ˙ versus γ˙
for these five rate sweeps. It is noteworthy that proportionality between N1 and
γ˙ was observed for LCP at low deformation rates for a concentrated LCP solution
in cresol [Kiss and Porter, 1980; Moldenaers and Mewis, 1992]. Proportionality
between N1 and γ˙ was also observed for colloidal suspensions, block copolymers
(especially those with higher molecular weight blocks) and multi-branched star
polymers [Kotaka and Watanabe, 1987; Masuda et al., 1987]. The Larson and
Doi [1991] theory for polydomain flows predicts that:
( ) ( )( )
−1 / 2
N1 / σ 12 = 2 λ2 − 1 ; λ = pd2 + 1 / pd2 − 1 (134)
where λ is a characteristic ‘tumbling’ parameter given by the domain aspect ratio,
pd. For thermotropic LCP the value of this parameter is λ = 1.01 to 1.05 indicating
that N1 > σ12 [Ugaz et al., 2001]. This is not the case for CPNC in Region II
where the ratio N1/σ12 < 1 and consequently λ = 4.4, hence the equivalent ellipsoid
aspect ration pd ≅ 1.6. At the higher shear rates, in the beginning of the power
374
Rheology
Figure 111 (a) Shear viscosity and (b) a ratio of the first normal stress
difference and the deformation rate, N1/ γ˙ , for PANC at 240 °C. A series of the
indicated wait time between the data points, Δt = 0 to 540, was used. See text.
law Region III, for LCP negative first normal stress was observed; this behaviour
was not found in CPNC.
It has also been reported that in solutions of hydrophobically modified alkali-
soluble emulsions G´ is nearly a linear function of ω, and in concentrated
suspensions of non-colloidal spheres N1 is proportional to γ˙ [Brady and Bossis,
1985; English et al., 1997]. Proportionality of N1 to σ12 (with the proportionality
375
Clay-Containing Polymeric Nanocomposites
factor being characteristic of the system) was also reported for the latter system
[Zarraga et al., 2000].
376
Rheology
Figure 112 Fourier transform rheology, FTR, data for PANC at 240 °C, after 600
s of shearing at 70% strain with imposed frequency of 10 Hz. The harmonic peak
(I3) at 30 Hz is evident.
Figure 113 Relative intensity of 3rd harmonic peak, I3/I1, for PANC at 240 °C.
The plot illustrates how the non-linearity varies with strain, frequency and
shearing time.
377
Clay-Containing Polymeric Nanocomposites
Figure 114 Relative storage moduli of PE-MA with Cloisite® 6A at T = 210 °C.
Curves for frequency ω = 0.12 and 119 rad/s are shown. Data [Lim and Park,
2001].
in spite of high clay content the dispersed assemblies were relatively large and
had low aspect ratio. The high value of tplat agrees with the image of delaminated
platelets hindered in their rotation by crowding of the encompassed volumes.
Furthermore the observed drift of G´ versus ω dependence after alignment toward
that of the matrix indicates that alignment is easier at higher frequencies than at
ω = 1 rad/s, which was used in LAOS. Considering the long period of platelet
rotation (see Equation 105) the frequency most likely affected the extent of
interaction between platelets without forcing them to rotate.
Similar CPNCs, containing PE-MA and silicates of different aspect ratios,
were studied by Wang et al. [2002]. The PE-MA was LLDPE grafted with
0.85 wt% MAH. The silicates were two organoclays (Cloisite® 20A, C20A and
Laponite® SCPX2231, SCPX) and a synthetic SiO2. The organoclays were both
intercalated with 2M2HTA and had the nominal aspect ratio, p = 100 to 200
and 20 to 30, respectively. The silica had spherical particles with diameter of ca.
1.8 μm. XRD did not show diffraction peaks down to 2θ = 2°; hence d001 > 4.4 nm.
As it is to be expected, the initial slope, g´ = d lnG´/d lnω, a measure of deviation
from linear viscoelasticity, decreases with nanofiller content and aspect ratio.
Note that the matrix alone showed a lower value than that expected for a linear
viscoelastic liquid (g´ = 2), indicating that the system is phase segregated, with
MA domains acting as local crosslinks.
The data in Figure 115 indicate that g´ decreases with clay aspect ratio and
concentration. Other factors, such as the degree of exfoliation and potential
association of the intercalated clay platelets have also been identified [Lepoittevin
et al., 2002a,b]. Association is suspected in the system containing MMT
intercalated with MT2EtOH (Cloisite® 30B).
378
Rheology
Figure 115 The initial slope of the storage modulus versus frequency dependence,
g′≡ (∂lnG′/∂lnω)T for LLDPE-MA with two organoclays C20A and SCPX (with
aspect ratio: p ≅ 100-200, and 20-30, respectively) and with silica (p = 1). Data
[Wang et al., 2002].
While the end-tethered CPNC with PA-6 as a matrix showed rheological behaviour
similar to LCP, other CPNC may show behaviour resembling that of filled
polymers with yield stress. The review by Giannelis et al. [1999] provided several
examples of such behaviour. For example, the steady-state shearing of a
poly(dimethyl0.95 diphenyl0.05 siloxane) containing up to 35 wt% of MMT
intercalated with 2M2HTA (Cloisite® 6A) showed a steep increase of low-shear
viscosity with clay loading [Krishnamoorti et al., 1996]. In this case exfoliation
(suppressed at high loadings) seems only to intensify the known filler effects.
However, the authors also studied end-tethered PCL and PA-6 nanocomposites
with exfoliated MMT. Judging by the reported log G´ versus log ω plots, at a
MMT loading of 1 to 3 wt% the behaviour resembled that described in the
preceding parts for PA-6 based CPNC (LCP-type), but at a clay loading of 5 and
10 wt% the CPNC behaved as a filled-system. Note that at these high loadings
the platelets are crowded, unable to tumble along the flow lines.
Galgali et al. [2001] prepared CPNC by melt blending PP (82-97 wt%;
MFI = 3 and Mw = 300 kg/mol) with maleic anhydride grafted PP (PP-MA,
Polybond 3200) as compatibiliser and Cloisite® 6A (MMT-2M2HTA). The ratio
of PP-MA to organoclay was either 0:1 or 1:1. The mixtures were characterised
by TEM and XRD at T = 200 °C. Dynamic flow measurements were performed
at T = 200 °C and ω = 0.06 to 100 rad/s on samples annealed in a controlled
stress rheometer for t = 0 to 3 h. The ‘terminal’ slope of log G´ versus log ω at the
lowest frequencies, ω = 0.06 to 1 rad/s, depended on the compatibiliser and clay
content as well as on annealing time (see Figure 116). The data were analysed
using the linear function:
go′ ≡ lim ( d log G ′ / d log ω ) = ao + a1 w PP− MA + a2 wclay + a3 t (135)
ω →0
379
Clay-Containing Polymeric Nanocomposites
Figure 116 The initial slope of the storage modulus versus frequency
dependence, g′≡ (∂lnG′/∂lnω)T for PP/PP-MA/ Cloisite® 6A. Upper line for CPNC
without compatibiliser (PP-MA), lower for PP-MA content the same as that of
Cloisite® 6A. Data from [Galgali et al., 2001].
380
Rheology
381
Clay-Containing Polymeric Nanocomposites
Figure 117 Storage shear modulus at constant frequency (G´ at T = 180 °C and ω
= 10 rad/s) versus interlayer spacing, d001, for PP with 4.8 wt% MMT intercalated
with (from the bottom left) tri-decyl amine (C13), di-tri-decyl amine (2C13), a
mixture of these (C13+ 2C13), and stearyl amine (C18). Data [Solomon et al., 2001].
intercalant parallel those between intercalated stacks in the PP matrix – the latter
are responsible for the rheological response.
To study the viscoelastic non-linearity Solomon et al. used shear flow reversals.
First, a CPNC specimen was sheared for 300 s at γ˙ = 0.005 to 1.0 s-1 recording
the value of the shear stress (σ12), then the flow was stopped for a time, trest, and
the specimen was re-sheared at the same rate of shear, but in the opposite direction.
As has been observed for LCP and CPNC with PA-6 as the matrix, the magnitude
of the stress overshoot (σmax) increases with trest. The authors constructed master
curves by plotting: (σmax/σ∞ - 1)/c versus trest (where σ∞ is the value of σ12 at long
time and c is MMT loading). The linear scaling with c indicates that during non-
linear deformation the stress response originates in the individual clay domains,
thus the network is destroyed by deformation. The stress overshoot is related to
the distribution of particle orientations in CPNC and the stress-induced destruction
of the network. Furthermore, the linear scale suggests that the domain size is
independent of loading. It is interesting to note that, not unexpectedly, the
magnitude of the stress overshoot depended on the rate of shearing (see
Figure 118). The anisometric structure of the CPNC was considered responsible
for the non-linear flow behaviour.
CPNC of PP with organoclay and PP-MA was prepared by melt compounding
[Li et al., 2003]. The ratio of compatibiliser (containing 0.31 wt% of MAH) to
organoclay was 3. Strong non-linear viscoelastic behaviour was observed at
organoclay loadings exceeding 2 wt%, i.e., 8 wt% of organoclay + PP-MA. The
interlayer spacing only slightly expanded from that of neat organoclay, viz. from
d001 = 3.5 to 4.2 nm. The strong non-linearity in the dynamic response indicated
the formation of a 3D structure readily altered by pre-shearing. Similarly, as for
PA-based CPNC, (see Figure 109 and Figure 110) stress overshoot was observed.
382
Rheology
Figure 118 The ratio of the maximum stress overshoot to its plateau value
versus the rate of shear, γ˙ . Data [Solomon et al., 2001].
Considering the low degree of clay dispersion, it is unlikely that the origin of the
observed non-linearity is the platelet/platelet interaction. Similarly, since the degree
of PP-MA maleation was low, it is doubtful that it phase-separated from the PP
matrix. Thus, the most probable structure responsible for the non-linear
viscoelastic behaviour is the interaction between domains of organoclay tactoids
embedded in a cloud of the compatibiliser, the latter bonded to the clay platelets.
Okamoto et al. [2001a,d] studied the rheology of CPNC with PP-MA as the
matrix. The system was prepared by melt compounding at T = 200 °C maleated-
PP (PP-MA, 0.2 wt% MAH) with 0, 2, 4 and 7.5 wt% of MMT intercalated
with stearyl ammonium ion (ODA). TEM showed fine dispersion of the silicate
stacks ca. 193 to 127 nm long and about 5 to 10.2 nm thick, respectively.
According to XRD the interlayer spacing of the organoclay increased from only
d001 ≅ 2.31 to 3.24, 3.03 and 2.89 nm, respectively. The PP crystalline lamellae
thickness and spherulite diameter did not depend on clay content. For the
rheological study the rotating clamps, Meissner-type elongational RME rheometer
was used at T = 150 °C and Hencky strain rates ε̇ = 0.001 to 1.0 s-1.
The stress growth function in elongational flow, log η E+ versus log ε̇ for the
three CPNC compositions showed strain hardening (SH). The latter function is
defined as a logarithm of a ratio of the stress growth function in elongation to
three times that for the linear viscoelastic response in shear, with both values
taken at the same deformation time, t, viz.:
(
SH ≡ log η E+ / 3ηS+ ) t
(136)
SH has been observed for entangled polymers (e.g., LDPE), for highly
polydispersed resins (e.g., some LLDPE where Mw/Mn = 10 to 50) as well as for
the new bimodal metallocene PO. Partial crosslinking as well as dissolution of
ultrahigh molecular weight polymer into its standard resin are also known to
induce SH. The phenomenon is essential for several processing operations, viz.
383
Clay-Containing Polymeric Nanocomposites
384
Rheology
Figure 119 Typical strain hardening plot for a single-phase polymer, viz. for
branched PC at 270 °C [Utracki and Sammut, 2000; unpublished].
Figure 120 Strain hardening parameter, SH, versus Hencky strain at indicated rates
of extension, ε̇ , for CPNC of PP-MA with 4 wt% of C18-MMT (d001 = 3.03 nm).
Data [Okamoto et al., 2001]. The absence of superposition of data for constant values
of ε̇ indicates the presence of a 3D network of interacting organoclay particles.
385
Clay-Containing Polymeric Nanocomposites
et al., 2001a, d; 2002; Nam et al., 2002]. The foams of PP-MA and CPNC with
2 wt% organoclay had closed cell structures with pentagonal and/or hexagonal
faces. For the higher clay concentrations, the cells had closed spherical structure.
The foamed CPNCs had a high cell density of 107-108 cells/ml, the homogeneity
of cell size was in the range of 20-120 μm, the cell wall thickness was 5-15 μm,
and the low mass density was 0.05-0.3 g/ml. Within the cell walls clay particles
were biaxially aligned along the cell boundary. TEM showed that MMT platelets
were oriented parallel to the wall surface. In the junction of three adjacent cells
the platelet orientation near the walls was parallel to the proximate one with a
random orientation in the centre of the three-cells junction.
However, it seems that SH is not the only mechanism responsible for enhanced
foamability of nanocomposites – it has been shown that CO2 foaming of either
PMMA-based CPNC or neat PMMA geometrically constrained 75-100 μm thick
films follows a similar mechanism and leads to a decrease of cell size and increase
of cell density [Siripurapu et al., 2002].
The batch foaming of PP-based CPNC (clay content 2, 4, and 7.5%) was
carried out in a high-pressure cell equipped with a microscope and high-speed
digital video recording camera [Taki et al., 2003]. Significant reduction of the
bubble size (from 155 to 34 μm) and increase of cell density (from 2.5 to 220 cells/nL)
has been observed. Furthermore, the foam compression modulus increased by a
factor of 6.These observations were confirmed in the sequel publications. Thus,
preparation of micro- and nanocellular foams in PLA-based CPNC has been
accomplished [Fujimoto et al., 2003; Ray and Okamoto, 2003]. Foaming of
PLA/organoclay nanocomposites has been conducted using supercritical CO2.
Compared to neat PLA foam, the CPNC foam showed smaller cell size and higher
cell density, confirming that the dispersed silicate particles acted as nucleating
sites for cell formation and the increase in SH stabilised the bubble growth. The
biaxial flow-induced alignment of the platelets along the cell boundary also had
a positive effect on the strength of the bubble wall, hindering coalescence. PC-
based CPNC were also successfully foamed [Mitsunaga et al., 2003]. The relatively
easy foamability of CPNC with supercritical CO2 to give materials with small
cell diameter (nanofoams with 200 nm diameter bubbles have been produced)
may be in part due to the high solubility of CO2 in most polymers. Even in the
case of insolubility (e.g., PEG swells but does not dissolve in CO2) its presence
increases the free volume content, thus macromolecular mobility, which on the
one hand leads to the expansion of interlayer spacing [Zhao and Samulski, 2003]
and on the other to higher foaming rates.
As recent events demonstrate, CPNC foaming is close to commercialisation.
For example, PU-based CPNC foams with submicron size cells combining
exceptional mechanical, thermal, and barrier properties have been identified as
prime candidates for high efficiency insulation in refrigerators [Domszy, 2004].
The patenting activities also reflect the high expectations from this technology.
For example, a general patent for foaming CPNC was applied for [Lee et al., 2003].
Its claims are quite broad, specifying a diversity of polymers (PS, PMMA, PP, PA,
PU, elastomers, and their blends), of organoclays (of MMT, HT, FH, saponite,
laponite, and beidellite), incorporated in amounts ranging from ≤ 0.5 to ≤ 20 wt%,
and using from ≤ 1 to ≤ 7 wt% of a blowing agent (supercritical CO2). The resulting
closed or open cell foams should have cells with diameter ranging from 15 to
20 μm, and cell density from 106 to 109 cells/ml. Extrusion or batch foaming quality
depends on the CO2 content, melt temperature, and pressure drop rate.
386
Rheology
387
Clay-Containing Polymeric Nanocomposites
388
Rheology
d001 = 2.66 nm, smaller by about 0.3 nm from the value in monomer suspension.
SPN suspended in MMT was fully exfoliated, while PMMA/SPN nanocomposite
showed a small shoulder at d001 ≅ 4.55 nm. For the St/SPN suspension, a small
shoulder was found at d001 ≅ 3.85 nm, i.e., reduction of the interlayer spacing of
neat SPN. The PS/SPN nanocomposites showed strong diffraction peaks,
demonstrating that in this case polymerisation leads to ordered intercalated
nanocomposites.
The frequency sweeps for the suspensions showed two types of rheological
behaviour. The suspensions of intercalated MMA/STN and St/SPN systems
indicated solid 3D, gel-like behaviour with frequency-independent dynamic
moduli. By contrast, the exfoliated MMA/SPN suspension showed strong
frequency dependence. The data indicate that at 10 wt% loading in the monomer
the expanded, intercalated clay stacks strongly interact with each other. However,
surprisingly, the exfoliation into individual platelets seems to eliminate the
interactions. For the polymerised CPNC systems only a viscoelastic temperature
sweep was carried out.
Kim et al. [2002] emulsion polymerised PS in the presence of Na-MMT highly
swollen in water. CPNC containing 0, 2, 5 and 10 wt% of clay were prepared.
Polymerisation increased d001 from 1.195 nm determined for dry Na-MMT to
1.511 nm measured for the three CPNCs. Thus, in these nanocomposites the
interlamellar galleries of MMT were expanded to h = 0.55 nm hence slightly
larger than estimated from the Flory diameter of the paraffinic chain (0.45 nm),
but significantly smaller than that of PS (0.83 nm). As a result, the clay was
poorly dispersed in the PS matrix. The flow curves, log η versus log γ˙ , showed a
simple pseudoplastic behaviour, following the dependence:
η = ηo ⎡1 + (λγ˙ ) ⎤
1− n
(137)
⎣⎢ ⎦⎥
Here, ηo is the zero shear viscosity, λ is the longest relaxation time, and n is a
power law exponent. From the values of ηo the intrinsic viscosity listed by the
authors, [η] = 112 and the aspect ratio p = 270 was calculated. Thus, the assemblies
of intercalated MMT platelets are highly anisometric. In consequence, scans
conducted by increasing and decreasing the rate of shear resulted in a hysteresis
loop, with the former scan data forming the upper and the latter scan data forming
the lower part of the loop. The size of the loop increased with clay concentration.
Three PS grades from Nova Chem with Mw = 310, 270, and 230 kg/mol were
melt compounded in a TSE (T = 200 °C, screw speed of 200 rpm, feed rate of
5 kg/h) with 1 to 20 wt% of Cloisite® 10A (MMT-2MBHTA) [Tanoue, et al.,
2003b]. It was found that each re-extrusion of CPNC reduced the zero-shear
viscosity, ηo, by about 30%. This is particularly interesting since increasing the
residence time in a TSE by a factor of up to 10 did not reduce further the CPNC
matrix viscosity. Similarly, extrusion of neat PS had only a small (ca. 2%) effect
on ηo. Thus, the combination of oxygen, temperature and organoclay was
responsible for the degradation of PS.
The rheological properties of these CPNCs were measured in the steady shear
and dynamic mode at 160, 200 and 240 °C. The time-temperature (t-T)
superposition was found valid, with the horizontal and vertical shift factors being
nearly independent of the organoclay content and PS grade. The extrapolated
zero-shear viscosity and zero-shear storage modulus slightly increase with
organoclay content. According to the results of strain sweeps (γ = 0~100%,
389
Clay-Containing Polymeric Nanocomposites
T = 200 °C, ω = 6.28 rad/s) for γ > 40%, the storage and loss moduli of all
specimens (including PS) decreased with strain. The frequency sweeps showed
that the storage and loss modulus increase with organoclay content. At low
frequency (ω < 0.1rad/s), the initial slopes of the log G´ or log G´´ versus log ω (g´
or g´´, respectively) decreased with organoclay content, e.g., for 0 to 10 wt%
organoclay g´ decreased from 1.9 to 1.6, and g´´ from 0.99 to 0.95. In steady-
state shear flow tests in a capillary rheometer, the power law index of the shear
viscosity decreased with increasing organoclay content. The extensional flow
behaviour of the PS matrix and the CPNC were also studied. It was found that
incorporation of the degraded organoclay resulted not in strain hardening, but
in a small strain softening effect, similar to that observed by Takahashi [1996]
for polymeric composites with solid particles.
Sohn et al. [2003], studied PS with Cloisite® 25A (MMT-2MHTL8). A solvent
(chloroform) casting method was used to prepare CPNC with 0, 2 and 10 wt%
of organoclay. Upon mixing with PS the organoclay interlayer spacing increased
from d001 = 1.94 to 3.27 nm. The dynamic flow measurements were carried out
at 200 °C. In spite of the achieved expansion of the interlamellar galleries, the
rheological data show small increases of both, G´ and G´´ moduli – a behaviour
typical to composites, but not nanocomposites. Thus, similarly as in the work by
Ren et al. [2000], here also only a monolayer of PS could be inserted into the
organoclay gallery space.
As these studies on PS-based CPNC indicate, preparation of CPNC with PS
as the matrix has been largely unsuccessful. The exceptions are the systems where
amine-terminated PS was used as intercalant (as in publications from Friedrich’s
or from Qutubuddin’s laboratories), to directly bond to the clay surface and to
form a miscible blend with the matrix. Evidently, PS is immiscible with alkyl-
intercalants. The macromolecular diffusion into interlamellar galleries most likely
originates in the tendency of aromatic molecules (i.e., benzene rings) to complex
with surface cations. However, once the first macromolecule is inserted, on the
one hand the attractive sides are shielded and on the other the interaction between
benzene side groups and clay expose the paraffinic chain. As a consequence, the
intercalated stacks of organoclay particles phase-separate from the matrix. The
situation is worse when during melt compounding the intercalant decomposes
and bare clay platelets re-aggregate into stacks with mineral clay spacing, e.g.,
d001 ≈ 1.4 to 1.7 nm.
390
Rheology
exfoliated – concentration had only a small effect on d001. TEM showed highly
anisometric aggregates, ca. 200 nm thick and several micrometres long.
Rheological properties of these systems were measured in the steady-state
and dynamic shearing modes in parallel-plate geometry at 120 °C. The steady-
state data were fitted to the generalised Carreau-Yasuda equation:
2 (
1− n ) / 2
η = ηo ⎡1 + (λγ˙ ) ⎤ (138)
⎣⎢ ⎦⎥
During steady-state shearing the systems showed a pseudoplastic behaviour.
Addition of organoclay increased the shear viscosity – the strongest effects were
observed for C15A, then C20A and the weakest for C25A. Evidently, increasing
the concentration of organoclay also increased the strength of the rheological
signal. From the cited values of ηo for the CPNC with C25A, the intrinsic viscosity
[η] = 44 and the aspect ratio, p = 155 were calculated, confirming the TEM
observations of anisometric aggregates. Shearing while increasing and then
decreasing the deformation rate produced hysteresis loops, with the maximum
loop height observed for the highest hs material near the rate of shear: γ˙ ~ 1/λ.
The concentration dependence of the relative shear viscosity was fitted to the
Krieger-Daugherty [1959] equation:
[ ][]
− η φmax
ηr ≡ η / ηφ →0 σ 12 = const = 1 − φ / φmax (139)
For the multiphase systems, this relation must be taken at constant stress, σ12 = const.
For monodispersed particles, the maximum packing volume fraction, φmax, has a
unique, theoretically predicted value. For polydispersed suspensions, its value
depends on the polydispersity of size, shape and orientation of the dispersed
particles, thus it has to be treated as an adjustable parameter.
Dynamic measurements were carried out to analyse the CPNC structure within
the linear viscoelastic region at strain γ = 0.03. G´ and G´´ were measured for
nanocomposites containing C25A at clay content 0 to 17 wt%. The moduli
showed a monotonic increase at all frequencies. The initial slope of the storage
modulus, g´ ≡ d log G´/d log ω < 2 was observed for all concentrations (including
neat PEG). A solid-like behaviour was particularly pronounced at w ≥ 9 wt% of
organoclay. This may indicate that within this region, the clay aggregates are
unable to rotate hence they are prevented from relaxing. It was reported that
organoclay enhanced thermal stability of the nanocomposites.
Gelfer et al. [2002] prepared CPNC by melt blending commercial organoclays
with either poly(ethylene-vinylacetate) (EVAc; 3.1 and 8.15 mol% VAc) or
neutralised poly(ethylene-methacrylic acid) (PEMA; 3.1 mol% methacrylic acid).
The reason for using these copolymers originated from the observation that
organoclay is easier to disperse in highly polar polymers. Thus, EVAc and PEMA
were used as models for studying the structure, property and processing
relationships in CPNC. The organoclays were: Cloisite® 6A (C6A; d001 = 3.59 nm),
Cloisite® 20A (C20A; d001 = 2.47 nm), and Nanomer I30 E (I30). They all contain
MMT intercalated with (1) 2M2HTA (6A and 20A) or (2) N-tallow alkyl
trimethylene diamine chloride (?) (I30 usually comprises MMT-ODA). The
intercalant content was 45 wt% in C6A, and 30 wt% in C20A and in I30. XRD
of the CPNC indicated intercalation with d001 = 2.1 to 4.1 nm. In all systems, Tm
and crystallinity were not significantly affected by the presence of organoclays,
391
Clay-Containing Polymeric Nanocomposites
suggesting that clay particles were shielded from the matrix by the intercalant
molecules and predominantly confined to the amorphous phase.
Small strain oscillatory experiments were carried out at constant strain
amplitude (γ = 0.06), frequency 0.1 < ω < 100 rad/s and T = 120-200 °C (above
Tm). Under these conditions the specimens remained stable for t < 30 min. The
CPNC with EVAc as a matrix showed solid-like behaviour at small-strain
oscillatory shear, but it was able to yield and flow under a steady shear – the
characteristic performance of physically crosslinked systems. In contrast, the
CPNC with PEMA as matrix exhibited a melt-like rheological behaviour, with a
minimal contribution by the organoclays. The controlled stress rheometer was
used to determine the yield stress. The authors speculated that the carbonyl groups
of VAc in EVAc interact with the clay surface, resulting in physically crosslinked
structures. By contrast, the interactions between PEMA and the clay were
considered weak (due to repulsion between carboxyl anions and the negatively
charged clay surface) preventing the formation of structures in these systems.
The extrapolated ηo versus T showed an upswing at T > 200 °C, indicating physical
crosslinking. The time-temperature superposition has not been discussed, but
judging by the reported rheological data, its applicability to the studied systems
is dubious.
392
Rheology
able to interact with the matrix (e.g., end-tethered systems) results in significant
enhancement of strain hardening. This effect agrees very well with the ‘hairy clay
platelet’ (HCP) model of CPNC. Thus, in analogy to improved processability of
some resins by blending them with branched homologues (e.g., common industrial
blends of LLDPE with LDPE) one may use CPNC technology to improve film
blowing, blow moulding or foaming (and microfoaming) of difficult to process
resins. At high extensional flow rates, the platelets may be oriented perpendicular
to the stretch direction, which causes the transient viscosity to move into the
strain hardening region. Both effects are stronger for the end-tethered than the
free platelets systems, especially at higher clay loading.
393
Clay-Containing Polymeric Nanocomposites
394
Nucleation and Crystallisation
3.4
Nucleation and
Crystallisation
3.4.1 Introduction
Polymers may crystallise when: (1) their molecules have sufficiently regular
structure and mobility, (2) the temperature is: Tg < T < Tm, (3) there are nuclei
present and (4) the rate of crystallisation is sufficiently high.
Nucleation is the initial stage of the phase separation during which a new
phase is formed on a minute amount of substance that acts as a nucleus for
subsequent phase growth. In Nature, fog, rain or snow are formed through this
process. Nucleation of crystals requires seed crystals, viz. self-formed nuclei, dust
particles or nucleating agents. Thus, crystallisation may take place via a
homogeneous crystallisation mechanism, where the molecules self-assemble into
ordered entities having critical size for the crystal growth, or via a heterogeneous
crystallisation mechanism, where the molecules assemble on the surface of a
foreign body. In polymer technology, especially for injection moulding, the desired
high crystallisation rates often require the addition of nucleating agents.
A nucleating agent is a substance that forms nuclei for the growth of crystals
in a supercooled polymer melt. Virtually any solid body with a high energy surface
may act as a nucleating agent. However, for efficient nucleation it is necessary
that the crystalline structure of the nucleating agent closely matches the crystalline
structure of the polymer [Vesely, 1996]. Several specific crystalline or crystallisable
substances have been developed, viz. 4-biphenyl carboxylic acid, aluminium salts
(benzoate, phenyl-acetate, tert-butyl-benzoate), antimony compounds (trioxide,
phosphates), sodium salts (4-methyl-valerate, benzoate, β-naphthoate, caproate,
cinnamate, succinate), pigments, etc. These substances generate from 2 to
20 million nuclei per 1 mm3.
The nucleating agents may preferentially induce a specific crystallographic
form of the polymer. For example, addition to isotactic-PP of either 1,2,3,4-bis-
(3,4-dimethyl-benzylidene sorbitol) or N,N´-dicyclohexyl-2,6-naphthalate
dicarboxamide, preferentially generate α-iPP or β-iPP, respectively. The nucleating
efficiency depends on several independent variables, such as temperature, pressure,
stress, part thickness as well as the presence of other processing additives. For
this reason, during the last few years combinatorial methods have been used to
study polymer nucleation and crystallisation.
As stated above, an efficient nucleating agent must have a high-energy surface
– the larger the specific surface, the more efficient it is expected to be. Nucleation
involves initial adsorption of macromolecules on the surface. The process is
particularly efficient if the foreign body is able to provide an energetic matrix for
the formation of thermodynamically favourable crystalline forms. Alternatively,
the crystalline cell type and size of the nucleating agent may induce a transitory
crystalline polymer form that upon annealing transforms into a stable form of
395
Clay-Containing Polymeric Nanocomposites
higher packing density. Several researchers have reported this behaviour for CPNC
with PA-6 as the matrix.
The nucleating efficiency, ϕ, may be expressed in terms of the energy ratio
required to generate a nucleus in a heterogeneous nucleation over that in a
homogeneous one [Dobreva and Gutzow, 1993]. The authors assumed that
nucleation is the rate-determining step, while the extent of crystallinity is constant.
Thus, the nucleation rate, r, depends on the degree of supercooling, ΔTp = Tm - Tc:
{ }
r = A exp − En / ΔTp2 ; En = ωσ 3 Vm2 / nk B Tm ΔSm2
(140)
ϕ ≡ En (hetero) / En (homo) T ≈Tm
where En is the energy required to form a nucleus, ω is a geometrical factor, σ is the
specific surface energy, Vm is the molar volume of the crystallising substance, ΔSm
is the melting entropy, n is the Avrami exponent and kB is the Boltzmann constant.
According to Equation 140, the nucleating activity factor (ϕ) is given by the ratio
of the slopes of ln r versus 1/ΔTp2. Note that 0 ≤ ϕ ≤ 1, with ϕ = 0 indicates the
highest activity of the nucleating agent and ϕ = 1 indicates total lack of it.
Nanofillers such as clays may have strong nucleating effects. The wide variety
of intercalants, intercalating methods and compatibilisers may form a barrier
between the high-energy clay surface and the semicrystalline polymer matrix. In
this section the recorded effects of nanoclay on the crystallinity of CPNC will be
summarised. Since CPNC with PA and PP matrices are of great academic and
industrial interest the focus will be on these two classes of nanocomposites.
396
Nucleation and Crystallisation
homogeneous nucleation excepting the presence of a high energy solid surface that
lowers the magnitude of ΔG*. As a result the critical size of the nucleus is reduced,
which in turn leads to crystallisation at lower undercooling, thus:
[
ΔG* = 16σ ( Δσ )σ e Tm (Tm + T ) / 2Δh f (Tm − T ) ]
2
(143)
where Δσ is the specific interfacial free energy difference between the nucleus
and the nucleating agent. The overall crystallisation kinetics of blends is often
described by the Avrami equation [Avrami, 1939]:
{ }
α (t ) = 1 − exp − kt n (144)
α(t) is the weight fraction of a crystalline part at time t, whereas n and k are equation
parameters. The Avrami index (n) depends on the type and geometry of nucleation
and the crystal growth, thus it may be written as n = nnucleation + ngrowth. The Avrami
rate parameter k, is often expressed in terms of the crystallisation half-time, t1/2:
k = (ln 2) / t1n/ 2 (145)
Derivation of the Avrami equation is based on several assumptions, such as the
shape constancy of the growing crystal, the constant rate of radial growth, lack
of induction time, the uniqueness of the nucleation mode, complete crystallinity
of the sample, random distribution of nuclei, constant radial density, primary
nucleation process (no secondary nucleation) and absence of an overlap between
the growing crystallisation fronts. Furthermore, the often-cited form of the
dependence is simplified – as Ga ęski [1995] pointed out, the relation is only
valid for sporadic or instantaneous nucleation. The derived expressions are
different for crystallisation in films and in the bulk.
Pérez-Cardenas et al. [1991] developed a modified Avrami expression,
separating the primary and the secondary (subscripts ‘p’ and ‘s’, respectively)
crystallisation effects. Thus, the crystalline weight fraction, α, was written as:
α = αp + αs (146)
Accordingly, the crystallisation proceeds in three steps: (I) the initial primary
crystallisation, (II) mixed primary and secondary crystallisation and (III) pure
secondary crystallisation. The authors expressed the weight fraction of the polymer
crystallised by primary and secondary crystallisation as ζ. In consequence, the
crystallisation may be described by two equations:
⎡ t ⎤
( ) ⎢⎣ ∫ ( )
1 − α = exp − kt n − k ′t n′ ⎢kn(1 − ς ) xp kt n + k ′t n′ τ n−1 dτ + 1⎥ ; α ≤ ς (147)
⎥⎦
0
{ } { }
1 − α = (1 − ς ) exp k ′t * n′ exp k ′t n′ ; α > ς (148)
Now, six parameters are required to describe the process: k and n (the primary
crystallisation parameters) depend on crystallisation temperature, the nature of
primary nucleation and the fast growth; the secondary crystallisation parameters,
k´ and n´ depend on the conditions under which the slow crystallisation of the
remaining amorphous regions takes place, ζ, indicates the weight fraction of
material crystallised up to the moment the primary crystallisation ends and t*
indicates the start of the pure secondary crystallisation.
Furthermore, Avrami theory is limited to isothermal processes. Since polymer
processing is mostly non-isothermal, the theory has been extended by Ozawa
397
Clay-Containing Polymeric Nanocomposites
⎧ t ⎫
α (t ) = 1 − exp ⎨− k (T )nt n−1 dt ⎬
∫
⎩ 0 ⎭
⎧⎪ T (149)
dT ⎫⎪
n −1
⎛T −T⎞
α (T ) = 1 − exp ⎨− k (T )n⎜ o
∫ ⎟ ⎬
⎝ R ⎠ R⎪
⎩⎪ o
T
⎭
where k(T) and n are Avrami’s isothermal parameters. For DSC scans the following
expression has been successful:
[α ′ (T
p p )] [ (
− Tons / β 1 − a p )] = (n − 1) − [ E(T
p )] [
− Tons / RTp2 ] (150)
where : Tp = Tons + βt and α ′p ≡ dα / dt = (1 − α )nkt (
n −1 )
where β is the heating rate, Tons is the onset temperature, Tp is the peak temperature
reached after time t, and E is the activation energy of the crystallisation process.
In a semicrystalline homopolymer, the change in free energy of melting per
mole of monomer is given by:
ΔGu(T) = ΔHu - TΔSu (151)
where ΔHu and ΔSu are the enthalpy and the entropy changes on melting,
respectively. For an infinitely thick crystal at equilibrium melting temperature
Tm, ΔGu(Tm) = 0 and:
T m = Δ Hu / ΔS u (152)
The value of Tm can experimentally be determined from Hoffman-Weeks plots,
where the experimental melting point is plotted as a function of the crystallisation
temperature, Tc. Extrapolation of experimental data to the Tm = Tc line gives the
equilibrium value of Tm.
Xu et al. [2001] studied the nonisothermal crystallisation kinetics of CPNC
with POM or with PP [2002] as the matrix. Two CPNC with POM were prepared
in a roller mill at T = 175 to 180 °C; the first comprised 5 wt% of Na+-MMT and
the second MMT-3MHDA. The interlayer spacing in these systems was d001 = 1.92
and 3.52 nm, respectively. The nonisothermal crystallisation kinetics were
investigated by DSC at 5 to 40 K/min cooling rate. The difference in the values of
the Avrami exponent n between POM and the nanocomposites suggests a
tri-dimensional growth with heterogeneous nucleation. At a given cooling rate
the crystallisation of neat POM was slightly slower than that of either
nanocomposite. The activation energies, 387, 330, and 329 kJ/mol were
determined for the nonisothermal crystallisation of POM, POM/Na+-MMT
nanocomposite, and POM/MMT-3MHD, respectively.
A similar process was used to prepare nanocomposites with PP with 3 wt%
MMT-3MHDA. A 3 mm thick sheet was compression moulded at 180 °C. The
interlayer spacing was d001 = 3.88 nm. The crystallisation rate increased with
increasing cooling rates for both PP and its nanocomposite. The crystallisation
rate of CPNC was higher by 40% at a cooling rate of 5 K/min, but virtually
398
Nucleation and Crystallisation
identical at the fastest cooling rate of 40 K/min. The activation energies were
estimated as 189 and 156 kJ/mol for PP and nanocomposite, respectively. Thus,
incorporation of 3 wt% of organoclay into PP affected the matrix crystallisation
more than 5 wt% in POM.
General procedures for evaluating crystallinity in polymeric systems by XRD
and DSC have been developed, e.g., by Murthy and Minor [1990] and by Khanna
and Kuhn [1997], respectively. Additional information on the topic can be found
in [Mathot, 1994; Chan et al., 1995; Hammami et al., 1995], etc.
399
Clay-Containing Polymeric Nanocomposites
α-form has a planar zigzag chain conformation, the metastable (pseudo-) hexagonal
γ-form has a twisted chain, while the β-form is less well identified and often considered
to be an intermediate stage between the two others. The α-form is most common,
readily obtained during melt processing. A nearly pure α- and γ-form may be obtained
by, respectively, treating the specimen in superheated water vapour at 150 °C, and
by reversibly complexing it with iodine from KI aqueous solution [Penel-Pierron et
al., 2001a,b]. Uniaxial drawing increases the α-form content and reduces that of the
γ-form. The tensile strength is higher for the α-form, while the γ-form shows better
toughness. The solid/solid transition of α-crystal into γ-crystal, observed during heating
or cooling, is known as the Brill transition.
At the crystallisation temperature, Tc > 450 K PA-6 crystallises in a mixture
of α- and γ-forms, whereas above this limit essentially in nearly a pure α-form
[Privalko et al., 1979]. Thus, the α-form is more stable at higher temperatures.
The authors reported that addition of glass beads or aerosil to PA-6 did not
change the molecular mechanism of crystallisation. PA-66 crystallises in at least
six forms, of which the αI- and β-form dominate. Incorporation of organoclay
into PA-6 increases the nucleation density, the proportion of the γ-form in the
crystal as well as modifying the total crystallinity content. While the former two
effects are generally accepted the latter is more controversial – some authors
report enhancement, some others reduction while newer publications indicate
that both may be present within specific ranges of conditions, e.g., using a different
cooling rate or annealing method.
Kojima et al. [1994] used XRD and DSC to study orientation and crystallinity
of the exfoliated PA-6/MMT system. The platelets of MMT and the γ-form of
PA-6 crystallites were reported parallel to each other. The α-form was not detected.
Incorporation of 0.2 to 0.8 vol% MMT increased the degree of crystallinity of
PA-6 (to 31%) by 5 to 7%, but the effect did not depend on composition. In the
following publication it was reported that in injection moulded tensile bars the
orientation depended on the depth, but the γ-form of PA-6 still dominated the
crystalline phase [Kojima et al., 1995]. In the surface layer of the moulding,
MMT platelets and chain axes of crystalline PA-6 were parallel to the surface. In
the intermediate layer the MMT platelets remained parallel to the surface of
tensile bar, but the chain orientation rotated 90o (hence orienting perpendicularly
to both, bar surface and MMT). In the central layer the platelets were randomly
oriented along the flow axis with chain axes perpendicular to them.
Usuki et al. [1995] studied CPNCs of PA-6 containing ca. 5 wt% of MMT,
synthetic mica, saponite or hectorite (CEC = 1.2, 1.0, 1.0 and 0.5 meq/g,
respectively). Prior to reactive exfoliation in ε-caprolactam, the clays were
pre-intercalated with ω-amino lauric acid (ADA). Owing to end-tethering, the
concentration of –COOH macromolecular chain ends was about twice as large as
that of –NH2. The authors established correlations between the performance (e.g.,
tensile strength, modulus, HDT), the strength of the clay-polymer interaction
(determined by the 15N-NMR chemical shift, CP) and the degree of crystallinity, X
(wt%). The latter was calculated from the DSC-measured heat of fusion, taking
the literature value for the heat of fusion of PA-6 crystal as 188 J/g. Surprisingly, it
was found that X decreased upon incorporation of organoclay. At the same time,
the mechanical performance (e.g., tensile modulus) increased with CP from 1.11
for PA-6 to 2.02 GPa for CPNC with mica. These observations are summarised in
Figure 121 – note that excepting the degree of crystallinity, X (wt%), the other
performance characteristics for CPNC diverge from those of PA.
400
Nucleation and Crystallisation
Liu et al. [1999] prepared CPNC by melt blending PA-6 in a TSE with 1 to
18 wt% of MMT (CEC = 1.0 meq/g) intercalated with ODA. After compounding
at T = 180 to 220 °C, the CPNC with more than 10 wt% of organoclay showed
intercalated structures with d001 increased from 1.55 to 3.68 nm. However, at
low MMT content the samples were exfoliated. In accord with the Usuki et al.
[1995] results, the authors observed a difference in crystallisability between PA-6
and its CPNC – addition of any amount of clay reduced the supercooling effect
to a common level, indicating enhanced nucleation. However, by contrast with
the Usuki et al. [1995] results, here all specimens (with 0 to 6.7 wt% MMT)
showed about the same crystallinity. The difference most likely originates in the
different internal structure of these CPNC – in the former work the reactive
exfoliation resulted in end-tethering, whereas compounding PA-6 with pre-intercalated
MMT generated exfoliated CPNC (at lower clay content), but without end-
tethering. XRD of PA-6 showed a virtually pure α-crystallographic form, whereas
the polymer in CPNC crystallised mainly in the γ-form.
Wu and Liao [2000] prepared CPNCs of exfoliated synthetic saponite in a
PA-6 matrix using the reactive route with a unique pre-intercalation step; synthetic
clay was dispersed in water/ε-caprolactam/phosphoric acid solution, then the
mixture was polymerised at T = 80 to 270 °C under pressure. The authors do not
provide information about the platelet dispersion. XRD and DSC were used to
study the effect of clay on crystallinity, which in turn was related to performance.
The specimens containing 0, 2.5 and 5 wt% clay were pressed into sheets at
240 °C, then either slowly cooled or quenched to room temperature. Slow cooling
Figure 121 Crystallinity, relative tensile strength, TS/TS(PA), and relative HDT
(expressed in Kelvin), HDT/HDT(PA) as functions of the 15N-NMR chemical shift,
CP. Systems: PA-6 with 5 wt% of exfoliated clay – see text. Data [Usuki et al.,
1995].
401
Clay-Containing Polymeric Nanocomposites
resulted in nearly pure γ-form crystals in the sample containing 2.5% clay, nearly
pure α-form in the sample containing 5 wt% clay and polymorphic crystals in
PA-6. By contrast, quenching yielded a nearly pure γ-form for the sample with
5 wt% clay, predominantly α-form for PA-6 and intermediate polymorphous
composition for the sample containing 2.5 wt% clay. To transform γ- into α-form
required 2 h heating at 210 °C. Addition of synthetic saponite increased the
crystallisation rate, but the crystallinity was not determined. The tensile modulus
and HDT showed significant improvements.
Akkapeddi [2000] used a melt compounding method for the manufacture of
PA-6 based CPNC. Thus, organoclay of MMT or hectorite was dispersed in PA-6
at a level of 2 to 5 wt% of clay. The author reported that clay platelets had
strong surface nucleation effects that promoted faster crystallisation and a higher
level of crystallinity in relation to that of neat PA-6 (particularly at the surface
and in thin-wall injection mouldings). For example, in 1 mm thick PA-6 injection
moulded bars the crystallinity was 16 to 18%, while in CPNC (4 wt% clay) the
crystallinity was 50% throughout the specimen. It is noteworthy that whilst in
PA-6 specimens the skin had lower crystallinity than the core, in CPNC the
situation was reversed.
Giza et al. [2000] reported enhanced crystallinity in spun fibres of PA-6/MMT
(from Ube). While the crystallinity content in drawn fibres of PA-6 was about
51%, in those containing 2 and 5 wt% clay it was 59 and 63%, respectively. Part
of the reason for the difference may be the higher drawing temperature for CPNC
(170 °C) compared with PA-6 (150 °C). Furthermore, the high-speed drawing
that produced the highest crystallinity was also instrumental in transforming the
γ-form into predominantly α-form. Increased crystallinity translated into higher
modulus, viz. the tensile modulus for CPNC with 0, 2, and 5 wt% clay was
about 8, 9 and 10 GPa, respectively.
Intercalated or exfoliated CPNC were prepared by extrusion compounding
of PA-6 with ca. 3 wt% of pre-intercalated MMT, Cloisite® 30B (C30B);
d001 = 1.8 nm or Cloisite® 6A (C6A); d001 = 3.6 nm [Varlot et al., 2001]. The
compounds were injection moulded into 4 mm thick bars, which subsequently
were characterised by XRD. In accord with Kojima et al. [1995], the authors
reported significant variation of crystalline morphology with depth. Thus in the
three specimens: PA-6, PA-6 + C30B, and PA-6 + C6A, the surface layer was rich
in γ-form. The central, bulk layer of the injection moulded bar of PA-6 showed
preponderance of α-form, whereas γ-form dominated the two other specimens.
The CPNC showed MMT platelets aligned with the flow direction. The average
distance between MMT platelets in a PA-6A sample was determined from the
SAXS spectra to be ca. 35 nm. The same value was calculated from the
composition, assuming perfect exfoliation and uniform distribution of the
platelets.
VanderHart et al. [2001] used solid-state proton and 13C NMR to study 17 CPNC
compositions based on PA-6, provided by Ube Ind. and SCP. Except three samples
that contained laponite clay, the CPNC comprised natural, pre-intercalated MMT
dispersed either by in situ polymerisation or by melt compounding. The clays
were found to promote growth of the γ-form of PA-6 in all CPNC samples, while
the α-form characterised the neat PA-6. The total crystallinity in neat PA-6 was
40% – all in α-form. In CPNC the crystallinity was ca. 33 to 45% with the α-
form ranging from 2 to 75% (after injection moulding and annealing). However,
most specimens annealed at Ta = 214 °C showed only a partial conversion of γ-form
402
Nucleation and Crystallisation
to α-form (e.g., from 4 to 19%). The CPNC showed higher Tc and Tm than that
of PA-6. Since the main objective was to study paramagnetic effects there is little
more information on crystallinity.
To prepare CPNC with PA-6 as a matrix, Liu and Wu [2002a,b] used a three-step
method. Thus, Na-MMT (CEC = 0.8 meq/g) was intercalated with trimethyl
hexadecyl ammonium bromide (3MHDA). The precipitate of the reaction in H2O
was dried under vacuum then compounded in an internal mixer with the diglycidyl
ether of bisphenol-A (MW = 360 g/mol). In the last step the doubly intercalated
MMT was dispersed in molten PA-6 by means of compounding in a TSE at ca.
230 °C. The product containing 5 wt% clay was used in crystallographic studies
published in several articles, summarised below. More recently, the work was
extended to a PA-66/MMT system [Liu and Wu, 2002a; 2003]. A higher
crystallisation temperature for CPNC than that for neat PA-66 (Tc = 237 instead
of 226 °C), reduction of spherulite size, the presence of a γ-phase instead of an
α-phase were reported. Similar behaviour was observed for an exfoliated PA-66/MMT
system [Zhang et al., 2003].
The DSC and XRD studies on the influence of the cooling rate on the
crystallinity in PA-6 and CPNC demonstrated that the two materials behave
differently [Wu et al., 2001a]. Thus, as the cooling rate increases the rate of
crystallisation of PA-6 decreases while that of CPNC increases. In Figure 122
two separate sets of experiments are presented. The DSC data represent
experiments with well-defined cooling rates, whereas those measured by XRD
are plotted versus estimated ones. The dependencies are similar. The XRD data
show even stronger divergence of behaviour between PA and CPNC than DSC.
Furthermore, WAXS data indicated that PA-6 was highly polymorphous – only
at the slowest cooling rate was nearly pure α-form obtained. By contrast, the
Figure 122 Crystallinity versus cooling rate for PA-6 and PA-6 containing 3 wt%
of doubly pre-intercalated MMT. Two methods were used: DSC with well defined
cooling rates and XRD with roughly estimated cooling rates. Data [Wu et al.,
2001]. See text.
403
Clay-Containing Polymeric Nanocomposites
CPNC diffraction showed nearly pure γ-form – only at the slowest cooling rate
did the α2-peak-emerge.
A partial explanation for the diverse behaviour of PA-6 as a neat resin and as
a nanocomposite matrix can be gleaned considering the results of an annealing
experiment, displayed in Figure 123 [Liu and Wu, 2002a]. Granules of PA or
CPNC were placed between two glass slides, heated in an oil-bath up to 250 °C
for 10 min, and then quenched in liquid N2. The films were annealed in an oil-
bath at different Ta for 1 h, re-quenched and their crystallinity was determined
by XRD. In the Figure the α- and γ-form crystalline content is plotted versus Ta
– the total crystallinity is a sum of these two forms. During the compounding
and pelletising some crystallinity in PA-6 and CPNC certainly developed. However,
this crystallinity was to be eliminated by keeping the specimens for 10 min at
250 °C. Thus, the subsequent quenching generated 0 and 48% crystallinity in
PA and CPNC, respectively. The 1 h annealing of PA-6 at T ≥ 100 °C
characteristically formed g-crystals that subsequently converted to α-form. The
total crystallinity reached a maximum value of 36% at 180 °C. By contrast,
CPNC maintained ca. 49% of crystallinity in the γ-form up to ca. 130 °C. Above
this temperature γ- progressively converted to α-form – the latter reached its
maximum content of ca. 19% at 180 °C. Thus, the presence of organoclay
increased the total crystallinity of the PA-6 matrix well above the level observed
for the neat resin, and it had stabilised the γ-form to higher temperatures before
the onset of the solid-solid phase Brill transition from γ- to α-form. It is noteworthy
that the DSC-determined Tm of PA-6 and its CPNC was 223 and 219 °C,
respectively, in good agreement with the known melting points for the α- and γ-
crystals.
FTIR studies of PA-6 and CPNC led to the conclusion that the presence of
organoclay weakens the hydrogen bonding in PA-6. The γ-form was found
404
Nucleation and Crystallisation
preferentially located near the clay platelets, whereas the α-one preferentially in
the bulk [Wu et al., 2002a].
Murase et al. [2002] used FTIR, XRD and DSC to study the structure of PA-6
with 2 wt% of either synthetic mica or natural MMT. The PA-6/mica was prepared
by melt polymerisation of ε-caprolactam while the PA-6/MMT was industrial
resin from Ube Ind. The films were prepared by pressing at 250 °C for 2 min
followed by quenching into an ice-water bath and then annealing at 110 °C for
6 h. In PA-6 only the α-form was found, in the Ube nanocomposite both α- and
γ-crystalline forms, and in the mica-containing CPNC only γ-form crystals were
detected. The latter composition also showed the highest degree of crystallinity
of about 58% followed by that of PA/MMT and PA-6 (37%). Judging by the
reported results, it seems that mica in the studied CPNC was only intercalated,
whereas MMT in the Ube nanocomposite was exfoliated. Thus, it is difficult to
speculate whether the observed difference in the composition of the crystalline
phase is due to the nature of these two clays or to the degree of exfoliation.
Kamal et al. [2002] studied the crystallisation kinetics of PA-6 and its CPNC
(Ube PA-1015B and –1015C2, respectively) under pressure P = 50 to 200 MPa.
Isobaric volume changes associated with the crystallisation process were
determined at constant T and P, from which the crystallinity was calculated as:
X(%) = 100(V0 – Vt)/(V0 – V∞) (153)
where V0 is the initial (melt) volume, Vt is the volume at time t, and V∞ is the
volume at the end of crystallisation. Isobaric heating or cooling was used to
determine the melting or crystallisation temperatures of PA-6 in its neat state
and in CPNC. The data were fitted to a linear dependence:
Tm,c(°C) = ao + a1P(MPa) (154)
The numerical values of the parameters ai, along with the correlation coefficient
squares, r2, are listed in Table 57. It is noteworthy that the Tm for both resins
follows the same dependence, whereas Tc of the CPNC is lower by about 6 °C
than that of neat PA-6. It is also interesting that within the experimental error of
these measurements, the pressure gradient of Tm and Tc, dTm,c/dP = a1, is about
the same for PA-6 and CPNC.
The kinetics of crystallisation were studied at constant T and P. For both
resins, the data plotted according to the linearised Avrami equation showed two
intersecting linear dependencies. Apparently, the crystallisation started with the
γ-form, and then proceeded to the α-form. Thus, within the first zone the γ-form
Tm Tc Tm Tc
405
Clay-Containing Polymeric Nanocomposites
was dominant while within the second zone the α-form dominated. The Avrami
exponent n for the γ-form was between 1.0 and 3.2 in PA-6 and between 0.9 and
2.6 in CPNC. Its value for the α-form was between 1.0 and 2.1 in PA-6 and
between 1.2 and 2.6 in PNC.
In Figure 124 and Figure 125 the crystallisation rate of, respectively, PA-6
and PANC is expressed as the crystallisation half-time, t1/2, versus the free volume
( )
parameter, h = h P˜ , T˜ , where P˜ , T˜ are reduced pressure and temperature,
computed for each resin from the Simha-Somcynsky eos. Evidently, the kinetics
of crystallisation not only depend on h, but on P as well. To more clearly see the
effects of the independent variables, the experimental data were fitted to a linear
dependence, t1/2 = t1/2(h, P). The correlation coefficient squared, r2 = 0.74 to 0.95
was obtained. At the same value of h and P, the rate of crystallisation of the
α-crystals is systematically slower (t1/2 larger) than that of the γ-crystals. PA-6 in
CPNC crystallises faster than in its neat form. Surprisingly, in these isothermal
and isobaric experiments the pressure seems to play a secondary role to h as far
as the crystallisation kinetics is concerned. This was not the case for the isobaric
scans (at constant scanning rate) where high pressure slowed down either melting
or crystallisation in PA and CPNC.
Bureau et al. [2002] reported on the crystallinity and mechanical properties
of compression moulded PA-6 and its CPNC (Ube Ind., PA-1015B and 1015C2).
Specimens were moulded at 250 °C for 90 sec at P = 0.7 MPa, then either cooled
to room temperature under pressure at a rate of ca. 30 °C/min, or quenched in
ice water. Some quenched specimens were subsequently annealed at 80 °C for
24 h under vacuum. It was expected that these procedures would produce
specimens containing, respectively: the α-form (cooled), amorphous PA-6
(quenched), and the γ-form (annealed).
The DSC scans of PA-6 specimens showed a crystallisation peak followed by
an α-form melting peak at Tm = 221 °C. The crystalline content was estimated
as: 31% (cooled), 7% (quenched) and 21% (annealed). DSC scans of cooled or
quenched CPNC showed a double melting point, Tm = 213 and 221 °C, indicating
a polymorph with either γ- (in the cooled sample) or α-form (in the quenched
sample) predominating. The crystalline content in both these two samples was
ca. 25%, thus lower for the cooled specimen (than that in neat PA-6) and
significantly higher in the quenched specimen, indicating rapid nucleation by
MMT. Identification of the a- or g-form was confirmed by XRD and FTIR.
The tensile test results are summarised in Table 58. There is strong correlation
between the mechanical behaviour and morphology. All PA-6 specimens showed
necking with strain at break varying between 120% and 670%, depending on
the moulding condition. For the cooled CPNC specimens, higher Young´s modulus
and yield stress (with brittle fracture without necking) was observed. The tensile
strength and the Young´s modulus of the CPNC were ca. 15% higher than those
of PA-6. 25% polymorphous crystallinity in CPNC yielded a higher tensile
modulus than PA-6 with a 31% α-form crystalline phase. The data indicate that
improvements of rigidity and strength caused by addition of MMT are related to
the reinforcing effects of the nanofiller and not to the increased γ-crystals content.
The effect of matrix molecular weight on the kinetics of isothermal and non-
isothermal crystallisation in a PA-6/MMT system was studied by Fornes and
Paul [2003]. Incorporation of ca. 0.5 to 1 wt% clay resulted in the highest PA-6
crystallisation rate. While for neat PA-6 the crystallisation rate decreases with
molecular weight, in the case of CPNC the maximum crystallisation rate was
406
Nucleation and Crystallisation
Figure 124 Half-time for crystallisation of the γ- and α-forms in PA-6 versus the
free volume fraction parameter, h. Solid points are experimental, open are
computed from the linear fit to Equation 94. Data [Kamal et al., 2002]. See text.
Figure 125 Same dependence as in Figure 124 but for a CPNC sample of 2 wt%
organoclay in a PA-6 matrix (Ube PA-1015 C2). Data [Kamal et al., 2002]. See
text.
407
Clay-Containing Polymeric Nanocomposites
408
Nucleation and Crystallisation
the crystallisation rate, but at higher loading (i.e., 6 and 10 wt% MMT) the rate
decreased. The thermograms for all specimens showed multiple melting peaks.
However, such crystallisation parameters as the Avrami’s exponent, n, the
crystallisation temperature, and the heat of crystallisation were virtually
independent of the MMT content. In the following publication [Liu et al., 2004],
CPNC of PA-1010 was prepared by melt compounding with up to 10 wt% of
MMT pre-intercalated with either methyl tallow dihydroxyethyl ammonium
(MT2EtOH) or trimethyl hexadecyl ammonium (3MHDA) salts. XRD showed
significantly better clay dispersion for the MT2EtOH series (than 3MHDA), which
in turn resulted in superior mechanical performance. At 7 wt% MMT loading
the glass-transition temperature increased by 8.5 and 1.0 °C for the specimens
with MT2EtOH and 3MHDA, respectively. Addition of the former organoclay
accelerated the crystallisation rate of the matrix and changed its crystallisation
behaviour.
Wu et al. [2002b] studied the nucleating effect of MMT on the crystallisation
of PA-1212. The exfoliated CPNC was prepared by melt compounding of pre-
intercalated MMT with PA-1212. The film (ca. 0.5 mm thick) was moulded at
10.0 MPa and 200 °C for a few minutes, then quenched. Non-isothermal
crystallisation and melting tests were conducted in a DSC under N2. The sample
was heated to 220 °C and kept at this temperature for 10 min, then cooled at a
rate of 5 to 40 °C/min to 50 °C, and then re-heated to 200 °C at a rate of 10 °C/min.
For PA-1212 and its CPNC, an increased cooling rate shifted the Tc to lower
temperatures, as well as reducing and broadening the Tc peak. Compared to PA-1212
the CPNC had narrower exothermic peaks at higher temperatures. In Figure 126
the peak crystallisation temperature of PA-1212 and its CPNC, Tc, is plotted
versus the cooling rate, r. The overall time of crystallisation, tc ≡ (Ti-Te)/r versus
r is also presented (the subscripts i and e indicate the initial and final temperature).
Thus, addition of organo-MMT shifts the Tc to a higher temperature and shortens
the crystallisation time, tc. Both these functions indicate enhanced nucleation.
The authors also calculated the time for the initiation of crystallisation (ti) as
well as the nucleating activity coefficient, ϕ = 0.71. As expected, these parameters
also indicate enhanced nucleation by MMT. Optical microscopy under polarised
light, POM, confirmed this conclusion – the spherulites in neat resin were about
15¯25 times larger than those in its nanocomposite.
409
Clay-Containing Polymeric Nanocomposites
410
Nucleation and Crystallisation
organoclay, and then mixing the doubly intercalated clay with maleated-PP and finally
with PP. Exfoliated and well-dispersed clay platelets were observed under the TEM.
Kato et al. [1997] simplified this procedure by melt-mixing PP with oligopropylene
modified by MAH (PP-MA) and MMT intercalated with stearyl-ammonium salt
(ODA). CPNC with a high degree of exfoliation was obtained when PP-MA was
able to (1) bond to the clay and (2) be miscible with the PP matrix.
There are several variants of these procedures, with different amounts of the
PP-MA compatibiliser, of different structure, molecular weight and MAH-content.
Since these variables control the mutual miscibility of PP with PP-MA, this type
of CPNC shows a wide range of properties. For example, pre-intercalation and
compatibilisation may results in a system where the clay particles are shielded
from the matrix, preventing direct PP-clay contact, hence the matrix crystalline
structure entirely depends on the behaviour of the PP/PP-MA blend. In such a
CPNC the effect of clay on matrix crystallisation may be negligible.
There are two major differences between CPNC with PA and that with PO
matrix. (1) ω-Amino acid may be used to intercalate clay, thus after polymerisation
the clay is in full contact with the matrix. By contrast, owing to the strong
hydrophobicity of PO-macromolecules such a structure could not form in the
latter systems. (2) The crystallinity of PA rarely exceeds 50%, thus is significantly
411
Clay-Containing Polymeric Nanocomposites
lower than that in isotactic PP where X = 60 to 70% is often observed. Since the
intercalated clay platelets cannot enter the crystalline domains, they must be
concentrated in small pockets of the amorphous or meso-crystalline phase. This
means that the local concentration is about three times higher than the average,
thus (excepting low clay loading of ca. w ≤ 0.5 wt%) the platelets are unable to
freely rotate and form parallel stacks with local ordering – full exfoliation is
difficult to achieve.
The National Chemical Laboratories (NCL) in Pune conducted systematic
studies of clay effects on crystallisation of PP and the resulting performance of
the CPNC. Hambir et al. [2001] prepared PP-based CPNC with MMT (CEC =
1.35 meq/g) intercalated with octadecyl amine (ODA) and compatibilised with
maleated PP (MA-PP). XRD gave the interlayer spacing of d001 ≅ 2.5 nm. The
isothermal crystallisation of the PP and PP/MMT-ODA systems was carried out
by DSC. The thermograms indicated that the clay presence narrows the
crystallisation peak and reduces the crystallisation time hence it accelerates PP
crystallisation. As shown in Figure 127, crystallisation in neat PP and in its CPNC
may have different activation energy, but this conclusion hinges on the validity
of two data points at low temperatures (T = 100 and 136 °C) where reduced
chain mobility may already start slowing down the crystallisation rate. Optical
microscopy under polarised light showed a dramatic change of morphology –
large, well-defined spherulites in specimens crystallised at 122 °C PP, but
crystallites in the form of a fibrous mat in those crystallised at 142 °C CPNC.
In the following publication from the same laboratory [Kodgire et al., 2001]
PP was compounded in a single-screw extruder (SSE) with 12 wt% MA-PP and
4 wt% of commercial organoclay, either Cloisite® 6A (C6A; MMT, CEC = 1.4 meq/g
intercalated with 2M2HTA), or Nanomer I.30 (MMT, CEC = 1.35 meq/g
intercalated with ODA). The XRD-determined interlayer spacing in Na-MMT was
d001 = 1.2 nm, in C6A (two peaks) d001 = 1.2 and 1.8 nm and in I.30 d001 = 2.45 nm.
412
Nucleation and Crystallisation
Compounding with PP increased d001-values, but the system containing C6A was
exfoliated only after compounding with MA-PP, while that with I.30 intercalated
(d001 = 2.75 nm). However, the enhancement of mechanical properties was similar
for either CPNC (hence independent of the degree of clay dispersion) – ca. 35%
increase in the tensile modulus and about a 10% increase in the tensile strength. In
accord with the results reported in the preceding publication, the Tc of PP increased
after addition of clay from 122 °C (for neat PP) to 142 °C. Furthermore, in CPNC
the crystallites formed a fibrous mat that coarsened with time, but did not transform
into spherulites. Thus, clay nucleated a very specific PP morphology.
Another publication from this laboratory provides additional information
[Hambir et al., 2002]. This time the ODA intercalated clay was prepared in
house and used along with C6A. Furthermore, three PP resins (Mw = 164, 241
and 362 kg/mol) and two MA-PP resins (Mw = 188 kg/mol, MAH = 1%; and
151 kg/mol, MAH = 0.64%) were used. The isothermal crystallisation of PP and
PP/clay was studied by DSC at Tc = 115 to 131 °C. The PP/clay systems showed
a sharper crystallisation peak than that of PP. Thus, crystallisation of PP was
accelerated by organoclays. Furthermore, the crystallisation half-time depended
on the organoclay content, Mw of PP as well as on the presence of MA-PP.
However, the change of Mw from 241 to 362 had a more pronounced effect than
addition of up to 4 wt% of organoclay. The crystallisation activation energy
seems to be more influenced by the Mw of PP than the other variables. Thus,
incorporation of organoclay resulted in enhanced nucleation and faster
crystallisation of the PP matrix. The clay also changed the macromorphology of
the crystalline phase – in CPNC instead of spherulites fibrillar structures have
been observed. However, since the authors did not calculate the unit cell, it is
unknown whether the addition of organoclay modified the crystal cell structure,
e.g., from the common α-monoclinic into the more desirable β-hexagonal one.
Saujanya and Radhakrishnan [2001] studied the crystallisation of PP in the
presence of calcium phosphate nanoparticles (CaP). These were prepared from
CaCl2 and Na3PO4 in a MeOH solution of PEG. Varying the concentration ratio
of PEG to CaCl2 from 0 to 32, resulted in reduction of β-ortho CaP (monoclinic)
particle diameter from d = 82 to 7 nm. It is noteworthy that in the presence of
CaP PP crystallises in spherulitic form with a monoclinic α-crystalline cell
structure. At 2 wt% CaP the t1/2 and the ultimate spherulite size decreased with
the particle size from 45 to 20 μm. The strong nucleation efficiency of CaP
originates in high surface energy and large surface area, viz.:
ln(G/Go)∝1/d (155)
where G is the crystallisation rate in the presence of CaP and Go without it. The
optical transparency of the PP/CaP-nanoparticles system was higher than that
containing conventional CaP at the same concentration. The DSC data showed
that incorporation of CaP increased the crystallisation temperature of PP from
110 to 114 °C and reduced the width of the crystalline peak as compared to PP.
The heat of fusion of neat PP was determined as 77.9 J/g whereas that of the
nanofilled PP as 132.9 J/g, indicating that in the presence of 2 wt% CaP the
crystallinity of PP nearly doubled. Such a large effect has not been observed for
compatibilised PP/organoclay systems. The most likely reason is the presence of
an organic phase around the clay particles. Since the intercalant molecules are
immiscible with PP, they form a barrier, separating the crystallisable matrix from
the high-energy clay surface.
413
Clay-Containing Polymeric Nanocomposites
414
Nucleation and Crystallisation
from d001 = 1.199 (for Na-MMT) to 2.596 nm (for MMT-HDA). The PETN
containing 2 to 4 wt% MMT-HDA was only intercalated (d001 = 3.104 nm).
Furthermore, as the concentration of the organoclay increased to 6 wt% the
interlayer spacing decreased to d001 = 2.662 nm, indicating that at higher
concentration the organoclay aggregates (also observed in SEM). DSC
measurements of these CPNCs have shown that the glass-transition temperature
(Tg), melting temperature (Tm), and heat of fusion (ΔHm) are nearly independent
of the organoclay loading (see Table 61). Thus, the total crystallinity of PETN
does not seem to be affected by MMT-HDA. The structure of these CPNCs is a
phase-separated matrix with intercalated, internally ordered organoclay domains
dispersed in it. Nevertheless, incorporation of the organoclay did enhance the
thermal stabilities and mechanical properties (maximum in the tensile strength
and modulus was obtained for 4 wt% loading).
Imai and his colleagues from AIST prepared PET-based CPNC by melt, and
then solid-state polymerisation in the presence of ca. 3.7 ± 0.2 wt% of clay [Imai et
al., 2003; Saujanya et al., 2003]. Fluoromica (FM), FM pre-intercalated with
triphenyl dodecyl phosphonium bromide (3PPC12), or FM pre-intercalated with
triphenyl di(methoxycarbonyl)phenoxy decyl phosphonium bromide (3PPPC10)
were used. The interlayer spacings were: d001 = 1.33, 1.82, and 1.86 nm, respectively.
For the crystallisation studies neat PET (PET-0), CPNC with FM (PET-1) and CPNC
with FM-3PPPC10 (PET-2) were used. The isothermal crystallisation tests showed
that the crystallisation rate, and crystallinity increase in the order from PET-0 to
PET-2; the opposite tendency was observed for the activation energy. The results
seem to indicate that, at least for the crystallisation of PET, the degree of dispersion
is more important than the surface energy of the dispersed clay. This observation
may explain the small effect of organoclay on PET crystallisation, reported by
Wang et al. [2003b; 2004], and by Ou et al. [2003].
Recently nanocomposites with poly(trimethylene terephthalate) (PTT) have
been prepared using the solution intercalation or melt compounding method,
and their crystallisation behaviour was studied [Ou, 2003; Liu et al., 2003]. The
first author used MMT pre-intercalated with cetyl-pyridinium chloride (CPC),
whereas the others used MMT-MT2EtOH. For both systems XRD indicated
1 74 237 31
2 73 238 31
3 75 238 30
4 75 238 32
6 74 236 30
415
Clay-Containing Polymeric Nanocomposites
intercalation with short stacks dispersed in the matrix. From the DSC thermograms
the authors concluded that organoclay behaves as a nucleating agent, enhancing
the crystallisation rate of PTT. As in other systems, here also a maximum
crystallisation rate was observed at relatively low organoclay loadings.
416
Mechanical Behaviour
3.5
Mechanical Behaviour
One of the reasons for the interest in CPNC is enhancement of the mechanical
performance of the matrix polymer at low clay loading. For example, addition
of 2 wt% of organoclay to PA-6 increased the flexural modulus by 26%, and
tensile strength by 14% [Ube Ind., 2000]. Similarly, dispersion of 2 and 5 wt%
of vermiculite in PP increased the tensile strength by 18 and 30%, the tensile
modulus by 20 and 54%, and the storage modulus by 204 and 324%, respectively
[Tjong et al., 2002]. A thorough review of the theories of mechanical behaviour
in a multiphase polymeric system can be found in the PhD thesis of D. Colombini
[1999].
(
Kerner : Ec = Em 1 + ABφ f ) / (1 − Bφ ); f Gc / Gm = Ec / Em
A = (7 − 5ν m ) / (8 − 10ν m ) (157)
( )(
B = E f / Em − 1 / E f / Em + A )
(
Neilson : Ec = Em 1 + ABφ f ) / (1 − ΨBφ ); f Gc / Gm = Ec / Em
Ψ = 1 + [(1 − φ f ,max ) / φ ]φ
2
f ,max f
417
Clay-Containing Polymeric Nanocomposites
Halpin-Tsai (H-S) rigorously derived the tensile modulus in the stress direction,
Ec:
( )(
Ec / Em = 1 + 2 pκφ f / 1 − κφ f ) (158)
κ = ( Er − 1) / ( Er + 2 p); Er ≡ E f / Em
Here p is the aspect ratio defined in this book as p = (platelet diameter)/(platelet
thickness). For the modulus in transverse direction p = 1 may be assumed. For p
→ ∞ Equation 158 converts into Equation 156 with fL → 1. The predicted
behaviour is illustrated in Figure 129.
According to Brune and Bicerano [2002] the above relationships may be used
only for predicting the modulus of fully exfoliated CPNC with oriented, clay
platelets perfectly adhering to the matrix. When the clay platelets are only
intercalated then the variables: p, Ef, and φf obtained from fitting the equations
to data must be consider empirical. On the other hand, the authors derived the
following relationships between these variables for exfoliated and intercalated
(symbols with prime) systems:
[
p ′ = ( p / N ) / 1 + (1 − 1 / N )( s / t ) ]
[
φ ′ = φ 1 + (1 − 1 / N )( s / t ) ] (159)
Er + (1 − 1 / N )( s / t )
Er′ =
1 + (1 − 1 / N )( s / t )
In this relation the aspect ratio, p´, the volume fraction, φ´, and the tensile modulus,
E´, refer to the platelet stack composed of N-clay layers, each with thickness t
and the interlamellar gallery spacing, s ≅ d001 – 0.96 nm. However, since the
Figure 128 Relative tensile modulus for Ef /Em = 100 or 1000 in the stress and
transverse to it directions. See Equation 156.
418
Mechanical Behaviour
Figure 129 Predictions of the Halpin-Tsai Equation 158 for relative modulus in
the stress direction for Ef /Em = 100 or 1000 and p = 10 or 1000.
dependence does not have the correct upper limit for the s/t ratio, the parameter
N in the dependence should be replaced by:
φ
N ′ = N + (1 − N )( s / t ) (160)
1−φ
Evidently, Equations 157 to 159 are valid for idealised, well-oriented CPNCs
where the platelets are perfectly bonded to the matrix. The important teaching
of this theory is the strong influence of the degree of dispersion on the relative
modulus, Ec/Em = E´/Em. In Figure 130 variation of the relative modulus for
intercalated CPNC is plotted as a function of the number of platelets in the stack,
N, and the size of the interlamellar gallery expressed as: s/t = (d001/t) – 1 ≅ d001 – 1.
The role of this parameter is to express the modification of the macromolecular
behaviour within the galleries. It is noteworthy that the steepest decline of
performance is predicted for stacks containing 2 to 3 platelets, i.e., for these
most often observed in CPNC. In other words, the modulus of a truly exfoliated
system is at least twice as high as that obtained for the most common ‘exfoliated’
ones.
Brune and Bicerano [2002] proposed a further refinement to the above
treatment for disk-shaped filler particles. The aim was to correctly predict the
effects of the aspect ratio. The derived equation is in a scaled form:
Ec ( p) − Ec ( p = 1) 2( p − 1) Ef
Es ≡ = ; Er ≡ (161)
Ec ( p → ∞) − Ec ( p = 1) ( Er − 1)(1 − φ f ) + 1 + 2 p Em
The relation virtually traces the prediction of the Halpin-Tsai relation (see
Figure 131). Within the customary range of the clay content, φf < 5 vol%, it is
insensitive to composition, but it strongly depends on Er and p. It is important to
note that when a high Er value is required, platelets with larger aspect ratio
ought to be used. Considering that E(clay) ≅ 170 GPa and the modulus of
unoriented, unfilled engineering plastic ranges from 2 to 4 GPa the clay platelets
419
Clay-Containing Polymeric Nanocomposites
Figure 130 Prediction of the Brune-Bicerano theory (see Equation 159) of the
relative modulus of intercalated CPNC versus the average number of platelets in
the stack for the interlayer spacing, d001 ≅ (s/t) + 1. For the most common value of
d001 ≅ 3 nm stacks of ca. three platelets show only 40% of the modulus expected
for exfoliated CPNC.
Figure 131 Scaled tensile modulus versus aspect ratio according to Halpin-Tsai (H-
T) and Brune-Bicerano (B-B) equations. Moduli ratio: Er = Ef /Em = 100 or 1000,
filler volume fraction, φf = 0.01 or 0.05. Both relations provide equivalent
dependence, insensitive to φf but sensitive to Er.
420
Mechanical Behaviour
with p ≅ 200 would reach about 90% of the theoretically possible modulus. For
CPNC with more ductile polymeric matrices clay with still higher p should be
used.
Hui and Shia [1998] derived a simplified H-S theory for the tensile modulus
of oriented fibre or flake reinforced composites. The simplification involved the
assumption that the Poisson’s ratio, νm = 0.5, is the same for both components
and that there is perfect adhesion between filler and matrix. For flakes oriented
in the stress direction the modulus is given by:
−1
⎧⎪ φ ⎡1 3 ⎤ ⎫⎪
Ec = Em ⎨1 − ⎢ + ⎥⎬
⎪⎩ 4 ⎣ ξ ξ + Λ ⎦ ⎪⎭
ξ ≡φ+
1
+ 3(1 − φ )
(
(1 − g) − gp2 / 2 ) (162)
Er − 1 1 − p2
Λ ≡ (1 − φ )
( )
3 1 + 0.25 p2 g − 2
; g ≅ π / 2p
1− p 2
Predictions of Equation 162 are higher and are more sensitive to the aspect ratio
than those from Halpin-Tsai (H-T) Equation 158.
The Hui-Shia (H-S) theory was evaluated using the tensile modulus data for
CPNC with PDMS as the matrix [Shia et al., 1998]. The experimental results did
not follow the theoretical predictions of H-T and H-S theories. To explain the
discrepancy the authors postulated that the difference originates in imperfect
bonding between the matrix and clay. This introduced two ‘effective’ quantities
into the H-S model: the aspect ratio and clay volume fraction. Both were assumed
to depend on the interfacial shear stress, σi, determined by fitting the data to the
equation – the calculated σI-value was in the range of kPa. The interfacial shear
stress was further decomposed into an intrinsic and a frictional shear stress, the
former decreasing with the increasing volume fraction of the inclusion and the
latter increasing linearly with strain. For the CPNC studied, the effective friction
coefficient was calculated as 0.0932.
However, as shown in Figure 132, in the whole range of concentration the
data are well described by Brune-Bicerano Equations 159-161, with Ef = 170 GPa
and Em = 1 MPa. The numerical values of the remaining variables were taken
from Shia et al. [1998]. The least squares fit gave a reasonable value of the aspect
ratio, p = 239. The number of platelets in the stack increased from the initial
value of N = 2 to 4 at the highest concentration. The standard deviation and the
correlation coefficient squared were: σ = 0.18 and r2 = 0.995, respectively.
Ji et al. [2002] expanded Takayanagi’s two-phase model into three-phases:
the matrix (m), interphase (i), and filler (f), randomly distributed in the matrix.
The filler particles may be spherical, cylindrical or lamellar. The incorporation
of an interphase is particularly important for the nanoparticles. According to the
model, the three phases are connected to each other in series and in parallel. The
realistic representation of a filled system is then reduced to three idealised regions,
A, B, and C connected in series. The general form of the derived relation is:
1 1− β β −ϕ ϕ
= + + (163)
Ec Em (1 − α )Em + αEBi (1 − α )Em + (α − λ )ECi + λE f
421
Clay-Containing Polymeric Nanocomposites
Figure 132 Relative modulus versus clay content for CPNC with PDMS as the
matrix. Experimental data [Shia et al., 1998] and theoretical prediction from
Brune-Bicerano (B-B) theory. See text.
where α, β, ϕ and λ are idealised dimensions of the interphase and filler regions
determining the volume fraction of each of the three components, viz. Vf = λϕ; Vi
= αβ – λϕ; and Vm = 1 – Vf - Vi. The moduli of the composite, matrix and filler
are given as: Ec, Em, and Ef. The interphase modulus is defined for the model
regions B (in series) and C (in parallel) as EBi and ECi , respectively. When particles
are relatively large the interphase contribution is negligible, Vi → 0 and
Takayanagi’s equation is recovered.
The principal advantage of this theory is incorporation of the interphase
contribution. As stated before, the authors consider two types of interphases
connected to other phases either in parallel or in series. In the case of CPNCs
these may be treated as the interphase inside the stack of clay platelets, and that
between the stacks and the matrix. The two types depend on the distance from
the filler surface respectively, linearly and exponentially:
1 ln( E0 i / Em ) (164)
E Bi
=
E0 i − Em
[ ]
; ECi = E0 i + Em / 2 with : E0 i / Em ≡ k
where E0i is the interphase modulus on the filler surface at τ = 0 and k is one of
the model parameters. The platelet and the interphase shapes were assumed to
be square, thus:
422
Mechanical Behaviour
1 1−
=
[2(τ / t ) + 1]V f
+
[2(τ / t) + 1]V − V
f f
Ec Em ⎧1 −
⎨
⎩
[2(τ / t) + 1]V ⎫⎬⎭E + [2(τ / t ) + 1]V (k − 1)E
f m f m / ln k
Vf
+
⎧1 −
⎨
⎩
[2(τ / t) + 1]V ⎫⎬⎭E
f m
⎩
[ ]
+ ⎧⎨ 2(τ / t ) + 1 V f − V f ⎫⎬( k + 1) Em / 2 + V f E f
⎭
(166)
For CPNC the controlling parameters are: the dispersed particle size: t << ϕ = λ,
thickness of the interfacial region (τ), filler-to-matrix modulus ratio (Ef/Em), and
a parameter (k) describing a linear gradient change in modulus between the matrix
and the surface of the particle. Since t and Ef/Em are in principle known, the
model has two adjustable parameters: τ and k; validity of the model can be judged
by the ‘reasonableness’ of these parameters computed from fitting Equation 166
to the experimental data.
To test their model, Ji et al. [2002] prepared CPNCs of PA-6/MMT and measured
the tensile properties. The experimental data were fitted to the theoretical
dependence with τ = 7 nm and k = 12. It is worth recalling (see Section 3.1.7) that
the thickness of the solidified layer of organic compounds on the surface of clay
platelets as determined in the surface force analyser (SFA) ranges from ca. 3 to 12
nm, with most of the values centred near 6 nm. For polymers the layers with
reduced segmental mobility stretched to a distance of about 100 nm. However,
these measurements were taken in a liquid not solid state. In the model the two
parameters, τ and k characterise the interphase: τ its thickness and k its rigidity.
The computed value of τ = 7 nm well agrees with the thickness of the PA-6 layer
that is adsorbed on the clay surface and solidified in the molten state, e.g., at
240 °C. Evidently, this is a highly satisfactory outcome! As shown in Figure 84,
the solidification was found to significantly reduce the free volume in molten
polymer. Reduced free volume should translate into higher modulus, thus k > 1
would be expected. The experimental value of k = E0i/Em = 12 is high (especially
since Ef/Em = 40 was assumed), but it may be reasonable (the ratio of the crystalline
to the amorphous modulus for the same polymer ranges from 2 to 6 [Ferry, 1980]).
In this book there are several tables listing the tensile modulus versus clay
loading (inorganic part). These values were used to generate Figure 133. The aim
was not to prove or disprove any of the listed theories, but to show how the best
CPNC performs in an amorphous polymer matrix (PS), in a semicrystalline end-
tethered exfoliated matrix (PA-6), and in a semicrystalline not tethered matrix
with a compatibiliser (PP). For these systems MMT was used with an average
aspect ratio p = 200 to 300. The results indicate that independently of the matrix
the CPNC modulus doubles at clay content of about 5 wt%. CPNC comprising
fluoromica (FM) instead of montmorillonite (MMT) has lower modulus, most
likely caused by lower aspect ratio, p. Lower modulus is also observed for systems
with poorly dispersed clay platelets.
In dilute systems the tensile modulus linearly increases with clay loading
following the relation:
[]
E R ≡ E / Em = 1 + η φ = 1 + aw ; w ≤ 8wt% (167)
423
Clay-Containing Polymeric Nanocomposites
Figure 133 Relative tensile modulus versus clay content for CPNC of PA-6, PP,
PLA and PS with montmorillonite (MMT), as well as for PP with fluoromica
(FM). See text.
Here the reinforcing factor [η] is the hydrodynamic volume, for monodispersed
hard spheres (p = 1) it is equal to the Einstein value of 2.5. The parameter
[]( ) []
a = η / 100 ρ f / ρ m ~ η / 314 . The lowest predicted value for hard spheres is a
= 0.008. For poorly exfoliated PP, PA-6 and polylactic acid (PLA) the values of
ER increase with the slope a = 0.07. Substituting the equivalent value of [η] into
Equation 107, gives the aspect ratio: p = 93. On the other hand, fully exfoliated,
best performing systems follow the dependence with a = 0.20 equivalent to p = 200.
The latter value is close to that expected for the commercial organoclays with
MMT. It is noteworthy that the values for PP reinforced with FM can also be
approximated by Equation 167 with a = 0.13 equivalent to p = 150. This value is
close to p = 132 calculated from data by Zilg et al. [1999a].
It has been universally accepted that the values measured for CPNC following
well-established procedures for polymeric specimens represent the inherent material
behaviour. However, the same PS/organoclay or PP/organoclay/compatibiliser
system tested in two laboratories resulted in not only different values, but also
different tendencies for increasing clay content. Part of the answer can be found
in the recent work by Uribe-Arocha et al. [2003]. The authors prepared CPNC
of PA-6 (with 0 and 5 wt% clay) by injection moulding the specimens with
thickness of 0.5, 0.75, 1.0 and 2.0 mm. These were subsequently tested by DMA
and in a tensile tester. Both methods showed only a small effect of thickness on
the performance of PA-6. However, the effects for CPNC with 5 wt% clay were
severe. As an example, Figure 134 displays the dependence of the tensile modulus
(E) on specimen thickness (t). The data indicate that increasing t from 0.5 to
2 mm does not affect the tensile modulus of neat PA-6, while it reduces E(CPNC)
by ca. 25%. Similarly, for PA the stress at 2% strain ranged from ca. 46 to52 MPa,
whereas for CPNC specimens with thickness: t = 0.5, 0.75, 1.0 and 2.0 mm the
stress at 2% strain was: 84, 84, 72 and 61 MPa, respectively. Other measured
parameters showed similar dependencies.
424
Mechanical Behaviour
Figure 134 Tensile modulus versus specimen thickness for PA-6 and its CPNC
with 5 wt% clay. Data [Uribe-Arocha, 2003].
Explanation for this behaviour rests in the skin-core structure of injection moulded
specimens. The data show only limited effect of skin on PA-6 behaviour – the
molecular alignment near the mould surface was not too severe. In the case of
CPNC, the orientation of clay platelets near the wall causes significant
improvement of modulus. It is noteworthy that theoretically the ratio:
E(perfect orientation)/E(random orientation) = 1/2
thus the observed decrease by 50% is reasonable. Specimens with thickness
t ≤ 0.75 mm had similar stress-strain dependence, whereas there is significant
reduction of yield stress, σy, for thicker specimens. SEM of these specimens tested
under uniaxial loading showed multiple voiding in the core. After this initial
stage (evidenced by necking) the skin with aligned clay platelets maintained the
load – the specimen failed when the skin broke.
During the last few years a new method of computation of mechanical
properties of nanocomposites has been developed. This multiscale approach is
most advanced for systems containing carbon nanotubes [Odegard et al., 2002].
The method consists of three-steps: (1) atomic/molecular dynamics (MD)
modelling of the nanoparticle and its interactions; (2) construction of a
representative volume element (RVE); and (3) computation of macroscopic
behaviour of the nanocomposite from RVE, using either classical continuum
expressions or a finite element method (FEM). The latter method was used by
Sheng et al. [2004]. For CPNC the authors applied a multiscale modelling strategy
assuming that: (1) at a length scale of millimeters, the structure is one of high
aspect ratio particles within a matrix; (2) at micron-scale, the clay particles are
either exfoliated or in the form of intercalated stacks; (3) at a nanoscale the
interactions between the matrix and nanoparticles must be computed. In addition,
the matrix may be amorphous or semicrystalline. In the latter case the effects of
425
Clay-Containing Polymeric Nanocomposites
426
Mechanical Behaviour
σ c = σ mφ m + FRσ f φ f ; σ R = 1 + φ f ( FRσ r − 1)
⎡ tanh(u) ⎤
FR = ⎢1 − ⎥ 1 − sec h(u) (170)
⎢⎣ u ⎥⎦
[ (
u = p Gmφ f / E f 1 − φ f )]
where Gm is the matrix shear modulus, Ef is the flake tensile modulus and FR is
the filler strength reducing factor. For the aliphatic polyester (APES)/clay system
[Lee et al., 2002b] the calculated value of FR = 0.667 leads to a value for the
tensile strength of clay platelets σf = 125 MPa, approaching the expected strength,
but still smaller by a factor of about 1.8. It should be noted that the definition of
FR in Equation 170 predicts that: 0.666 ≤ FR ≤ 0.900.
Kerner’s composites theory provides the following relation for the tensile
strength:
( )( )
σ c = σ m 1 + ABφ f / 1 − Bφ f ; where :
A = (7 – 5ν m ) / (8 − 10ν m ) (171)
( )(
B = σ f /σm −1 / σ f /σm + A )
427
Clay-Containing Polymeric Nanocomposites
The dependence is identical to that shown in Equation 157 with strength (σ)
replacing the modulus (E).
Finally, an interesting relation was proposed by Turcsáyi et al. [1988]. The
authors corrected for the decreasing load bearing cross-section of a specimen
and for the effects of the interfacial interactions:
( )( ) { }
σ R ≡ σ c / σ m = 1 − φ f / 1 + 2.5φ f exp Bφ f ; where :
(172)
B = (1 + A ρ l ) ln(σ / σ )
f f i m
In Equation 172 Af and ρf are the specific surface area and density of the reinforcing
particles, while l and σi are the thickness and strength of the interphase. It is
worth noting that B < 0 for σi < σm – the other variables only scale the effect. The
dependence predicted by Equation 172 is illustrated in Figure 136. For the yield
stress of composites to be about equal to that of neat polymer the value of the
B-parameter should be about 3. Substituting the largest possible values (Af =
750 m2/g; ρf = 5000 kg/m3 and l = 100 nm) indicates that this condition would be
met if σi > 1.01σm. Thus, for nanocomposites able to adsorb and solidify the
macromolecules one may expect that the tensile strength will increase with loading
of clay platelets.
Figure 136 Relative tensile strength of CPNC as a function of the clay platelet
volume fraction and the interaction parameter B from Equation 172 [Turcsáyi et
al., 1988].
428
Mechanical Behaviour
used by fracture mechanics are impact tests, steady-state deformation (at stresses
exceeding the strength of the material) and fatigue [van der Giessen and
Needleman, 2002].
In the latter case the fatigue crack grows when the stress intensity (cycling
between σmin and σmax) is much smaller than that needed for crack growth under
steady-state loading. The cycling causes failure at stresses well below the tensile
strength level. Analysis of this behaviour is done by determining the stress versus
number of cycles to failure (S-N diagram) curves, usually followed by studies of
the mechanism of crack propagation and determination of the fracture energy.
Fatigue crack growth will take place if and only if the following three conditions
are met: (1) the stress amplitude, σa = σmax – σmin exceeds a critical value; (2) the
maximum stress intensity σmax exceeds its critical value; and (3) there is an energy
dissipation process during the cycle (fatigue fracture cannot occur in a fully elastic
system without memory). Above the threshold stress value, the crack growth
rate, ∂l/∂N, is a function of the stress amplitude, σa. To generate an S-N diagram
the specimen may be subjected either to constant stress amplitude or to the mean
stress, respectively defined as [Moet, 1986]:
σa = σmax – σmin; σmean = (σmax + σmin) / 2 (173)
Construction of the S-N curve is time consuming since for statistically valid results
ca. 10 samples have to be tested at each stress level.
In Figure 137 a schematic S-N plot for PS is shown [Sauer et al., 1976]. The
specimens were tested at a frequency of 1600 cycles/min at constant maximum
stress, σmax = 17.25 MPa, systematically varying sa from about 4.75 to 17.25 MPa.
There is a substantial difference in the material behaviour when cycling is done at
the same level of stress amplitude, but either fully in tension, e.g., σmin = 0 and σmax
= 17.25 MPa, or in tension and compression, e.g., σmin = -8.62 and σmax = +8.62 MPa
Figure 137 Schematic representation of the S-N plot for PS at 500 Hz. After [Sauer
et al., 1976].
429
Clay-Containing Polymeric Nanocomposites
where ci are material parameters, while A and V are specimen surface area and
volume, respectively.
The data schematically shown in Figure 138 are based on the reversed load
fatigue tests of polyoxymethylene (POM or acetal) at different levels of frequency:
ν = 0.167 to 10 Hz and stress amplitude, σa. At low frequency and low σa the
conventional FCP fracture mechanism was observed and the data followed the
FCP-type dependence, shown in Figure 137. However, when the frequency and
stress amplitude exceeded the critical values for POM, the number of cycles to
failure, N, dramatically decreases forming TFF-branches, each for a specific
frequency. Evidently, the two mechanisms lead to significantly different
morphology of the fractured surfaces. Stress concentration caused by a notch
reduces the critical value of the energy rate, thus it increases the probability of
the TFF mechanism.
The FCP mechanism often starts by craze formation which, depending on the
material and test conditions, leads either to cracks or shear banding, which in
turn proceed to the crack propagation stage. The crack opens either in a single
craze or shear band. The initiation is best described in terms of the fracture
mechanics stress intensity factor, σth ∝ l / r where l is the crack length and r its
radius of curvature. Growth of the crack length with the number of cycles during
the fatigue test was found to be proportional to the amplitude of the stress
concentration factors in the tensile mode, σKI = σI, max – σI, min:
∂l / ∂N = co Δσ lm (175)
where co and m are characteristic constants of this ‘Paris law’ equation. Continuum
theories that assume that the crack growth rate is proportional to the crack opening
displacement predict the exponent value: m = 2. Nguyen et al. [2001] have
430
Mechanical Behaviour
Figure 138 S-N plot for two mechanisms of failure in POM: thermal fatigue failure
(TFF) and fatigue crack propagation (FCP). After [Crawford and Benham, 1975].
431
Clay-Containing Polymeric Nanocomposites
γ-form. In these nanocomposites the level of crystallinity is also higher than that
in neat PA-6, which in part accounts for the increased values of E and σy as well
as for the reduction of εb.
The data in Table 62 show that addition of 2 wt% of organoclay (equivalent
to 0.64 vol% of MMT) has a large effect on the tensile (Young´s) modulus, E,
especially when the matrix is plasticised by the moisture. There is also a significant
increase of the yield (or ultimate) strength, σy. However, the elongation at break,
εb, is reduced – the dry CPNC specimens are particularly brittle. From the fracture
test data the stress intensity factor, KIc, and the fracture energy, Jc, were computed.
For CPNC the values of these parameters are also below those for neat resin.
Noteworthy is the difference in the moisture effect on the fracture mechanics of
PA and CPNC – while for PA the humidity changes linear-elastic behaviour into
an elastoplastic one; for CPNC linear-elastic behaviour is observed for both, dry
and conditioned specimens.
These results are in good agreement with data reported by Gloaguen and
Lefebvre [2001], who also studied the Ube material. The authors carried out
tensile tests at constant strain-rate of 10-3 s-1, recording the stress, linear strain,
and volume strain (a specific video-extensometer was used). CPNC showed brittle
behaviour at room temperature (εb = 5-7%). At T = 80 °C (above the glass
transition temperature, Tg) the elongation at break for PANC was higher than
that for PA-6 (εb = 900 versus 800%). The authors also reported large volume
expansion during tensile tests; about twice as large for CPNC as that for the
matrix polymers, PA-6 or PP. The cavitation in CPNC was large and orientation-
dependent, similar to that observed in HIPS. In the authors’ opinion, the cavitation
originates in local damage at the polymer/clay interface, and thus in an unspecified
nanoscale defect (crystalline organisation in the vicinity of the clay platelet,
localised necking and fibrillation, nanoscale interfacial cavitation, etc.).
The recent publication by Bellemare et al. [2002] describes fatigue test results
for the same two Ube resins (PA-1015B and PA-1015C2). The measurements
432
Mechanical Behaviour
433
Clay-Containing Polymeric Nanocomposites
only intercalated (d001 = 3.21 nm). With increasing clay loading the modulus
slightly increased (ca. 15% at 12.5% loading), while the values of σy and εb were
reduced, which is consistent with a particulate-reinforcement mechanism. In
compression tests the presence of clay had marginal effects on the stress-strain
behaviour. Results of the fracture toughness measurements were expressed in
terms of the stress intensity factor, KIc, and the energy release rate, GIc, which is
a measure of the new surface energy, ν1. Both these parameters reached a local
maximum at a clay loading of about 3.5 wt%. At this clay concentration the
value of KIc and GIc was higher by about 68 and 170% than those of the matrix,
respectively. Atomic force microscopy in the tapping mode was used to determine
the surface area after fracture, ΔA = Ameasured/Aprojected. Plotting the energy per
surface area (GIc = 2 × surface energy):
GIcreduced = GIc / (1 + ΔA) (176)
as a function of the clay content showed that GIcreduced is about constant. Therefore,
the primary mechanism for toughening in the intercalated systems is the creation
of new surfaces. The authors expressed the opinion that intercalation affords
property improvements that are unavailable to fully exfoliated systems.
Incorporation of organoclay into rubbers leads to materials with a new set of
properties, viz. high stiffness, tensile strength, reasonable elongation at break
and tear strength [Nah et al., 2001]. In their preliminary report the authors stressed
the unique fracture surface morphology of CPNC with NBR as the matrix. At
15 phr loading of organoclay the tear strength, Gc, was nearly 4-times higher
than that of the matrix and comparable to that of carbon black (CB) filled rubber.
At the same time the modulus of CPNC was at least twice as large as that of
CB-filled rubber.
In summary, it seems that in CPNC (with clay particles intercalated or
exfoliated, end-tethered or not), fracture proceeds by a crazing-and-cracking
mechanism, frequently with large volume expansion during the fracture. To date
pure shear banding fracture without volume expansion has not been observed
for CPNC. The initiation may indeed be a mineral contaminant or a nanoscale
defect at the polymer/clay interface. According to Bureau et al. [2001] the internal
energy change per unit crack length, Jc, is significantly lower in CPNC than in
the neat polymer.
434