Documentos de Académico
Documentos de Profesional
Documentos de Cultura
Polymer
Composites
Second Edition
Editor
R.N. Rothon
Filled Thermoplastics
Chris DeArmitt and Michael Hancock
8.1 Introduction
8.1.1 Thermoplastics and Typical Applications
Thermoplastics have become an essential part of our everyday lives. Our cars and appliances
contain more and more plastics every year. Even our clothes are often made from synthetic
thermoplastics. They are a very important class of material for many reasons. They combine
good mechanical and electrical properties with low density and high formability. Clearly,
the driving force for their success has been that they can often provide an overall solution
that is less expensive than that achievable with other materials such as glass, wood, metal,
thermosetting polymers or ceramics. Thermoplastics, as implied by their name, are materials
that flow upon heating, and harden when cooled. They can be formed using a wide variety
of techniques, such as injection moulding, thermoforming, blow moulding and rotational
moulding. Injection moulding in particular allows complex shapes, so it is possible to
integrate several smaller parts into one larger part, thus saving on assembly costs. As well
as being easily processed when molten, they also have the potential to be recycled by remelting them to form new articles, or burnt and used to generate electrical energy. New
legislation is being introduced to encourage recycling of used products; this is expected to
favour thermoplastics over other materials, which are not as easy to reprocess.
Thermoplastic demand in Western Europe is 37 x 106 tonnes compared to 10 x 106 tonnes
for thermosetting polymers. A breakdown of thermoplastics by application area is given in
Figure 8.1.
Some of the main properties and applications are given next for the five main thermoplastics,
which together account for 75% of the total thermoplastics market.
Polyethylene (low density) LDPE, (linear low density) LLDPE: 7.6 x 106
tonnes
Properties: Flexible, translucent, very tough, weatherproof, good chemical
resistance, low water absorption, easily processed by most methods, low cost.
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Polystyrene (general purpose) GPPS: 3.1 x 106 tonnes combined with high
impact polystyrene (HIPS)
Properties: Brittle, rigid, transparent, low shrinkage, low cost, excellent X-ray
resistance, free from odour and taste, easy to process.
Applications: Toys and novelties, rigid packaging, refrigerator trays and boxes, cosmetic
packs and costume jewellery, lighting diffusers, audio cassette and CD cases.
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density, modulus and yield strength can be predicted by the rule of mixtures, according
to the volume fraction of each component. In other cases, there are more complex
mathematical models that can be used to describe and predict properties as the volume
fraction of the ingredients is varied.
Sometimes, the inclusion of filler can chemically or physically modify the polymer phase
to such as extent that it becomes more difficult to apply simple models. It is important to
realise that these complications may occur, and to look for them when characterising
composites. This will help in the understanding and design of new composite materials.
One example of this behaviour is changes in crystallisation, such as nucleation of crystal
growth [10-14] and changing of the crystal phase of the polymer [15, 16]. Chemical
degradation of the polymer may be catalysed by the filler, or impurities in the filler,
especially transition metals [17, 18]. Another common example is where the filler surface
adsorbs stabilisers and antioxidants, which are then unable to protect the polymer during
processing and during its service life [19-21]. Alternatively, mechanical degradation may
occur when high levels of filler cause unduly high viscosity, thereby inducing chain scission
due to the excessive shear needed to process the material.
In this chapter, an attempt has been made to mention each of the factors that influence
composite design and performance. For a given application, one must identify the key
properties that are important and concentrate on those. It will be seen that there are
many different parameters to consider and that in some cases, optimisation of one
precipitates an inevitable worsening of some other property. There is no one optimal
composite; rather the goal is to seek the best balance of properties through compromise
and an awareness of the entire picture in terms of economics and performance. In cases
where the filler is less expensive than the polymer, then the goal is to increase the filler
loading as much as possible, while still retaining sufficient processability and properties.
Conversely, when the filler is more expensive than the polymer on a volume basis, then
one seeks to identify the minimum filler loading that gives sufficient properties.
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c =
f p
pm f + f (1 m f )
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In order to dampen sound, a material must be able to absorb vibrational energy (sound)
and transform the energy into thermal energy (heat). The loss factor, tan , is the parameter
that best describes the sound damping ability of materials [5]. It is the inelastic component
of the materials response to deformation. The loss factor can be measured by dynamic
mechanical thermal analysis (DMTA), which shows its behaviour with changes in
frequency and temperature. It is common to select a matrix with a high tan in the
frequency range to be damped. Then, high-density filler can be added in order to further
improve performance. Mica is also used, as the platy particles cause multiple reflection
of the sound waves so they may be absorbed in the composite instead of passing straight
through [5]. Adding too much filler should be avoided however, because this leads to
particle-particle interactions, and eventually percolation, where a continuous path exists
from particle to particle. Under those conditions, the acoustic energy can pass through
the interparticle contacts, largely avoiding interaction with the matrix.
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concentrate known as a masterbatch. After it emerges from the die, the molten polymer
string is usually cooled rapidly by running it through a water bath. The polymer is then
dried and lastly, the cooled polymer strand is chopped into small granules using a pelletising
machine. If the material is to be stored before use, then it is common to seal the pellets to
protect them from contamination and water pick-up.
The extrusion step is not particularly costly in comparison with the price of the raw materials,
but the cost is still significant and impacts on the overall economics of the final material. It
is therefore worthwhile to devote effort to optimisation of the extrusion process in terms
of increased throughput (productivity) and decreasing energy consumption and machine
wear. In the authors opinion, the subject of throughput does not receive the attention it
deserves. There are countless reports of the mechanical properties of thermoplastic
composites but no mention of the extrusion characteristics of the materials. For a meaningful
comparison of different composites, one must consider not only their mechanical and
aesthetic properties, but also the relative economics of extrusion.
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8.2.4.3 Dispersion
Good dispersion is nearly always beneficial for the properties of a composite so one tries
to optimise the dispersion of filler. The level of dispersion can be measured directly or
indirectly. The most common direct measurement is to perform scanning electron
microscopy (SEM) on a cross-section. It is advisable to use two different magnifications
to examine the filler distribution on a macroscopic and dispersion on a microscopic
scale. An indirect measurement is to measure the unnotched impact strength of the
composites, as that property is sensitive to agglomerates. In a rather insightful study,
Hornsby showed the degree of dispersion of filler as it passed through a twin-screw
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extruder [25]. This was achieved by using a clamshell extruder that could be stopped
and opened so that samples of compound could be removed for analysis. It was found
that the greater part of the dispersion was imparted in the melt zone where the pellets of
polymer are just melting. The high viscosity in that region requires a high energy input
and encourages deagglomeration. Feeding the filler into the unmelted polymer may give
good dispersion, but it also results in higher wear of the extruder so that this approach is
only advisable for soft, surface treated fillers. It is more usual to add the filler when the
polymer is already molten although a multitude of feeding possibilities exist [25].
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It is often not possible to use the same mould for filled and unfilled polymer because the
change in shrinkage gives parts that are out of specification. On the other hand, adding
filler to a polymer allows its shrinkage to be systematically tuned. This tuning method is
useful for example, if one is attempting to use an existing mould with a different polymer.
Filler may be added to the newly chosen polymer to achieve similar shrinkage to that of
the previously used polymer. Injection moulding tools (moulds) are very expensive and it
is preferable to keep using the same mould rather than purchasing a new one specifically
made to accommodate the new polymer.
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Most fillers, while having good dielectric properties and resistivities, are in general worse
than a plastic. Also, incorporation of a filler will introduce flaws and interfaces, charged
ions and traces of water (all fine particles adsorb some water from their environment) and
hence reduce electrical properties. Usually, however, because of the good electrical properties
of the plastic, fillers may be used simply as an extender, the composite still giving good
properties. Calcined clay (produced at just above 1000 C) and other calcined silicates, do
not degrade electrical performance as severely as other fillers, because of low water pickup, and immobilisation of matrix ions. Conversely, metakaolin, because of its highly reactive
surface absorbs ions and thus improves the electrical performance of polymers such as
plasticised PVC and ethylene vinyl acetate (EVA) copolymers [47]. Due to their good
insulation characteristics thermoplastics can suffer from tracking, i.e., the build-up of surface
charge which then discharges across the surface, because that path has less resistance than
passage through the plastic. Filler particles can reduce this problem by acting as a physical
barrier and by distributing the charge before critical build-up occurs [48, 49].
In many cases, it is beneficial to introduce some level of electrical conductivity into a
polymeric material [5, 22]. The highly insulating polymers are susceptible to static build
up. This may be a nuisance, attracting dust to the surface, or it may lead to damage of
sensitive electronic parts, when manufacturing integrated circuits, for example. Even
very low levels of surface conductivity will resolve this problem [6]. Organic based
antistatic additives are available or alternatively conductive fillers such as carbon black,
graphite, or metals may be added [6].
Sometimes, a material of much higher conductivity is required. One example is for
electromagnetic interference (EMI) shielding [22]. This is achieved by adding a sufficient
level of conductive filler. Initially, as one adds more conductive filler, the conductivity does
not rise appreciably, because the conductive particles remain isolated from one another. As
the filler loading is gradually increased, the conductivity suddenly rises sharply, by many
orders of magnitude, approaching the conductivity of the conductive filler itself, and then
levels off [50]. This discontinuity is known as the percolation threshold and it signifies the
volume percentage of filler required to attain a continuous network of interconnected
particles throughout the matrix [22]. Usually, 10-30 volume percent of filler is needed to
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As mentioned previously, the addition of filler may also change the amount of crystallinity
in the polymer. As polymer crystals are impermeable even to low molecular weight species,
an increase in crystallinity also results in improved barrier properties, through increased
tortuosity [54]. This effect is expected to be especially prevalent for fillers that induce a
high degree of transcrystallinity.
Dispersion and wetting of the filler can also affect the permeability of the composite. It
has been shown that PE filled with 25 volume percent calcium carbonate was actually
four times more permeable to oxygen compared to the unfilled reference PE. This was
attributed to poor wetting of the filler, so that the diffusant was able to travel unimpeded
along the polymer/filler interface. In contrast, stearic acid coated calcium carbonate at
the same loading resulted in three times lower oxygen permeability than the unfilled PE
[55]. Similarly, Tiburcio and Manson showed that the water vapour permeability of
glass-bead filled phenoxy films decreased sharply as the degree of adhesion between the
filler and the matrix was increased [56].
In some cases, it is desirable to increase the permeability of a polymeric material. One
example is breathable films. For example, calcium carbonate filled PP films are first
made by solvent casting, or extrusion casting or as blown film and subsequently stretched
to delaminate the filler polymer interface [57]. High filler loadings are used to ensure
interconnecting voids, giving unimpeded diffusion [58].
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Filled Thermoplastics
affected by the filler particle size. Particle size effects are allowed for to some extent in
the modified Kerner equation by the introduction of an effective filler volume fraction.
The most important filler parameter affecting modulus is its shape. Unfortunately, when
the filler is non-spherical theories become much more complicated and the reader is
advised to refer to Chows review [61]. Shape factors can be incorporated in the models
mentioned previously but are only useful when applied to very high aspect ratio materials,
e.g., fibres. There is also an almost insurmountable problem with particulate fillers: the
difficulty and effort to measure aspect ratios of micrometre sized particles. Pukansky
examined the effects of 11 different fillers in polypropylene [69] and concluded that
Youngs modulus is affected by the amount of bonded polymer, which is in turn related
to surface area, and therefore to both particle size and shape. That observation helps to
explain the strong effect that nano-fillers have on the modulus of a composite. Schreiber
and Germain showed that modulus depends on the strength of interaction between the
polymer and the filler surface [62].
To exemplify the effect of fillers on a thermoplastic, PP homopolymer filled with differing
filler types and consequently very different shapes is shown in Figure 8.2. It can be seen
that a linear fit can be used successfully for most of the fillers. The exception is mica,
which deviates from linearity at high filler levels where interparticle interactions become
important. The modulus values also reflect the expected shapes of each of the fillers.
Similar trends are reported for other common polymers [22].
Figure 8.2 The effect of common fillers on the tensile modulus of PP homopolymer
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Filled Thermoplastics
polymers like polystyrene, acrylonitrile-butadiene-styrene (ABS), polycarbonate and
polysulfone [1]. Addition of glass fibre to semi-crystalline polymers gives an HDT
approaching the melting point of the matrix. In the case of amorphous polymers,
incorporation of glass fibre gives an HDT (at 1.8 MPa stress), which is close to the Tg of
the matrix. For this reason, filler is most commonly used in semi-crystalline polymers
where the HDT is improved most because the crystalline regions help transfer stress to
the filler under load [70].
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Figure 8.4 The effect of common fillers on the yield strength of PP homopolymer
reinforcement, platy fillers are better and fibrous fillers are best of all [5, 30]. Usually, it
is considered that spherical fillers such as calcium carbonate and dolomite do not reinforce
at all, and in fact they usually reduce the yield strength of the material (Figure 8.4).
However, that is not necessarily true, as it has been shown that it is possible to increase
the yield strength of PP by using very fine spherical filler with a mean diameter of 0.01
m [78, 79]. This improvement must be due to the high surface area of the filler as the
filler is isotropic. The high surface area increases overall polymer-filler adhesion and
thereby improves yield strength.
It is observed that spherical fillers do not reinforce whereas platy fillers like mica may do,
and glass fibres are most effective (Figure 8.4). In this particular example, talc does not
reinforce, probably because the talc grade used did not have sufficient anisotropy. As with
yield strength, the data shown is for PP homopolymer, but similar trends are seen for a
wide range of other thermoplastics [3, 22]. The filler creates an additional complication
especially for injection moulded parts. Namely, during mould filling, the filler distribution
becomes non-homogeneous due to the flow. One consequence is flow lines and weld lines.
These are created when two fronts of molten polymer meet. For an unfilled polymer the
melt can easily mix when two melt fronts meet and so the mechanical properties are normally
unchanged (except for the special case of liquid crystalline polymers). The uneven distribution
of filler at the weld lines creates a weak point, so for example, the measured yield strength
and elongation to break are reduced. This effect is not as great for isotropic fillers but for
more anisotropic fillers the yield strength may be reduced by more than fifty percent. It is
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Filled Thermoplastics
therefore essential to design with this in mind. This can be done by designing parts to avoid
weld lines and by judicious placement of injection points. Additionally, it should be
remembered that the reported mechanical properties for composites are for ideal specimens
with no weld lines, whereas the actual yield strength in the part may be far lower.
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(a)
(b)
Figure 8.5
(a) Effect of stearate coating level on a ultrafine calcium carbonate (d50: 0.8 m) on
the properties of polypropylene
(b) Effect of particle size of stearate coated calcium carbonate on the properties
of polypropylene
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8.4.2 Nucleation
It is widely recognised that fillers may affect the crystallisation of polymers [96]. The
filler may increase the rate of cooling, as mentioned previously, and may thereby affect
crystallisation. Some polymers have more that one type of crystal phase, which occur
preferentially when cooling within a certain temperature range [97, 98]. These crystal
types have different mechanical properties [99, 100] and therefore, the relative amount
of each phase will influence to the properties of the thermoplastic composite.
In other instances, the filler may nucleate crystal growth. This is often beneficial, as it
causes the material to harden more rapidly on cooling, giving the possibility of faster
production. In fact, it is common practice to add a small amount of fine talc to nucleate
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Filled Thermoplastics
Figure 8.6 The effect of some common fillers on the impact strength
of PP homopolymer
8.4.3 Transcrystallinity
Transcrystallinity may occur when a polymer is cooled in contact with a highly nucleating
filler or surface [95, 102]. Usually, polymer crystals are spherulitic, growing out radially
from the nucleation site [2, 85, 86]. In contrast, when crystals are nucleated very close
together, they impinge on each other almost immediately, and are forced to grow in one
direction, away from the nucleating surface [95]. For a polymer where only one crystal
form occurs, it has been shown that the microstructure of the transcrystalline phase is
the same as that for the spherulites [103]. The transcrystalline layer is typically 10-30
m thick, which means that for higher filler loadings, the whole matrix may be composed
of transcrystalline material [95]. Transcrystallinity has been reported in several systems
including glass [104], PET [105, 106] and some types of carbon fibre in PP [107], as well
as Kevlar fibres in Nylon 6,6 and even in Nylon-PP blends.
Sheets of transcrystalline PP have been prepared by cooling PP from the melt in between
PET (Melinex) sheets and the properties studied [108]. This rather elegant work by Fowkes
and Hardwick showed that the transcrystalline sheet had a much higher Youngs modulus
(1.09 GPa) compared to the control PP sample that was quenched to give a fine spherulitic
sheet (0.67 GPa). The tensile yield strength of the transcrystalline material was also higher
at 25.0 MPa, compared to 18.6 MPa for the spherulitic sheet. Some of the properties were
much worse compared to normal, spherulitic PP. For example, the transcrystalline sheet
showed just 4% elongation to break and an energy to failure of just 28.0 kJm-2, compared
to >300% and 48.5 kJm-2, respectively, for the fine spherulitic analogue.
Clearly then, the filler can greatly influence the type and level of crystallinity, leading to
profound changes in the properties of the resultant composite material.
8.4.4 Interphase
Aside from changes in crystallinity, there is another way in which the presence of filler may
alter the host polymer. It has been shown that polymer adsorbs onto the filler and that this
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Filled Thermoplastics
adsorbed material has different properties compared to those of the bulk matrix [68, 71,
109, 110]. Pukansky and Fekete have written a review of the importance of the interphase
in thermoplastics [9]. The relevance of the interphase to adhesion at planar interfaces, and
in composites, has been discussed by Berg [109]. As expected, the thickness of the interphase
varies depending upon the extent of interaction between the polymer and filler. It has been
shown that the thickness of the interphase is proportional to the reversible work of adhesion
[8]. Reported thicknesses are usually in the range 0.0040.15 m, depending upon the
polymer filler combination and the method used to estimate the thickness [9, 22]. It is
anticipated that the interphase thickness should be influenced by the ubiquitous van der
Waals forces plus any specific chemical interactions such as Lewis acid-base or hydrogen
bonding or covalent bonding [22]. Therefore it should be affected by surface treatment of
the filler. The degree to which the interphase affects the properties of the composite should
also therefore depend on the total surface area of the filler [22] and is therefore especially
important for nano-composites.
The surface tension of liquids is easily measured by a wide variety of methods, whereas
it is much more difficult to measure the surface energy of solids. A comprehensive overview
covering methods applicable for liquids and solids is presented by Adamson [111].
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viscosity of the polymer melt both disfavour wetting of the filler [111, 112]. Dynamic
wetting in composites is an area that deserves further study in order to understand and
optimise wetting under real processing conditions. Some studies have been performed, in
particular for fibre reinforced composites [117].
The spreading coefficient represents the thermodynamic driving force for the liquid to
spread onto and wet the solid (Equation 8.5). For spontaneous spreading to occur, the
spreading coefficient must be positive, implying a contact angle of zero.
S L / S = S ( L + SL )
8.5.4 Adhesion
The degree of adhesion between the filler and polymer is expected to influence the mechanical
properties of the composite. This can be predicted theoretically, although it is much more
difficult to prove experimentally. It is a major challenge to change the adhesion between
the polymer and the filler without invalidating the experiment by unintentionally altering
other parameters [109] such as filler dispersion level or polymer crystallinity.
Even so, many workers have tried to correlate the calculated reversible work of adhesion
with the mechanical properties of composites. Studies on planar surfaces have shown
that measured adhesive bond strengths are, at best, only one tenth of the calculated
value based on van der Waals interactions alone. It might therefore be assumed that the
reversible work of adhesion would have rather limited utility as an indicator of adhesion
at the interface. Despite that, it has been shown numerous times that the reversible work
of adhesion often does correlate rather well with the mechanical properties of composites,
in particular yield strength [8, 109]. Berg addressed the question of whether it was
worthwhile to use concepts such as reversible work of adhesion to predict and tune
adhesion [109]. The conclusion was that the approach is reasonably effective already
and will improve in the future.
The first criterion for good adhesion is intimate contact, that is good wetting of the
surface. Wetting is a necessary, but not sufficient, condition for good adhesion [109]. In
addition, one should seek to maximise the work of adhesion. The simplest case is to
consider the work of adhesion to be attributable solely to non polar (London) forces
between the materials. This is indeed the case when at least the adhesive (polymer melt)
or adherand (filler surface) is non-polar. So, for thermoplastics such as PE, PP and
polytetrafluoroethylene (PTFE) this simple case should apply.
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Filled Thermoplastics
Sinicki and Berg varied the Lewis acid-base interactions systematically and found a
correlation between adhesion measured by peel testing and the calculated thermodynamic
work of adhesion [118].
Schreiber and Germain used plasma treatment to alter the Lewis acid-base balance of
three fillers [62]. These were then compounded into two different matrix polymers. Firstly,
polyethylene (LLDPE), which is completely apolar and cannot form Lewis acid-base
interactions. The other polymer was poly(ethylene-vinyl acetate) [EVA], which is based
on polyethylene, but contains some (28 mole%) acetate groups, which they found to be
Lewis acidic (although acetate groups are also reported to be Lewis basic [109]). They
then measured tensile modulus and elongation at break to assess the affect of adhesion
on mechanical performance of the composites. In LLDPE, a fluoropolymer (PTFE-like)
coating on the filler gave lowest modulus and highest elongation to break, attributed to
poor adhesion. An ammonia plasma was used to give a polar, Lewis basic surface. For
this combination, the modulus was lower and the elongation to break higher than for
the untreated filler. This was consistent with reduced adhesion compared to the untreated
filler, but better than for the fluoropolymer coated filler. The modulus and adhesion
were maximised when the filler was plasma treated with methane to make the surface
non-polar like the polymer.
When the matrix polymer was changed to EVA, the results were quite different. In that
case, the highest modulus and least elongation to break were recorded for the ammonia
plasma treated filler. This was interpreted as being due to enhanced adhesion from the
bonding between the Lewis acidic groups in the polymer and the Lewis basic sites
introduced on the filler surface through ammonia treatment.
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Lewis basic probes. This shows that the dispersant should be chosen to optimise its
affinity for the filler or pigment.
It is important to ensure that the chosen surface treatment agent does in fact bind to the
filler. If the additive does not bond to the surface then it cannot fulfil its function. Excess
additive is, at best, a waste of money, but in some cases it may have worse consequences
such as destabilising the polymer. For example, it has been shown that calcium stearate,
a common dispersant, can destabilise polyolefins and cause yellowing, by interacting
with the antioxidant [127].
8.5.6.1 Dispersants
As mentioned, dispersant design and mode of action are well understood by surface
and colloid scientists [43, 112-115]. In that field, the term dispersant refers to any
additive that reduces the interparticle interactions, thereby encouraging dispersion of
the particles. This is achievable via a number of mechanisms using low molecular weight,
oligomeric, or polymeric additives [128]. Steric stabilisation is most relevant to mineral
fillers in polymers because it is the main way to achieve colloidal stability in low polarity
solvents. This stabilisation mechanism operates by strong adsorption of a layer of
organic additive that physically prevents close interparticle approach.
Stearic acid and metal stearates are widely used as dispersants, especially in cases where
high filler loadings are required. Examples are polyolefins filled with aluminium hydroxide
or magnesium hydroxide where 60 weight percent of filler or more may be needed to
achieve sufficient flame retardancy [129, 130]. Of course the correct level of addition
depends upon the amount of filler surface to be covered, and therefore upon the amount
of filler, and its specific surface area. Excess additive is to be avoided as it can seriously
destabilise some polymers and give yellowing problems [127].
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It is often assumed that coupling (adhesion) is good, but that is not always the case. For
example, good coupling is undesirable during extrusion, because it would dramatically
increase the torque (and energy) needed for extrusion. This would reduce extruder
throughput and that would result in a significantly more expensive material. Coupling is
advantageous when high yield strength is required, but it is often detrimental to the
elongation at break. Impact strength is more difficult to predict, it may increase or decrease
depending on the filler polymer combination. The effect of coupling agents on modulus
is less clear. The equation for describing modulus has no term for adhesion between filler
and polymer, so coupling agents should not affect modulus (Equation 8.4). However,
there are reports that they do affect modulus. This may be due to increased orientation
of the filler or due to the way that the modulus was determined. The modulus should be
determined at low stress, in the linear part of the stress-strain curve, where filler debonding
has not yet occurred, and should therefore be insensitive to adhesion.
8.6 Aesthetics
8.6.1 Introduction
Often thermoplastic composites are used in applications where the consumer will see the
part [131]. In those instances, it is vital to consider the aesthetic aspects of the material
as well as the mechanical, electrical and other properties. Fillers affect the surface finish,
colour and scratch-resistance of the composite and these factors should be optimised to
give a marketable product.
8.6.2 Colour/Pigmentation
Pigments may be either organic or inorganic particles that are added to give colour to a
plastic, as opposed to dyes, which dissolve in the plastic. Pigments can be considered as a
special class of filler, and they influence the polymer in much the same way as any other
filler would. So, for example, they can lower the thermal stability of the polymer matrix
[18], adsorb antioxidant and nucleate crystallisation of the polymer. They also affect the
mechanical properties in the same way as any other filler, but usually pigments are used at
concentrations that are too low to significantly affect modulus, yield strength or HDT. It is
essential to disperse pigments thoroughly in order to achieve the maximum tinting strength,
and to avoid agglomerates, which would lower the impact strength, as discussed previously.
As dry powders, several common fillers appear white, because they scatter light strongly,
and it might therefore be supposed that they would make good pigments for polymers.
This is usually not the case however, because the amount of scattering is determined by
the difference in refractive index between the particulate and continuous phases. This
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Filled Thermoplastics
refractive index difference is small for common fillers and thermoplastics and so scattering
is limited. In fact, in some cases the filler is invisible in the polymer because the refractive
indices match very closely. An example is glass beads in PVC. Calcium carbonate is
available in high whiteness and gives a mild pigmentary effect, but if high whiteness is
required, then a pigment of higher refractive index, such as titanium dioxide, must be
used. Titanium dioxide and carbon black are used to protect against UV radiation as
they scatter and adsorb it, respectively. It should be noted that commercial titanium
dioxide is always has an inorganic coating, e.g., aluminosilicate, plus an organic additive
such as a polyol or silicone [132]. This is necessary because naked titania can oxidatively
degrade polymers when exposed to UV light.
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Fillers often affect the stability of polymers via a variety of mechanisms. Although this is
recognised, at least to some extent, it has not been studied as thoroughly as the stability
of unfilled polymers. As the stability and recycleability can be critical issues, hopefully
this subject will receive more attention in the future.
Thermoplastics are usually processed in the molten state, at temperatures in the range
150-350 C depending on the melting point and viscosity of the polymer. There are
many standard stabilisation packages on the market, often containing a process stabiliser
and a long-term stabiliser. Most of the stabilisers are synthetic, although recently, a natural
hindered phenol, -tocopherol (vitamin E) was found to be effective in polyolefins [141143] and has been commercialised. For further information, the reader can consult books
explicitly dedicated to stabilisation of polymers [132, 144].
During service, most polymers experience mean temperatures in the range 20-40 C,
whereas peak temperatures may be much higher for short periods. The mechanical
properties of polymers depend upon molecular weight, and it takes relatively little
degradation to seriously impair mechanical performance. The degradation may result in
crosslinking or chain scission depending on the chemistry of the polymer and the
conditions the polymer is exposed to.
By far the most important stabilisers are the hindered phenols, which are used in a wide
range of polymers including the polyolefins, (e.g., PE and PP), polyamides, polycarbonate
and PET. These stabilisers are effective both during processing at high temperature and
for long-term use under ambient conditions. For increased effectiveness, they are usually
combined with other stabilisers to attain an optimised combination of stabilisation and
other properties such as discoloration. Often, the antioxidant is physically lost, primarily
by extraction or volatilisation, rather than by chemical consumption [145]. The trend is
therefore to use higher molecular mass antioxidants [132, 139, 146].
Fillers may affect the stability of polymers via a number of mechanisms. The two most
important ones are discussed here. Those are the catalysis of degradation by the fillers
surface and the indirect lowering of stability that occurs when the filler surface adsorbs,
and thereby deactivates, the antioxidants.
393
394
Filled Thermoplastics
antioxidant concentration in the squalane. The results showed that the Irganox 1010
was completely ineffective until enough had been added to saturate the filler surface.
The 20 weight percent dispersion of calcium carbonate (specific surface area 5 m2g-1)
395
8.7.4 Recycleability
Thermoplastics may be recycled in a variety of ways such as mechanical recycling (collection,
sorting, and reprocessing), burning to give energy, or biological recycling [150, 151]. There
is a public perception that synthetic polymers are less friendly to the environment than
natural polymers such as cellulose, poly(lactic acid) and poly(hydroxyalkanoates). That
view is not supported by the facts. Life cycle analysis reveals a very different picture,
favouring the synthetic polymers, especially polyolefins [150].
Although thermoplastics and thermoplastic composites are potentially easy and
economical to recycle, in practice there are some impediments to the implementation of
widespread recycling. The main one is that the used materials must be collected, separated
and cleaned economically. This is feasible in some instances but often it is not. In general,
polymers are immiscible with one another, and, if melt processed as a mixture, the result
is phase separation to give domains of one polymer in the other. This morphology leads
to rather poor mechanical properties. Therefore, there are efforts to find better separation
techniques in order to avoid the problem or to use compatibilisers [152] that lower the
interfacial tension, improve the adhesion of the two phases, and encourage smaller
domains of the disperse phase.
Fillers European
consumption
Filled Thermoplastics
PVC
PP
PE
Thermoset
ETP
Total
850
75
50
100
1076
10
131
15
Talc
Calcined kaolin
120
7
Mica
Wollastonite
Kaolin
Total
862
small
small
Small
4
1
199
52
111
8
6
12
1236
397
CH2
CH
Cl
and commercial polymers have molecular weights between 50,000 and 120,000. They
have approximately 5% crystallinity. All PVC polymers are unstable to heat and light
with hydrogen chloride being evolved in an unzipping mechanism. The resulting polymer
chains are highly coloured, rigid and infusible. Stabilisers must be added to the PVC for
it to be processed and used satisfactorily. These are added in a compounding operation
at which time other additives can be added with little cost penalty. Density, refractive
index, Tg, melt viscosity and other properties are dependent on the additives used.
PVC is produced as a powder containing irregular grains with diameters between 65 and
170 m (for suspension grades, other types are different). These grains are quite complex
structures with a strawberry looking surface, because they are composites with very small
domains of 10-30 nm diameter which have agglomerated to form spherical primary
particles of 0.21.5 m in diameter. The surface of the PVC grain (except for the mass
polymer) is a skin of surfactants, polymerisation aids and other additives. During processing
lubricants, processing aids and plasticisers penetrate this structure aiding melting and
homogenisation. This process is known as gelation or fusion and fillers affect it significantly.
The level of fusion determines many of the properties of the final PVC article.
As a consequence of its complex chemistry and formulations, PVC is used in a very wide
range of applications, making it the plastic with the third largest tonnage. However, the
last few years have seen a very strong movement against PVC as a material because of its
chlorine content and the possibility that, during its production, converting and disposal,
chlorinated organic compounds known as dioxins may be formed. Possible formation of
dioxins is also of concern during burning and disposal. As a consequence of this converters
of PVC have made determined efforts to replace it with non-halogenated polymers. This
has led to some changes in the uses of fillers. There are also moves occurring to replace
the most commonly used lead-based stabilisers with organic and heavy metal free
stabilisers because of concerns over its toxicity. These changes impose more stringent
requirements on the purity of the filler. One of the most obvious changes is in colour
because lead stabilisers give much greater opacity than the alternatives.
398
Filled Thermoplastics
kilo tonnes
PVC Cables
250
uPVC Extrusions
110
Ultrafine coated
80
PVC Plastisols
25
PVC Flooring
177
133
PE Compound and
Masterbatch
100
PP Compounds
70
phr
100
Di-2-ethylhexylphthalate
50
100
properties of the calcium carbonate have little effect on the mechanical and electrical
properties of a PVC compound. This is shown in Figure 8.9 for the cable-sheathing
compound given in Table 8.3, in which the calcium carbonate filler is based on chalk
whiting that has been ground to different particle size distributions, and the compounds
were extruded as a flat strip. Gloss values show a significant particle size effect increasing
markedly with finer fillers. Many high-gloss cable covers are produced using ultrafine
fillers. Particle size also effects stress whitening and scratch marking.
As a generalisation, it may be said that insulation compounds will be filled with 40-70
parts per hundred resin (phr) and sheathing with 20-100 phr; filler loading, plasticiser
level and lubricants are used to control properties of the cable covering. In some
applications, such as high temperature resistant or high voltage compounds the electrical
properties obtained using calcium carbonate as filler are not good enough. In these cases
400
Filled Thermoplastics
metakaolinite (calcined clay produced at around 700 C) is used at between 5 and 15
phr, although loadings as high as 20 phr are sometimes encountered.
8.8.1.6 Footwear
Precipitated and 1-3 m grades are used for rheological control in rotational moulded
products and as extenders in injection moulded products.
401
8.8.1.7 Plastisol/Sealants
Mostly precipitated grades are used as rheological control additives in combination
with medium (2-5 m) or fine (1 m) grades as extenders, the latter at levels of
40-200 phr.
402
Filled Thermoplastics
8.8.2.4 Film
The market for uPVC film is diminishing under environmental pressure and
consequently the use of particulate fillers is also diminishing. Most of the film is
transparent for food packaging, display, blister packs and so on, and kaolins and
other silicate minerals are used as antiblocking additives, without detriment to colour
and transparency of the film.
403
CH2
CH
CH3
with n being about 2000. It is a linear polymer, essentially a hydrocarbon with many
similarities to PE, being chemically inert, flexible, tough and having fairly low softening
and melting points. The presence of the methyl groups, however, introduces several
significant differences. Tacticity is introduced due to the various spatial arrangements of
the methyl groups that are possible. Commercial polymers are 90-95% isotactic; that is
the methyl groups occur on one side of the polymer chains. This introduces some
crystallinity (approximately 50%), and higher softening points. However, the methyl
groups also induce greater susceptibility to oxidation and chemical attack (usually at the
hydrogen atom to the methyl group). It is the lightest common plastic with a specific
gravity of about 0.9. Ethylene can be polymerised at levels of 4-15% with propylene,
either randomly or as blocks to give copolymers that are more flexible and tougher than
the homopolymer. Alternatively the polypropylene may be compounded with ethylenepropylene rubber to give copolymers as a physical mixture or rubber-modified-grades
(depending on the level of the rubber). All suffer from oxidative instability and are always
stabilised in service. Particulate fillers and coupled glass fibres are used in all these polymers
for many applications to increase rigidity and heat distortion.
404
Filled Thermoplastics
or glass fibre are preferred. Mica and wollastonite are available with high aspect ratios
but their main use is in North America where their cost-performance ratio is advantageous;
in Europe, talc is most widely used.
Original developments in filled PP were compounds with much higher stiffness than the
unfilled, especially at higher than ambient temperatures, but which would be low cost to
match the styrenics, especially ABS. Talc, being widely available, low cost and usually
having a high aspect ratio is the preferred filler type, and all polypropylene compounders
have several talc-filled grades available. Typical uses are in: automotive components
such as air-filter covers, timing chain covers, heater boxes, and battery box tops, domestic
appliances, such as washing machine soap dispensers, and in some disposable food
packaging such as skeletal fruit packages. New initiatives on recycling, particularly in
the automotive industry, are tending to limit polymer types used. Polypropylene is strongly
favoured and this is helping drive the market for filled grades.
Crudely, the talcs that are used can be divided into five types: three based on pure talc
(less than 10% impurities) with top cuts of 300 BS mesh, 20 and 10 m; and two based
on less pure minerals with top cuts of 300 BS mesh and 20 m. Particle size has no effect
per se on rigidity but, depending on the method of processing, finer types may have
higher aspect ratios and therefore will give higher rigidities. Particle size does affect
composite impact and tensile strength with smaller particle size products giving higher
strengths [157], although the results are not unambiguous because methods of producing
fine talcs also produce higher aspect ratio particles [158].
Virtually all applications for talc-filled PP are those that do not require toughness or
high strains because the rigidity imparted by talc is accompanied by brittleness. The
toughness can be improved by changing the base polymer to a copolymer with ethylene
as comonomer, by incorporating ethylene-propylene rubber, or by changing the mineral
to stearate coated calcium carbonate. All methods, however, reduce the rigidity of the
composite compared with the talc filled equivalent. As discussed in [94], particle size
and coating of the calcium carbonate affect impact strength and toughness, while other
properties are not affected greatly. Loading of the coated calcium carbonate also affects
properties. Rigidity increases, and tensile strength decreases virtually linearly with loading
but impact strength can go through a maximum at between 20 and 40 wt%.
This high level of toughness coupled with a rigidity which is higher than the unfilled,
good flow in mouldings, good light and temperature stability means that calcium carbonate
filled PP is regarded as a separate material, with major uses in injection moulded garden
furniture, automotive components, food packaging, fibres, tapes and blown oriented PP
(BOPP) packaging film. A very rapidly growing market for fine coated calcium carbonate
is in breathable films, in which micropores form around the calcium carbonate particles
during film orientation (mostly oriented PP). In fibres and tapes, the stearate-coated
405
406
Filled Thermoplastics
but these can be lowered by branching. There is much argument about the Tg with values
from 20 C to 130 C being reported. They have softening points from about 77 C to
124 C. The main applications for filled polyethylene, film and bags, blow moulding and
electrical insulation dictate the required properties and limit the potential for fillers.
407
formed during the condensation polymerisation which occurs when an organic acid is
heated with an organic amine. The numbers which always occur with the name Nylon or
408
Filled Thermoplastics
polyamide refer to the types of acid or amine used in the production. The regular spacing
of the amide groups means that the polymers crystallise with a high intermolecular
attraction leading to high-strength polymers with high melting points. Levels of
crystallinity depend on thermal history and can vary from 15% to 50%. Nylon is fairly
hygroscopic and its Tg (temperature below which the polymer become brittle) and
mechanical properties depend on the amount of absorbed water.
Filled Thermoplastics
and compounders but do not give good enough properties to allow them to be used in
any significant amounts, although products containing kaolin, calcium carbonate and
talc have been reported. These may have the filler incorporated as a diluent in colour
masterbatches used in the plastic. Some very old patents cover the incorporation of china
clays and ultrafine calcium carbonates into the rubber before compounding this into the
polystyrene but again no noticeable commercial success has been achieved. Talc is used
in expanded polystyrene as a nucleating agent.
8.8.7.5 Others
The properties of particulate fillers in a number of other thermoplastics are being investigated
by plastics producers and academic institutions but usually with a low priority rating. This
activity has been growing less and less in recent years as companies, in particular, have
been reducing the staffing levels in the research and development departments.
8.9 Conclusions
Thermoplastic composites are all around us and their use is increasing every year. The
reason for this is that thermoplastics have an excellent combination of cost and
performance. The performance can often be further enhanced by addition of fillers while
maintaining a favourable cost. The recycleability of thermoplastic composites is an
advantage compared to rubbers and thermosetting polymers because the latter two types
cannot be melted and reshaped. This favours the continued growth of the thermoplastics
and their composites at the expense of other polymeric materials.
To understand and optimise composites, one must have an overview of all the different
economic, chemical, surface and physical aspects. Furthermore, one must have a clear
goal, and be able to correctly prioritise the properties of most import for the intended
application. The best composite is the one that makes the best compromise between the
multitude of properties, at the lowest cost.
The use of fillers has been increasing incrementally for many years and that trend is
expected to continue as the use of traditional fillers is optimised and as new nano-fillers
eventually become economically attractive.
What can we expect in the future? In the near future, composites must be designed with
re-use in mind. That means proper stabilisation so that the polymer can be recycled with
sufficient retention of mechanical and aesthetic properties. There will be an increased
tendency to use fewer, standard materials to reduce cost and to reduce the need for
extensive separation of materials for recycling. It can also be anticipated that products
will be designed for easy disassembly.
It seems probable that surface treated filler will become more popular. Although the
treatment adds cost it gives many advantages and when these are summed, the overall
cost and performance of the material may be better for the surface treated type. For
example, stearic acid coated calcium carbonate in PP homopolymer gives higher extruder
throughput, better gloss, better impact strength and improved stability (because it prevents
antioxidant from adsorbing onto the filler and becoming inactive). Any one of these
412
Filled Thermoplastics
benefits may not justify the extra cost of pre-treated filler, but taken together they give a
very attractive combination of price and performance.
Another trend for the future may be the increased use of single-screw extruders to make
composites. At the moment twin-screw extruders are used almost exclusively, because
they are able to achieve better dispersion. However, recent developments have improved
mixing in single-screw extruders. Therefore, it may become common to use single-screw
extruders because they are cheaper, easier to maintain and give higher throughput. Again,
surface treatment of the filler also helps here to give good filler dispersion even for a
single-screw extruder.
Progress in polymer composites has been held back because it is expensive and timeconsuming to prepare multiple formulations and then perform thorough mechanical testing.
It is possible to save time and money by screening new fillers, antioxidants, dispersants
and coupling agents in a model liquid instead of the polymer. The screening can then be
followed up by full testing, using the polymeric matrix. Hopefully, this method will be
used to help develop new filler grades and surface treatments, more quickly and cheaply.
Acknowledgements
We would like to thank several people for their assistance in writing this chapter. Firstly,
the editor Professor Rothon who has been a great help in making suggestions, proofreading and for general discussions. Professor John Berg (who deserves a special thanks
for being such a help with the section on adhesion), Professor Ulf Gedde, Professor
Aubrey Jenkins, Kevin Breese, Massimo Sanit, Carlo Tomaselli, Roy Goodman, Chris
Paynter, Richard Day, Anna Kron and Werner Posch are all warmly thanked for making
significant contributions by reading draft versions and for making valuable comments
that improved the quality of the chapter.
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