Nanocomposites: mixing CNT

s into polymers
 Outline

1.Introduction
2. Composites of multiwalled carbon nanotubes (MWNT) with polycarb
onate (PC) produced by masterbatch dilution technique
•Electrical resistivity
•Dispersion and alignment
•Influence of processing parameters on electrical resistivity
3. Composites of MWNT and SWNT with PC produced by direct incorp
oration
•Percolation of different commercial MWNT in PC
•Percolation of SWNT in PC
•Stress-strain behaviour
4. Summary
Benefits of CNTs to polymers

– Electrical conductivity
– Improvement of mechanical properties, especially stre
ngth
– Enhancement of thermal stability
– Enhancement of thermal conductivity
– Improvement of fire retardancy
– Enhancement of oxidation stability

– Effects at low CNT contents because of the very high

aspect ratio
How to introduce CNTs into polyme
rs
Melt mixing of CNT with thermoplas
tic polymers
 Preparation of the PC-MWNT
composites
• Masterbatch technology: polycarbonate(PC) + P
C based masterbatch (15 wt% MWNT)
– masterbatch (Hyperion Catalysis International, Inc, Ca
mbridge, USA) diluted with PC Iupilon E2000 (PC1),
PC Lexan 121 (PC2) or PC as used for the masterbat
ch (PC3)
– Haakeco-rotating, intermeshing twin screw extruder w
ith one kilogramm mixtures
– DACA Micro Compounder, conical twin screw extrude
r (4.5 cm3capacity)
– Brabender PL-19 single screw extruder
Characterization of the masterbatch
(PC + 15 wt% MWNT)
Dispersion in PC-MWNT
composites
Alignment in PC-MWNT
composites
Comparison for different set of PC
masterbatch dilution
Detection of percolation and influence of processing
conditions investigated by dielectric spectroscopy
Direct incorporation of different kind
s of commercial MWNT into PC
Comparison of direct incorporation of CNT, master
batch dilution, and CB addition
Direct incorporationof SWNT1 into PC
Direct incorporation of SWNT1 into PC
Direct incorporation of SWNT1 into PC
Direct incorporationof SWNT2 into PC
Direct incorporation of SWNT2 into PC
 Summary
• Melt mixing is a powerful method to disperse CNT into polymers
• Masterbatch dilution technique (based on a PC masterbatch)
– percolation in the range of 1.0 wt% MWNT
– suitable processing conditions can shift percolation to lower values (0.5
wt%)
– effects of mixing equipment and PC viscosity on percolation are small
• Direct incorporation method
– percolation strongly depends on the kind of CNT, production method (re
sulting in different sizes, purity and defect levels), and the purifying/modi
fication steps
– for commercial MWNT percolation occurs between 1.0 and 3.0 wt% and
is lower at lower MWNT diameters and higher purity
– HipCO-SWNT (CNI) percolation between 0.30 and 0.35 wt%
– stress-strain behavior of the composites: modulus and stress are
enhanced, elongation at break reduced especially above percolation
concentration
 Graphene–polymer composite
• Graphite oxide was prepared by the Hummers method from SP-1 graphite
(Bay Carbon), and dried for a week over phosphorus pentoxide in a vacuum
desiccator. Dried graphite oxide (50 mg) was suspended in anhydrous DMF
(5 ml, Dow-Grubbs solvent system), treated with phenyl isocyanate (2 mmol
, Sigma-Aldrich) for 24 h, and recovered by filtration through a sintered glas
s funnel (50 ml, medium porosity). Stable dispersions of the resulting phenyl
isocyanate-treated graphite oxide materials were prepared by ultrasonic exf
oliation (Fisher Scientific FS60, 150 W, 1 h) in DMF (1 mg ml-1). Polystyren
e (Scientific Polymer Products, approximate Mw = 280 kD, PDI = 3.0) was a
dded to these dispersions and dissolved with stirring (Fig. 1d, left). Reductio
n of the dispersed material (Fig. 1d, right) was carried out with dimethylhydr
azine (0.1 ml in 10 ml of DMF, Sigma-Aldrich) at 80 °C for 24 h. Upon compl
etion, the coagulation of the polymer composites was accomplished by addi
ng the DMF solutions dropwise into a large volume of vigorously stirred met
hanol (10:1 with respect to the volume of DMF used). The coagulated comp
osite powder (Fig. 1e) was isolated via filtration; washed with methanol (200
 ml); dried at 130 °C under vacuum for 10 h to remove residual solvent, ant
i-solvent, and moisture; crushed into a fine powder with a mortar and pestle,
and then pressed (Fig. 1f) in a hydraulic hot press (Model 0230C-X1, PHI-T
ulip) at 18 kN with a temperature of 210 °C.
Process flow of graphene–polym
er composite fabrication
• a, SEM and digital image (inset) of natural graphite. b, A typical AF
M non-contact-mode image of graphite oxide sheets deposited onto
a mica substrate from an aqueous dispersion (inset) with superimpo
sed cross-section measurements taken along the red line indicating
a sheet thickness of 1 nm. c, AFM image of phenyl isocyanate-treat
ed graphite oxide sheets on mica and profile plot showing the 1 nm
thickness. d, Suspension of phenyl isocyanate-treated graphite oxid
e (1 mg ml-1) and dissolved polystyrene in DMF before (left) and aft
er (right) reduction by N,N-dimethylhydrazine. e, Composite powder
as obtained after coagulation in methanol. f, Hot-pressed composite
(0.12 vol.% of graphene) and pure polystyrene of the same 0.4-mm
thickness and processed in the same way. g, Low (top row) and hig
h (bottom row) magnification SEM images obtained from a fracture s
urface of composite samples of 0.48 vol.% (left) and 2.4 vol.% (right)
graphene in polystyrene.
Advantages of Nanosized Additions
The Nanocomposites 2000 conference has revealed clearly the prop
erty advantages that nanomaterial additives can provide in comparis
on to both their conventional filler counterparts and base polymer. P
roperties which have been shown to undergo substantial improveme
nts include:
• Mechanical properties e.g. strength, modulus and dimensional stability
 Decreased permeability to gases, water and hydrocarbons
 Thermal stability and heat distortion temperature
 Flame retardancy and reduced smoke emissions
 Chemical resistance
 Surface appearance
 Electrical conductivity
 Optical clarity in comparison to conventionally filled polymers
Disadvantages of Nanosized Additi
ons
• To date one of the few disadvantages associated with na
noparticle incorporation has concerned toughness and i
mpact performance. Some of the data presented has su
ggested that nanoclay modification of polymers such as
polyamides, could reduce impact performance. Clearly th
is is an issue which would require consideration for appli
cations where impact loading events are likely. In additio
n, further research will be necessary to, for example, dev
elop a better understanding of formulation/structure/prop
erty relationships, better routes to platelet exfoliation and
dispersion etc.
Examples of Mechanical Property g
ains due to Nanoparticle Additions
• Data provided by Hartmut Fischer of TNO in the Netherlands relatin
g to polyamide – montmorillonite nanocomposites indicates tensile s
trength improvements of approximately 40 and 20% at temperatures
of 23ºC and 120ºC respectively and modulus improvements of 70%
and a very impressive 220% at the same temperatures. In addition
Heat Distortion Temperature was shown to increase from 65ºC for t
he unmodified polyamide to 152ºC for the nanoclay-modified materi
al, all the above being achieved with just a 5% loading of montmorill
onite clay. Similar mechanical property improvements were present
ed for polymethyl methacrylate – clay hybrids.
• Further data provided by Akkepeddi of Honeywell relating to polyami
de-6 polymers confirms these property trends. In addition, the furthe
r benefits of short/long glass fibre incorporation, together with nanoc
lay incorporation, are clearly revealed.
 Area of Applications
• Such mechanical property improvements have resulted i
n major interest in nanocomposite materials in numerous
automotive and general/industrial applications. These inc
lude potential for utilization as mirror housings on various
vehicle types, door handles, engine covers and intake m
anifolds and timing belt covers. More general application
s currently being considered include usage as impellers
and blades for vacuum cleaners, power tool housings, m
ower hoods and covers for portable electronic equipment
such as mobile phones, pagers etc.
 Gas Barrier
• The gaseous barrier property improvement that can result from incorp
oration of relatively small quantities of nanoclay materials is shown to
be substantial. Data provided from various sources indicates oxygen t
ransmission rates for polyamide-organoclay composites which are us
ually less than half that of the unmodified polymer. Further data reveal
s the extent to which both the amount of clay incorporated in the poly
mer, and the aspect ratio of the filler contributes to overall barrier perf
ormance. In particular, aspect ratio is shown to have a major effect, wit
h high ratios (and hence tendencies towards filler incorporation at the
nano-level) quite dramatically enhancing gaseous barrier properties. S
uch excellent barrier characteristics have resulted in considerable inte
rest in nanoclay composites in food packaging applications, both flexi
ble and rigid. Specific examples include packaging for processed meat
s, cheese, confectionery, cereals and boil-in-the-bag foods, also extru
sion-coating applications in association with paperboard for fruit juice
and dairy products, together with co-extrusion processes for the manu
facture of beer and carbonated drinks bottles. The use of nanocompos
ite formulations would be expected to enhance considerably the shelf l
ife of many types of food.
 Fuel Tanks
• The ability of nanoclay incorporation to reduce solvent tr
ansmission through polymers such as polyamides has b
een demonstrated. Data provided by De Bievre and Nak
amura of UBE Industries reveals significant reductions in
fuel transmission through polyamide–6/66 polymers by in
corporation of a nanoclay filler. As a result, considerable
interest is now being shown in these materials as both fu
el tank and fuel line components for cars. Of further inter
est for this type of application, the reduced fuel transmiss
ion characteristics are accompanied by significant materi
al cost reductions.
 Films
• The presence of filler incorporation at nano-levels has also been sh
own to have significant effects on the transparency and haze charac
teristics of films. In comparison to conventionally filled polymers, na
noclay incorporation has been shown to significantly enhance transp
arency and reduce haze. With polyamide based composites, this eff
ect has been shown to be due to modifications in the crystallisation
behaviour brought about by the nanoclay particles; spherilitic domai
n dimensions being considerably smaller. Similarly, nano-modified p
olymers have been shown, when employed to coat polymeric transp
arency materials, to enhance both toughness and hardness of these
materials without interfering with light transmission characteristics. A
n ability to resist high velocity impact combined with substantially im
proved abrasion resistance was demonstrated by Haghighat of Trito
n Systems.
 Environmental Protection
• Water laden atmospheres have long been regarded as one of the mos
t damaging environments which polymeric materials can encounter. T
hus an ability to minimize the extent to which water is absorbed can b
e a major advantage. Data provided by Beall from Missouri Baptist Col
lege indicates the significant extent to which nanoclay incorporation ca
n reduce the extent of water absorption in a polymer. Similar effects h
ave been observed by van Es of DSM with polyamide based nanocom
posites. In addition, van Es noted a significant effect of nanoclay aspe
ct ratio on water diffusion characteristics in a polyimide nanocomposit
e. Specifically, increasing aspect ratio was found to diminish substanti
ally the amount of water absorbed, thus indicating the beneficial effect
s likely from nanoparticle incorporation in comparison to conventional
microparticle loading. Hydrophobic enhancement would clearly promot
e both improved nanocomposite properties and diminish the extent to
which water would be transmitted through to an underlying substrate.
Thus, applications in which contact with water or moist environments i
s likely could clearly benefit from materials incorporating nanoclay part
icles.
Preparation and Characterization of Nove
l Polymer/Silicate Nanocomposites

• Five categories cover the majority of composites

synthesized with more recent techniques being
modifications or combinations from this list.
• Type I: Organic polymer embedded in an
inorganic matrix without covalent bonding
between the components.
• Type II: Organic polymer embedded in an
inorganic matrix with sites of covalent bonding
between the components.
Preparation and Characterization of Nove
l Polymer/Silicate Nanocomposites

• Type III: Co-formed interpenetrating networks of

inorganic and organic polymers without covalent
bonds between phases.
• Type IV: Co-formed interpenetrating networks of
inorganic and organic polymers with covalent
bonds between phases.
• Type V: Non-shrinking simultaneous
polymerization of inorganic and organic
polymers.
Preparation and Characterization of Nove
l Polymer/Silicate Nanocomposites

• The great majority of nanocomposites inco

rporate silica from tetraethoxysilane (TEO
S). The formation of the inorganic compon
ent involves two steps, hydrolysis and con
densation as seen in Scheme 1.
Polymers considered: PEO, PEO/PPO,
PVAc, PVA, PAN, MEEP
• A general synthesis for a base, acid, or salt catalyzed polyphosphazene, pol
yethylene oxide (PEO), and polyethylene oxide/polypropylene oxide (PPO/P
EO) block nanocomposite is as follows: 300 mg of polymer is dissolved into
10 mL of a 50/50 by volume tetrahydrofuran (THF)/ethanol mixed solvent in
a capped vial. To this solution is added TEOS (336 mg). A catalyst is then in
troduced as an aqueous solution (150 μl) and the mixture is capped and son
icated at 50oC for 30 minutes. The solution is aged from hours to days depe
nding upon the catalyst used in a sealed vial and poured into a Teflon mold
and loosely covered at room temperature. The nanocomposite self assembl
es as the volatile solvent slowly escapes during the condensation process.
• The synthesis of polyvinyl acetate (PVAc)/silicate nanocomposites requires
a different approach from the other nanocomposites. PVAc (300 mg) is diss
olved into an 50/50 by volume acetic acid/methanol (10 mL) mixed solvent i
n a capped vial. To this solution is added TEOS (373 mg). The solution is th
en sonicated for 5 minutes in a sealed vial at room temperature and poured
into a Teflon mould and loosely covered at room temperature. The nanocom
posite self assembles during the curing process, which typically lasts up to 2
4 hours. Additional heating at 100 °C for 30 minutes aids in removing lingeri
ng acetic acid from the nanocomposite.
 Applications
• One of the most interesting of these applications is as solid polymer
electrolytes (SPE) for lithium batteries. The polyphosphazene MEEP
is a well-known SPE with very high room temperature conductivity,
however it lacks the mechanical stability to be used in a practical de
vice (12). Traditional stabilization methods, such as deep UV or elec
tron beam crosslinking methods do improve the physical stability of
SPEs, however this crosslinking lowers ionic conductivity – tests per
formed in our laboratory revealed this to be a factor of 30-45 for ME
EP-like phosphazene polymers. This reduction is due to the addition
al covalent linkages formed during the crosslinking process that inhi
bit chain segmental motion and ion transfer. Since the nanocomposi
tes formed by the ceramic condensation process do not form bonds
to the polymer component, (Type I nanocomposites) mechanical sta
bilization is achieved without a great loss of ionic conductivity (13).
However, these nanocomposites have the highest tensile strength o
f any of the catalyst types studied; yet they were also found to be gl
assy and brittle.
Goal for Type I Nanocomposites
• The goal in the process is to form a compl
etely interpenetrating network (IPN) of bot
h inorganic and organic phases. Homogen
eous nanocomposites with good IPNs are
often stronger, more resilient, and optically
transparent, whereas heterogeneous com
posites are often mechanically weaker and
opaque.
 Novel Rubber Nanocomposites with
Adaptable Mechanical Properties

• Silica particles have become more important in tire applications sinc

e the introduction of the Green Tire® by Michelin. As a filler, silica h
as greater reinforcing power, such as improving tear strength, abrasi
on resistance, age resistance and adhesion properties than carbon
black [6-8]. However, due to the strong inter-particle hydrogen bond
s between hydroxyl groups, the agglomeration nature of silica is gen
erally believed to be responsible for the significant Payne effect whic
h brings about considerable rolling resistance for tire applications. In
order to reduce the filler-filler interaction and/or to enhance the mec
hanical properties of silica filled composites, researchers have been
working for many years on different strategies to improve silica-rubb
er interaction and, in turn, to reduce the rolling resistance. Among th
ese strategies, chemical modifications of rubbers by attaching functi
onal groups interacting with silica [9-22] and surface treatments of si
lica by reducing surface polarity with different silane coupling agents
[22-36] are the most popular techniques.
•
 Novel Rubber Nanocomposites with
Adaptable Mechanical Properties
• However, these techniques admittedly have quite a few drawbacks.
For the former technique, the chemical modification reaction of rubb
er was usually not applicable to commercial production and its degr
ee of modification was usually very low [9,11,14,18,22]. Additionally,
the chemical modification was limited to rubber chain ends [12,17,2
0], meaning that the final silica composite was unsatisfactory in term
s of reducing silica agglomeration. For the latter, the used coupling
agents are expensive and it could possibly lower the crosslinking de
nsity by reacting with the chemical ingredients for vulcanization. Thi
s technique would lead to lower overall cure rates [34,35], and at the
same time it degraded the mechanical performance of such silica fill
ed material for tire applications. In summary, due to these flaws non
e of the methods mentioned above could simultaneously ensure bot
h the ability in reducing the silica agglomeration and improving the
material performance.
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