2

Modif ication of Polymer Mechanical and Rheological

Properties with Functional Fillers
Marino Xanthos

2.1
Introduction
Parameters affecting the performance of polymer composites containing functional
f illers are related to:
1. The characteristics of the f iller itself, including its geometry (particle shape, particle size and size distribution, aspect ratio), its surface area and porosity, and its
physical, mechanical, chemical, thermal, optical, electrical, and other properties.
Relevant concepts introduced in Chapter 1 are further discussed in this chapter
and also in other chapters dealing with specif ic f illers and surface modif iers.
2. The type and extent of interactions at the phase boundaries, which affect adhesion
and stress transfer from the matrix to the f iller. Interfacial interactions are also
re- lated to surface characteristics of the f iller, such as surface tension and surface
re- activity. These are parameters that control its wetting and dispersion
characteris- tics. The importance of the interface is also emphasized in Chapters
4 6.
3. The method of incorporation of the f iller into the polymer melt (discussed
in Chapter
3) and
its distribution in the
f inal product
part;
processing/structure/ property relationships are brief ly discussed in this chapter
and are elaborated in other chapters covering specif ic f illers.
Given the overall importance of mechanical properties, this chapter focuses on parameters controlling such properties as related to the f iller, the f iller/polymer
inter- face, and the method of fabrication. Concepts presented below may also be
applica- ble to the modif ication of other polymer properties (e.g. permeability,
thermal ex- pansion) through the addition of functional f illers.

Functional Fillers for Plastics. Edited by M. Xanthos

Copyright 2005 WILEY-VCH Verlag GmbH & Co KGaA
ISBN 3-527-31054 -1

2.3 Modif ication of Mechanical Properties 19

2.2
The Importance of the Interface
Interactions at phase boundaries affect not only the mechanical behavior, but also the
rheology and processing characteristics, environmental resistance, sorption and diffusion, and many other properties of composites. The strength (tensile, f lexural) of a
composite and its retention at higher temperatures, after prolonged times, and under
adverse environmental conditions are particularly affected by interfacial adhesion.
The principal sources of information presented in this section are refs. [1 6].
The extent of adhesion at the polymer/f iller interface may be related to various parameters associated with adsorption and wetting. Factors related to adsorption of the
polymer onto the f iller are types of interfacial forces (primary, secondary bonds), molecular orientation/conformation at the interface, and polymer mobility. Contact angle, surface tension, and substrate critical surface tension are among factors related
to wetting.
For a drop of liquid in equilibrium on a solid surface, Youngs equation relates interfacial tensions at the solid/vapor interface, 1, liquid/vapor interface, 2, and solid/liquid interface, 12, with the contact angle, , which is a measure of the degree of
wetting taking a value of zero for ideal wetting.
1 = 12 + 2 cos
(2-1)
Critical surface tension, c, equals the surface tension of a liquid that exhibits zero
contact angle on the solid. Any liquid (melt) with a surface tension less than that of
the solids critical surface tension will wet the surface. Uncoated inorganic f illers may
have very high surface tension, > 200 mJm2, whereas polymers such as polystyrene
and polyethylene have lower surface tension, < 50 mJm2. Thus, polymer melts will
spread on the high energy surfaces of f illers, unless the c value of the f iller is
reduced by absorbed water layers ( = 21.8 mJm2), by contamination with low
surface tension impurities, or by surface irregularities. This will result in
incomplete wetting and void formation at the interface.
The need to minimize contact angle in order to maximize the work of adhesion,
Wa, is shown by the following YoungDupr equations:
Wa = 1 + 2 12
Wa = 2 (1 + cos)

(2-2)
(2-3)

The need to minimize unfavorable interfacial interactions by minimizing the interfacial tension, 12, can also be inferred from the following simplif ied GoodGirifalco equations:
12 = 1 + 2 2 (12)0.5
Wa = 2 (12)0.5

(2-4)
(2-5)

where is an interaction parameter that depends on polarity. Polarity is def ined

as the ratio of the polar component of the surface tension to the total surface tension.

2.3 Modif ication of Mechanical Properties 19

is maximal when the polarities are equal (approaching unity) and is minimal (approximately zero) when the polarities are totally mismatched. It follows that f inite 12
and low Wa are the result of disparity between polarities (as, for example, between a
non-polar polyalkene and a hydrophilic polar f iller surface). Surface modif ication of
f illers can reduce 12, modify the c of the f iller, and reduce polarity differences.
Surface modif ication of f ibrous or non-f ibrous f illers through the introduction of
new functional groups, or the modif ication of existing ones, may be accomplished by
oxidation, thermal treatment, plasma treatment, vapor deposition, ion exchange, or
through the application of additives that may react or interact with both the f iller and
the polymer matrix. Figure 2-1 [7] shows the structure of a hypothetical mineral and
the availability of multiple sites for either direct interactions or reactions with the
polymeric matrix or through additives such as coupling agents. Surface modif ication
of the mineral for improved adhesion can, in effect, convert an ordinary f iller into a
value-added f iller with multiple functionalities. Surface modif ication is further covered in detail in Chapters 4 6 of this book.

Structure and reactivity of a hypothetical silicate mineral. 1: interlamellar

spaces; 2: exchangeable cations (acidic potential); 3: variable valence species; 4: reactive
Fig. 2-1

hydroxylic species; 5: Lewis acids; 6: anion-exchange sites; 7: bridged hydroxyl groups (reproduced from ref. [7]).

2.3
Modif ication of Mechanical Properties
2.3.1
General
Modif ication of mechanical properties and, in particular, the enhancement of
modu- lus and strength is undoubtedly one of the most compelling reasons for
incorporat- ing functional f illers into thermoplastics. Appropriate selection of a f iller
based on its

2.3 Modif ication of Mechanical Properties 21

size and shape, modulus and strength, and density is of paramount importance in order to establish its potential reinforcing capacity and to provide guidelines for its
method of incorporation into the polymer. For directional f illers with a certain
aspect ratio (e.g. short f ibers and f lakes or platelets) embedded in thermoplastic
matrices, the load is transferred from matrix to f ibers or f lakes by a shear stress
and the ends of the f ibers or f lakes do not bear a load. As a result, the properties of
the resulting composites are inferior to those of equivalent composites
containing continuous f ibers or ribbons. Although in some cases thermoplastic
composites containing con- tinuous f iber or ribbons have been produced, the
methods suitable for the produc- tion of short f iber or f lake composites are
conveniently those that are normally used for the processing of unf illed
thermoplastics (e.g., extrusion, injection molding, blow molding). Rigid f iller
particles may break during such operations with a concomitant reduction in aspect
ratio.
In Table 2-1, average values for modulus and strength of commercially available
continuous and discontinuous inorganic f ibers/ribbons/f lakes of different densities
are compared. Data have been obtained from a variety of sources [1,8 15] and often
may be subject to variation, considering measurement diff iculties, particularly for
short f illers of different origins. In particular, the strength values should be viewed
with caution since they depend on the method of testing and the effects of f laws and
edges. Data for typical polymer matrices are also included, as well as for whiskers or
single-crystal platelets, which are considered to be virtually f law-free and, therefore,
have extremely high strengths. Metallic wires have relatively large diameters and are
typically used as continuous reinforcements. The densities of particulate mineral
f illers (e.g., calcium carbonate, silica, talc, kaolin, wollastonite, aluminum
hydroxide) range from 2.4 to 2.75 g cm3. The corresponding Youngs modulus
values have been quoted as ranging from 25 to 35 GPa [14,16]. Data are often
expressed in terms of spe- cif ic properties (modulus or strength over density). It is
obvious, therefore, that for a specif ic application requiring high stiffness and
strength combined with light weight, the choice of f iller with the optimal specif ic
properties would be desirable.
In the following sections, theoretical and empirical treatments that have been used
to describe composite modulus and strength are presented for continuous f illers
(as- pect ratio approaching inf inity), discontinuous directional f illers (f inite aspect
ratio,
>1), and particulates (aspect ratio unity). An attempt is made to demonstrate the
principles governing the mechanical behavior of polymer composites through model systems rather than real molded parts having variable f iller orientation and distribution. For ease of analysis, stresses are only applied in tension, since the situation
in f lexure or compression becomes signif icantly more complicated in multiphase,
multicomponent systems. The principal sources of information presented in the following sections on modulus and strength are refs. [8,10,12,14,15,1719]. Parameters
controlling other mechanical properties are also brief ly covered.

2.3 Modif ication of Mechanical Properties 21

Comparison of commercially available high aspect ratio
f ibers, ribbons, and platelets
Tab. 2-1

Filler

Density,
Tensile Axial Modulus, GPa
Strength, g cm3
(average value)
(average value)

Inorganic Fibers
E-glass f ibers
S-glass f ibers
asbestos (chrysotile) f ibers
boron

2.54
2.49
2.5
2.57

Organic Fibers
carbon f ibers
2500 carbon nanotubes
180000 aramid f ibers
2800 polyester (terylene)
nylon f ibers
UHMWPE (Spectra 900)

1.791.86 230 340 (713)[a]

1.2
1000 1700
1.45
124 (5)[a]
1.38
1.2
1.14
2.9
0.97
117

Natural Fibers
sisal f ibers
507 (A. Sisalana)
jute f ibers
(C. capsularis)
f lax f ibers
900 (Lin usitatissimum)
cotton f ibers
wood f ibers
400
(aver. tropical hardwoods)
wood f ibers (Kraft)
Metallic Wires
steel wire
tungsten
Whiskers
silicon nitride
silicon carbide
aluminum oxide
20000

76
86
160
400

1500
1900
2000
3600
3200

600
800
2600

1.5

16.7

24.1

1.52

110

1.50
0.6

1.1
13.5

350

1.0

72

900

7.9
19.3

210
407

2390
2890

3.2
3.2
4.0

350 380
480
700 1500

5000 7000
20000
10000

5978
480
500

up to 21000[b]
10000
6000 mica

Ribbons, Flakes, Platelets

glass ribbons
2.473.84
SiC platelets
3.2
AlB2 platelets
2.7
f lakes
2.72.9
175
exfoliated silicate
2.8 3.0
1000
nanoclay platelets
exfoliated graphite platelets
2.0
polymers
0.90 1.35
(excluding elastomers)

900

3000[c]
up to

170

1000
0.23.3

[a] Anisotropic f ibers; values in parentheses

relate to the radial direction.

[b] Extrinsic property depending on manufactur-

ing process.

Tensile Axial
MPa

10000 20000
8.595

[c] Maximum value for f lakes with perfect edges;

in practice, the strength of small f lakes can be

as low as 850 MPa.