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2

Particulate Fillers and Fibre Reinforcements

C. Vasile, A. Grigoriu and V. Blascu

2.1 Introduction

Important changes in the properties of plastics resulting from the incorporation of special
additives permit their use in applications where the polymer alone would have had small
chance to meet certain performance specifications. Fillers and reinforcements are solid
additives that differ from the plastic matrices with respect to their composition and structure.

The basic role of a filler is to fill, i.e., increase the bulk at low cost, thereby improving
economics while, by definition, the main function of a reinforcing filler is to improve the
physical and mechanical properties of the basic polymer. Out of these properties, stiffness
and strength are the most important among short-term properties in engineering
applications. Resistance to creep and fatigue failure are principal long-term properties.
The effect of heat on both these groups of properties is shown by the heat deflection
temperature (HDT) and dimensional stability. All these properties can be upgraded by
reinforcing fillers. Non-mechanical properties of the basic polymer, e.g., electrical
properties, abrasion resistance, flammability, may also be strongly modified by the presence
of reinforcing fillers. With fibrous fillers, the influence of the fibre aspect ratio and the
anisotropic effect of fibre orientation can further magnify the improvements. That is
why, the most effective reinforcing fillers are fibres of high modulus and strength.

Modern fillers can take on many of the functions of reinforcements. Usually, fibres and
lamina structure are counted as reinforcements, while the ball type additives are counted
as fillers. Inert fillers or extender fillers increase the bulk, solve some processing problems,
and lower the price; no improvement is seen in the mechanical or physical properties
compared with the unfilled polymer, although by a higher thermal conductivity, they
improve the production rates.

Active fillers, enhancers, and reinforcements produce specific improvements of certain


mechanical or physical properties, including modulus, tensile and impact strength,
dimensional stability, heat resistance, and electrical properties. Most particulate fillers
have a higher specific gravity than polymers, but some, such as hollow ceramic or glass
spheres, expandable beads, have been developed to reduce the weight of the compound.
Liquid extenders are used in elastomers. Particulate mineral additives are classified as
two- or three-dimensional. The two-dimensional silicates in layers (such as talc and mica)

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Handbook of Polymer Blends and Composites

essentially induce rigidity and thermal stability, but do not attain the stiffening effect of
fibre-type reinforcements. Average particle diameter, specific surface and surface energy
are decisive in the reinforcing effect of fillers in elastomers.

Enhancers and reinforcing fillers induce the following improvements in thermoplastics [1]:

increase in tensile strength and tensile stress at break, and in compressive and shear
strength,

increase of the modulus of elasticity, stiffness and hardness of the composite material,

increase of HDT and decrease of the temperature dependence on the mechanical


values,

improving creep behaviour and bend-creep modulus, as well as partial impact strength,

reducing the viscoelastic yield under load and lower shrinkage, giving good
dimensional stability.

The action of active fillers can be attributed to three causes [2-5], namely: (1) chemical
bond formation between filler and the material to be reinforced; (2) immobilisation of
polymer segments attached to the filler surface by secondary or primary valence bonds,
an interfacial layer with characteristic properties thus appearing; (3) when the polymer
molecules are subjected to stress with energy absorption, they can slide off the filler
surface; the impact energy is thus uniformly distributed and the impact strength increases.
Detailed theories on these aspects are presented in many reviews [5-13].

For their use in plastics the most important characteristics of fillers are: chemical
composition, particle shape, average diameter, grain distribution, specific surface and
value of surface energy, thermo-oxidative and UV-stability for outdoor applications and
moisture and water-soluble compounds content.

2.2 Fillers and Reinforcements and Their Requirements

Fillers and reinforcements can be differentiated by the aspect ratio (AR) which is the
ratio between length (or length and width) to thickness (L:T) - as follows [14]:

(a) Fillers as irregularly shaped granules having L:T > 1.

(b) Enhancers such as short fibres, e.g., wood flour, milled or chopped glass fibres,
wollastonite, whiskers (a mineral fibre as a single crystal fibre), talc, etc., with an L:T
varying from 10 to >> 100.

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Particulate Fillers and Fibre Reinforcements

(c) Reinforcements such as filaments, non-woven or woven textile products, L:T being
very large.

(d) Special active reinforcements used principally in elastomers, such as carbon black,
pyrogenic highly dispersed silica or precipitated ultrafine, carboxylated rubber coated
calcium carbonate.

For a controlled modification of the various properties of the composite materials, certain
characteristics of the filler/reinforcement are necessary.

The main requirements for the properties of fillers and reinforcements necessary to obtain
of composite materials that can be further used in specific applications are [1]:

The chemical purity of fillers is very important.

Low moisture absorption and high bulk density; they should preserve their properties
during storage prior to compounding.

Optimum compounding is achieved with fillers and reinforcements of a certain particle


size, intimate wettability through the polymer matrix, which does not present static
charge, no shortening of the reinforcing fibres taking place, which means a good
dispersion behaviour.

Filler particles should be as round as possible with a small specific surface, low surface
energy, and absorptivity, thus assuring a low viscosity during compounding.

A high compounding rate is obtained with fillers having low specific heat and high thermal
conductivity.

A composite with high tensile strength and high elongation is obtained when using a
filler/reinforcement having high strength in comparison with the matrix, high length/
diameter ratio, and good fibre/matrix adhesion, as well as a good distribution in the
matrix while, for high flexural strength, it is very important to obtain, additionally a
smooth surface in the finished article.

Fillers with low compressibility and small round particles are suitable for obtaining
composites with high compressive strength from crystalline polymers.

Fibrous or lamellar reinforcements with a high length/diameter ratio, high modulus of


elasticity in comparison with the matrix, high orientation in the direction of the force
profile and good adhesion are used for composites requiring high stiffness and high
modulus of elasticity.

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Handbook of Polymer Blends and Composites

There are high strand integrity products with good fibre feed and handling characteristics
in 3.17 and 4.76 mm chopped lengths. The high performance carbon/
polyetheretherketone (PEEK) types are pre-pregs in which continuous filament and
matrix have been combined by a form of pultrusion process. They require only placing
in position and heating to fuse the thermoplastic polypropylene (PP) matrix. The
interfacial bonding is improved. PP sheet moulding compounds and bulk moulding
compounds known as glass mat thermoplastics (GMT) are compounded in granules
for injection moulding and extrusion.

Good long-term behaviour and fatigue and weathering resistance of the composite
materials are achieved with filler/reinforcement with permanent polymer/matrix bonds,
good resistance to heat, light, water, chemicals, etc.

Also, a low cost results when low cost filler is used with low processing cost and
maximum possible degree of filling; the other requirements regarding the properties
being, of course, fulfilled.

It is well known that mineral fillers have a catalytic effect on resin cure and that the
effect is specific to each resin and each curing system. Thus, polyester resins cured with
a benzoyl peroxide initiator are less sensitive to the mineral surface than the same resin
cured with a cobalt-promoted ketone peroxide initiator. Glass fibres treated with a
chrome finish, retarded gelation of a polyester more than those treated with a silane
finish. Barium sulphate, calcium carbonate and zircon promoted a much faster cure
than an unfilled resin. With some materials such as clay, silica and talc, the inhibition
of cure is severe enough to limit their usefulness in highly filled systems. Most polymers
undergo shrinkage during cure. Therefore, many composites are translucent when
removed hot from the press, but they become opaque due to crazing as the composite
cools. Mixing finely divided particulate fillers with resin produces total expansion, yet
merely transfers interfacial stresses from a macro to a microscale. The result is that
particulate filled plastics generally have lower mechanical properties than the milled
filled plastics.

The value of filler depends on the difference between the coefficients of thermal
expansion that must have minimum values. Some thermal expansion coefficients of
the materials used in composites are given in Table 2.1.

The value of asbestos in high-temperature composites depends more on its close match
with the resins coefficient of thermal expansion than on fibres heat stability.

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Particulate Fillers and Fibre Reinforcements

Table 2.1 Linear thermal expansion coefficients of common


minerals and plastics
Material Coefficient of thermal expansion
x 10-6/C
Silica glass 0.6
E-glass 4.8
Boron 5.1
Graphite 7.8
Alumina (alundum) 8.7
Steel 10-14
Aluminium 23
Asbestos (chrysolite) 50
Wollastonite 65
Polyimide 38-54
Epoxy resin 45-65
Polyester 55-100
Phenolic 60-80
Polystyrene 60-80
PP 100-200
Silicone resin 160-1800

2.3 Particulate Fillers

2.3.1 General Description


Relatively large volumes of particulate fillers are used in many composites. When these
largely non-reinforcing fillers are added to the matrix resin, the net result is generally
lowering of the physical properties (loss of mechanical strength and dielectric properties of
the system) and, in many cases, increase in water absorption. While it is commonly accepted
that the obvious goal here is to lower compound cost by adding the maximum amount of
low-cost filler, it is increasingly recognised that, with many fillers some attraction does
exist between the filler and the polymer, particularly in polymers containing functional
groups. The overall net effects of this interaction are shown in the changes observed in
glass transition temperature and modulus of elasticity and in composites hardness.

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Handbook of Polymer Blends and Composites

The particulate fillers, which produce true reinforcing effects, are the fillers whose particles
have low aspect ratios (if needle- or rod-shaped) and which may be roughly spherical
(with various degrees of irregularity) or plate-like. The properties mainly improved by
particulate reinforcing fillers are stiffness, hardness and heat deflection temperature.
They also change the colour and the cost. Considerable research effort has been directed
to the use of silane coupling agents in composites [15].

The most common particulate fillers, which are used in one form or another in plastic
composites are listed in the next sections [1, 15-27]. With a few exceptions, these fillers have
been subjected to treatments with a silane coupling agent, in a variety of composites [5].

2.3.1.1 Silica

Mineral fillers are fillers/extenders/reinforcements. They are used as thickening liquid


systems, which make liquids more thixotropic; for aiding plate-out in PVC; and as
flatting agents. Examples are sand, quartz ( = 2.65 g/cm3, Mohs hardness of 7, high
abrasion rate), quartzite, perlite, tripoli, diatomaceous earth and novaculite.

Synthetic fillers are wet process silica, fumed colloidal silica and silica aerogel. Their
specific surface may be very large from 50 800 m2/g.

2.3.1.2 Silicate

Mineral fillers which can be cuboid with an AR of 1.4 4 are:

Kaolin is also known as porcelain earth and china clay, is lamina with an AR of 5 100,
s=500-600mJ/m2; c=0.91 W/m.K, cp= 0.92 J/kg K. It is used as an extender/pigment in
wire and cable, sheet moulding compound (SMC), bulk moulding compound (BMC)
and polyvinyl chloride (PVC) flooring, etc.

Mica Lamina has an AR of 5 - 100, = 2.8 g/cm3 , s=2400-5400mJ/m2 , c=2.5 W/m.K,


cp= 0.86 J/kg K. The flake form is used for reinforcement and improves dielectric, thermal
or mechanical properties and is low in cost.

Talc Lamina has an AR of 5 - 100, s=60-70mJ/m2, c=2.1 W/m.K, cp= 0.86 J/kg K. It
can be used as a filler extender/reinforcement and improves stiffness, tensile strength and
resistance to creep.

Wollastonite improves strength, reduces moisture absorption, induces higher heat/


dimensional stability, improves electrical properties.

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Particulate Fillers and Fibre Reinforcements

Asbestos Fibre has an AR >100.

Feldspar, nepheline, syenite are cuboid with an AR of 1. They are abrasive; speciality
fillers, easily wetted and dispersed, permitting transparency/translucency, are resistant
to chemicals and weathering.

Glass flakes/microspheres/hollow solid cloth fibres. Their properties depend on their


form: flakes s=1200 mJ/m2, hollow balls, 2-24 m, with an AR of 1, =2.45-2.55g/cm3.
They have reduced weight, improve stiffness and impact resistance, improve flow
properties and stress distribution.

Fibre has an AR of > 10, high strength, dimensional stability, heat resistance and chemical
resistance.

Synthetic fillers are calcium silicate and aluminium silicate.

2.3.1.3 Calcium Carbonate

Is naturally occurring as:

Chalk cube with an AR of 1; 10-45 m; s=65-70 mJ/m2; c:=2.4-3.0 W/m.K;


cp= 0.86 J/kg K

Limestone

Marble

Dolomite

Synthetic or precipitated calcium carbonate.

2.3.1.4 Metallic Oxides

Zinc oxide, iron oxide

Alumina

Hydrated alumina, alpha alumina mono- and tri-hydrate lamina with an AR of


5 100. They are used as extenders, flame retardants and smoke suppressants.

Magnesium

Titanium, s=650 mJ/m2.

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Handbook of Polymer Blends and Composites

2.3.1.5 Metals, Fillers and Filaments

These have good electrical and/or thermal conductivity or magnetic properties, they reduce
friction, and they are expensive.

Aluminium, needles or powder


Bronze
Fe powder
Zircon, milled.

2.3.1.6 Salts

Calcium phosphate
Calcium sulphate is an extender, which, increases impact, tensile and compressive
strength
Barium sulphate heavy spar is cuboid with an AR of 1.4-4. It is used as a filler and
a white pigment. It increases specific gravity, chemical resistance and frictional
resistance.
Potassium titanate (Fybex).

2.3.1.7 Other Fillers

Silicon carbide
Carbon black and graphite are lamina with an AR of 5 100. They are used as
fillers, pigments and antistatic agents. They are electrically conductive.
Carbon fibres
Ceramic microspheres
Organic fillers are wood flour, nut shells, corncobs, rice, and peanut hulls. They are
used as extenders/fillers.
Polymeric fillers s=15-60 mJ/m2. These are used as reinforcements and are lightweight.
Cellulose fibres have an AR of > 10
Whiskers have an AR of > 10.

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Particulate Fillers and Fibre Reinforcements

Calcium carbonates mainly occur naturally in the form of chalk, limestone, marble, etc.,
from which the filler is obtained by fine milling or synthesised by precipitation. Due to
its low price and to its improvement of polymer properties and ageing resistance, natural
calcium carbonate is the most important filler used in plastics. Natural and synthetic
calcium carbonate generally have a calcite structure, and may contain some aragonite of
metastable phase. Grinding of the calcite crystal is known to result in a aragonite structure.
Small amounts of finely dispersed calcium carbonate, silica, or various silicates reduce
sticking and improve the paper-like feel of polyethylene (PE) films.

The synthetic precipitated calcium carbonate fillers [28], are more expensive than ground
chalk. Due to their larger surface area, the shearing forces during processing are
appreciably higher, thus high filler addition is not possible. Ground calcium carbonate
takes the shape of sponge-like aggregates. Precipitated calcium carbonate having calcite
structure forms cube, spindle or rod shapes, while the aragonite structure exhibits a rod-
like shape. It has a higher absorptive effect on plasticisers, stabilisers, lubricants, etc.
The adhesion of the calcium carbonate-polymer matrix can be improved by a surface
treatment, commonly using stearates.

Ultrafine particles of 5-20 nm or 15-70 nm average diameter have been prepared by the
recarbonation process. The product has an aragonite structure and a good dispersability
in polymer matrix.

High quality carbonate fillers should have the following properties: high chemical purity,
low plasticiser absorption, high degree of whiteness being possible by partially substituting
the expensive white pigments, coloration in pastel shades, non-abrasive, non-toxic,
odourless, reduce shrinkage, increase stiffness and modulus of elasticity, improve the
surface quality of finished parts, improve stability and ageing resistance, reduce plate-
out effect, etc. The synthetic calcium carbonate has higher absorptive effects on plasticisers,
stabilisers and lubricants.

Dolomite is much more abrasive than calcium carbonate, it has a good wettability and
dispersability, but because of water solubility, weathering resistance is inferior to that of
calcium carbonate.

Calcium sulphate (gypsum) is mainly used in three different forms: dihydrate, a filler
which is used in foamed polymers, hemihydrate available in fibre form and anhydrite.
After treatment, the latter does not absorb moisture. Calcium sulphate offers a very
white acid resistant filler with low surface energy and low abrasiveness.

Barium sulphate has high density (4.3-4.6 g/cm3), Mohs hardness (2.5-3.5), and high
reflectivity. It is primarily used in foams, floor covering, and gives protection against
high energy radiation and sound deadening.

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Handbook of Polymer Blends and Composites

Talc is a natural hydratated magnesium silicate with the formula 3MgO.4SiO2.H2O.


Depending on the source, talc occurs in four particle shapes, fibrous, lamellar, acicular
(needle-shaped), and granular. It is water repellent and very soft. Particle size may vary
between 1 and 50 m. It resists temperatures up to 900 C and is unaffected by chemicals
and is not harmful for living organisms. Depending on its geological source it can be
found in various forms and colours, such as small closely compacted crystals or large
crystals, pink, green, grey-black or white in colour. It is used in commercial applications,
which determine its good slipping properties. In PP, talc gives a good balance of rigidity
and impact strength and has less adverse effect on the thermal stability of PP than asbestos.
It is a smooth, non-abrasive filler. It has high purity and gives very good long-term thermal
stability, making compounds ideal for use in packaging, including odour sensitive food
contact applications. Fine particle talc types show pronounced nucleating effects in
partially crystalline polymers.

Mica. Lamellar reinforcement mica is obtained from muscovite or phlogopite minerals


[1, 12]. The decisive factor, as the reinforcing action is the ratio of the diameter to the
thickness of the lamellae. Density is 2.8g/cm3, Mohs hardness 2.5 - 4, oil absorption 48-
500 g/100 g powder. It imparts high stiffness, high dimensional stability, and good dielectric
properties.

Silanisation of the filler surface facilitates the incorporation of mica in polyolefins (PO),
aminosilanes being used. A metallised form is also found.

Feldspar and nepheline syenite are characterised by: density 2.6 g/cm3, Mohs hardness
6.0 - 6.5, refractive index of 1.53, pH 8 9, oil absorption 13 - 14 g/100 g powder. Due
to the low oil absorption, they are used in thermosetting and PVC.

Silica and silicates are both natural and synthetic. The natural ones (diatomaceous earth,
novawite, perlite, quartz, quartzite, sand and tripoli) differ in their particle size, degree
of crystallinity, and hardness. -Quartz is, however, the hardest of the common minerals.
Quartz has a density of 2.65 g.cm-3 and a Mohs hardness of 7.

Synthetic silicates are obtained by relatively complicated procedures because of the fine
spherical primary particles, which can form agglomerates and aggregates. Depending on
the manufacturing process, the surface may be very large, attaining values of 50 to 800
m2g-1. Apart from the chemical composition, not all-synthetic silicas are crystalline. All
silicas and silicates are supplied with various silane coatings. They have the following
functions: shrinkage reduction, reinforcement, improvement of dimensional stability,
electrical properties, increase hardness, thickening, rheological and thixotropic effects.

Metals and metallic powders. Metallic powders consisting of aluminium, bronze, copper,
and nickel are always used in thermoplastics, if products with very high thermal or

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Particulate Fillers and Fibre Reinforcements

electrical conductivity are required. Additionally, heavy metal powders increase the
resistance to neutron and gamma rays [20].

Metals in fibre form and metallic oxides are also supplied as fillers and reinforcements
for selective changes such as aluminium oxide for improved electrical values, zinc oxide
for weathering stability, beryllium oxide to improve thermal conductivity, iron oxides
for magnetic effects, lead oxides for high density and magnesium oxide to increase stiffness
and thickening of unsaturated polyester resins, etc.

Kaolins, also known as porcelain earth and china clay, are hydrated aluminium silicates
possessing a clearly determinable crystal lattice with a plate-like, hexagonal structure.
Kaolin consists of primary and secondary kaolinites with the molecular formula, Al2O3
SiO2 2H2O containing Al2O3 (38.8%), SiO2 (45.4%) MgO (0.2%), K2O (0.97%) Na2O
(0.07%), FeO (variable). In their plate-like hexagonal lamellar structure, primary kaolin
has a length to thickness ratio of 10:1. Kaolins generally possesses a high degree of
whiteness and are electrically non-conductors; they are highly resistant to chemicals,
even to strong acids.

Kaolins used in polyolefin (PO) composites should have fine particles of 0.6 to 6 m,
Mohs hardness of 2.5, and a pH of 5.0 - 5.6.

The calcinated kaolin form is appreciably harder than natural kaolin; it considerably
improves the electrical properties of a polymer and reduces the water absorption (cable
insulation materials based PVC or ethylene-propylene-diene terpolymer; EPDM). Kaolin
is obtainable with various silane coatings that facilitate dispersion of the filler in the
plastics. Kaolin is the most important filler in rubber industry, after carbon black. The
rubber chemist distinguishes between hard (<2 m) and soft (coarse) kaolin, depending
on whether the finished product has a high or low modulus.

Carbon black is a special form of carbon obtained through partial combustion of liquid
or gaseous hydrocarbons. It can be used as a black pigment (particle dimensions of 15 to
20 m), as an improver of electric conductibility (particle dimensions of 17, 24, and 90
m), and as a filler/reinforcement material (particle dimensions of 23 to 28 m) [1, 12,
16]. Hollow carbon black spheres are used in foams.

Graphite powder imparts self-lubricating properties to plastics.

Aluminium trihydrate is a non-flammable white powder insoluble in water. It is generally


used as a flame retardant but it also acts as filler, increasing material stiffness and improving
flow and the electrical properties. It is a non-abrasive filler with a low density (2.4 g.cm-3)
and Mohs hardness ranging between 2.5 and 3.5. The polyester composites containing silane
treated-trihydrate show a 10-20% improvement of wet flexural strength compared to control.

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Handbook of Polymer Blends and Composites

Wollastonite is a naturally occurring calcium metasilicate available in surface coated


forms of various types. Purity after processing is about 97%. The particles are needle-
shaped, microfibrous, of about 50 m in size. New grades under development indicate
its strong growth and its potential for replacement of calcinated clay and other minerals
used in thermoplastics. Aspect ratio 15:1 or > 100, density 2.9 g/cm3, Mohs hardness
4.5-5, pH of 9 - 10, melting point 1540 C. In thermoplastics it competes with talc and
mica. The needle-shaped structure results in high stiffness, combined with good impact
strength, good electrical and thermal properties. It is used for its thixotropic effect in
surface coatings and thermosetting polymer composites.

Wood flour is obtained by fine milling of soft or hardwood wastes, leading to many sorts
with the following characteristics, such as: particle size 60 to 80 m, bulk density 182 to
285 kg/m3, specific volume 3.5 to 5.49 m3/kg. It improves the surface gloss.

Glass spheres or glass beads. Both solid (ballotini) and hollow glass spheres (glass
microballons) are obtained from sodium borosilicates or silica. As fillers, and also as
flame-retardants, solid glass spheres with diameters ranging from 4 to 5000 m are used.
For plastics, the size typically used is 30 m in diameter and densities of 2.5 g.cm-3.
Plastichem Ltd offers six standard size ranges, all with the same spherical shape,
transparent and compression-resistant; they have controlled granulometry and high
thermal stability. The shear forces between polymer and filler are low. Moulded parts
filled with glass spheres exhibit isotropic behaviour, shrinkage in the reinforced material
being the same in all directions, so that sometimes the properties can be predicted
beforehand. Solid glass microspheres (< 50 m) improve modulus, compressive strength,
hardness, and surface smoothness. Favourable flow properties permit high filler content.
The action of glass spheres is decisively influenced by their wettability, silanes are therefore
often used as coupling agents.

Density of the hollow glass spheres ranges from 0.3 to 0.6 g cm-3, their diameter is
usually between 10 and 250 m (sometimes even 850 m).

The size distribution of solid glass spheres determines the glass spheres type. For example,
A-glass (soda lime) spheres have a mean size from 11-22 m, while the dimensions of E-
glass (borosilicate) spheres range between 11-36 m.

They decrease density, usually impair the mechanical properties and are mainly used in
foams. Hollow microspheres are not reinforcing fillers in the true sense. They displace
the same volume of resin as solid spheres, but are lighter (weight reduction can reach 20
- 25% compared with mineral filled polymers). They are colourless but in bulk they
appear as a buff-coloured, free flowing sand-like powder. They are available in two
densities and wall thickness ranges. Their main uses are in syntactic foams based on
thermosetting resins, and as fillers to reduce simultaneously the density and the dielectric
constant of epoxy resins used as encapsulants in electrical applications.

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Particulate Fillers and Fibre Reinforcements

Moulding compounds containing glass spheres can be extruded or injection moulded.


Dimensional stability, lower viscosity and improved flow represent the main advantages.
The typical density is 1.1 g/cm3. They have low ionic leach and conductivity. In the
resins matrices they give opacity and whitening, allowing some replacement of titanium
oxide. Tensile, flexural and impact properties of compounds filled with hollow glass
spheres are similar to those of solid spheres. A small load increases the Izod impact
value, compared with the unloaded resin but, as sphere loading increases, the Izod value
tends to decrease. Organosilane coupling agents may prevent this decrease.

Expandable microspheres can also be used. They are thermoplastic microspheres


encapsulating a gas (a mixture of nitrogen and carbon dioxide as in Armoform spheres)
available both in non-expandable and pre-expandable form. Non-expandable spheres
have a density of 1.2 g/cm3 and mean particle diameter of 10 - 17 m. By heating (T
~100 C), the thermoplastic shell softens and the vapour pressure increases expanding
the sphere 34-50 times, creating ultra-light microspheres. They are used for foamed items
and for weight reduction. The pre-expanded form can be used with open or closed mould
applications. Recent developments in microspheres include for highly filled PP Ecosphere
hallow glass microballons from Emerson & Cuming.

Glass spheres are used as fillers in both thermoplastics and thermosetting compounds.

Table 2.2 lists some characteristics of glass spheres.

The viscosity of the melt is increased to a much lesser extent by glass spheres than it is by
irregular particles, e.g. clay, powdered quartz, or glass fibres. This makes the production
of complex or thin-walled mouldings easier with spheres-filled than with glass-fibre-
filled thermoplastics. In comparison with the basic polymer the principal effects on
properties include reduction of shrinkage, improvements in abrasion resistance (up to
750% in acrylonitrile-butadiene-styrene (ABS) cups), compressive strength, hardness,
tensile strength, modulus and creep. A cost saving of ~ 13 - 16% could be attained [7].

Conductive glass microspheres coated with silver are also manufactured. The silver coating
lowers the volume resistivity of the moulding materials to 0.03 cm. They are used for
manufacturing of electrically conductive moulding compounds, which are inexpensive.

Hollow lightweight ceramic microspheres (cemospheres), are used to complement or as


an alternative to hollow glass microspheres. They are made of a thoroughly inert ceramic
and have a specific gravity between 0.55 - 0.75 g/cm3, being significantly lighter than
conventional fillers and polymer matrices. The particle size is up to 500 m, in low
quality grades, and to 85 m in high quality grades. Loading level is ~ 40% by volume
even for a readily mouldable material. They reduce weight while improving rigidity,
stability and thermal insulation.

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Table 2.2 Properties of glass spheres


Property Value
Physical and general properties
Specific gravity (g/cm3) 2.46 - 2.49
Refractive index 1.51 - 1.53
Young's modulus (GPa) 68.95
Rigidity modulus (GPa) 29.65
Poisson's ratio 0.21
Coefficient of friction (glass on glass) 0.18 - 0.24
Hardness 515 - 540
Thermal properties
Strain point (C) 505
Annealing point (C) 548
Softening point (C) 730
Expansion coefficient (0 - 300C) 85 x 10-7
Mean specific heat (cal/g/C) 0.18 at 20 C
0.28 at 1000 C
True specific heat (cal/g/C) 0.18 at 20 C
0.32 at 1000 C
Thermal conductivity (cal/s.cm. C) 0.002 at 0 C
0.036 at 500 C
Thermal diffusivity at room temperature (cm2/s) 0.005
Electrical properties
Dielectric constant (1 MHz at 20 C) 7.0 - 7.6
Power factor (1 MHz at 20 C) 0.004 - 0.011
Volume resistivity at 250 C () 106.5 - 107
Dielectric strength (kV/cm) 4500
Chemical resistance
in water 4 h at 90 C 0.05% Na2O extracted
in 0.02 N H2SO4, 4 h at 90 C 0.05% Na2O extracted

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Particulate Fillers and Fibre Reinforcements

Expanded perlite particles are friable and vulnerable in plastics processing.

Other mineral fillers are: carbides, silicon carbide being used to increase the abrasive
action of polymers, molybdenum sulphide reduces the friction, ZnS is used for white
coloration, barium titanate for electrical applications, and barium ferrite to produce
magnetisation of polymers (magnetic seals).

2.3.2 Testing Methods

Testing of filled/reinforced materials is made primarily for determining the changes of


the properties noticed in the polymeric materials. Thus, mechanical (Youngs modulus,
tensile strength, etc.), thermal and burning properties, electrical properties, are taken
into consideration [25].

In the analysis and specification of fillers, several properties are of particular importance:

ASTM designation referring to particle size as D1366-86 [29]; C92-95 [30].

ASTM designation referring to surface area, D1510-99 [31].

ASTM designation referring to specific gravity, D153-84 [32]. ASTM designation referring
to bulk density, D1513-99ae1 [33]; to pH-value, D1512-95 [34], or oil absorption, D281-
95 [35], D1483-95 [36].

Other tests include the determination of purity, freedom from coarse particles, etc., and
other properties, extensively treated in several books [1, 5, 10, 21, 24 - 26].

2.3.3 Uses and Problems and Examples of the Applications [6-28, 37-43]

Typically, the presence of fillers causes a decrease of stabilisation performance due to


physical or chemical phenomena. The physical aspects of decrease are due to the
absorption of antioxidants onto the surface of the inert filler (observed especially for
calcium carbonate, carbon black and silicates). If the antioxidant is immobilised, it is
unable to protect the polymer. Usually, a modest increase in the amount of stabiliser is
sufficient to overcome this negative influence. Metallic (iron based) impurities in the talc
play a major role in the lack of stability in the final formulation because they catalyse
hydroperoxide decomposition. Manufacturers supply several grades of talc having various
effects on stability, or it is coated with epoxy resins. Other solutions to prevent the effect
on stability are the use of a formulation containing a metal deactivator. Calcium carbonate,
used in many articles from PO, improves processability, hardness, stiffness, environmental

53
Handbook of Polymer Blends and Composites

stress crack resistance and printability. The melt flow index, shrinkage, elongation, water
vapour and oxygen permeability decrease. Surface coating calcium carbonate use gives
high impact strength. The effects are much stronger in high density polyethylene (HDPE)
than in low density polyethylene (LDPE).

Molecular water diffuses readily even through the most water-resistant polymers. The
mechanical properties of mineral-filled polymers are most seriously affected when clusters
occur at the mineral-polymer interface.

2.3.3.1 Thermoplastics

Fillers and reinforcements suitable for polyolefins are [6-28, 37-40] mineral fillers such
as: natural and precipitated calcium carbonates, talc, mica, silica and silicates, metal
powders [37-39], kaolin, carbon black, aluminium trihydrate, wollastonite, wood flour,
asbestos, glass spheres, glass fibres and reinforcing fibres. Carbon fibres (graphite),
whiskers, etc., are also used.

Many non-black fillers such as talc, clay, silicates and carbonates continue to be used in
thermoplastics. Silanes, improve the dispersion of most mineral-filled thermoplastics and
provide protection under water immersion conditions. In many thermoplastics systems,
a relatively high load of low-cost filler can be tolerated with the addition of incremental
amounts of silane, coupling agents being used to restore the physical properties of the
composites to acceptable performance levels. A number of different fillers are used in PO
either as extenders or as physical properties modifiers. Clays are most used: in HDPE to
improve rigidity and tensile strength for automotive and pipe applications, while in
crosslinked PE to improve the dielectric constant. For very high voltage cables, surface
modified-clays are added.

Direct incorporation of fillers bypassing the preceding compounding stage is one of the
areas under investigation. Research activities are focused on the development of
inexpensive technological solutions, by combining cheap, spherical materials with more
expensive lamellar or fibrous reinforcements, and by minimising the interfacial tension
between fillers or reinforcements and the polymer matrix.

2.3.3.2 Vinyls

Fillers (extenders) are generally used in vinyls to lower the cost. The asbestos is used in
floor tile, to give dimensional stability, and processed clays are used especially to improve
the electrical properties in wire compounds. Silane-treated clays provide faster extrusion,

54
Particulate Fillers and Fibre Reinforcements

shorter Banbury mixing times and improve die wear and cables applications. For ethylene-
vinyl acetate copolymer (EVA) technical applications, the following fillers are used: calcium
carbonate for toys, heavy spar (barium sulphate) to increase resistance to X-rays and for
sound deadening, carbon black for electrically conductive articles, barium ferrite (even
up to 90 wt%) for magnetisable sealing strips, aluminium hydroxide as a flame retardant
and talc for stiffening.

The properties of PVC can be varied within large limits by additive use. Natural calcium
carbonates are by far the most important fillers for both plasticised and rigid PVC. In the
latter, only fillers with very small particles size that have been surface treated are used.
The quantity of incorporated filler can be increased in the presence of an impact modifier.
The results are: increased stiffness, lower shrinkage and reduced plate-out, notched impact
strength, enhanced ageing resistance and deflection temperature. Precipitated calcium
carbonate improves surface, shade, degree of whiteness, surface gloss and plate out.
Other fillers used in PVC articles are: talc, wood flour, silicates.

The high inherent stiffness of polyoxymethylene (POM) can be further increased by the
use of fillers. POM can be filled up to 80 wt% of glass spheres without any change in
processing conditions.

The glass spheres incorporated in polystyrene (PS) and styrene copolymers impart higher
stiffness, in particular at elevated temperature, along with higher compressive strength,
improved dimensional stability, higher HDT, but reduce impact strength. Other particulate
fillers used in PS are: calcium carbonate as extender, or nucleating agent, and fine, surface-
coated grades which serve as partial substitute of TiO2, while aluminium hydroxide
increases flame retardance. Up to 30 wt%, calcium carbonate is used in the production
of components for robots to improve mechanical properties of ABS, without appreciable
loss of impact strength.

In polyamides up to 50%, glass spheres may be incorporated. They improve tensile and
flexural strength, elongation at break, impact strength and HDT. Glass spheres permit
uniform shrinkage, close tolerance, good abrasion resistance and smooth surface of the
finished part. A notched impact strength enhancement can be obtained by the use of
surface coated glass spheres combined with glass fibres. Other improvements in
polyamides properties by using particulate fillers are: tensile strength, extrudability and
surface smoothing with silicon dioxide, stiffness, mechanical strength, hardness, thermal
and dimensional stability, surface quality with silicates (up to 40%); calcium carbonate
is a true reinforcement for polyamide (PA), increasing, besides mechanical properties,
the resistance to solvents; the amount of bronze can be up to 90 wt%, improving electrical
conductivity as aluminium, copper, lead, nickel and zinc also did. PA filled with up to
80% barium ferrite is used for small magnets while MoS2 improves slip properties.

55
Handbook of Polymer Blends and Composites

Reinforced polycarbonate (PC) is suitable for parts subjected to high static load and
which have to meet high requirements relative to dimensional accuracy, dimensional
stability and HDT.

The dispersability of TiO2 has improved by silane treatment both in PS and polymethyl
methacrylate (PMMA) as are metallic fibres in polytetrafluoroethylene (PTFE).

In polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), 20 wt% glass


spheres reduce the distortion tendency, impart high surface hardness, isotropic shrinkage,
good surface and lower machine wear compared with other type of fillers, especially the
fibrous ones. Calcium carbonate has a favourable effect on PBT properties, affecting
friction of PET magnetic tape. Wollastonite increases mechanical strength, but reduces
melt flow rate. In polyester thermosetting systems, solid glass beads can be used, as
follows: a) in hand lay-up (up to 60%) reduces warpage, water absorption, easier wetting-
out, better mould flow; b) in gelcoats (up to 20%) improve resistance to abrasion (loading
>20%), reduce staining, water absorption and cost; c) in casting (up to 100%) uniform
reduction in shrinkage, lower distortion, improved gel and cure time, while filled resin
viscosity is lower than with other fillers, water absorption is reduced and resistance to
abrasion considerably increased.

For most uses, epoxy resins are filled with particulate inorganic fillers. In addition to
decreasing cost, these fillers serve to increase hardness, act as heat sink for the exothermic
curing reaction, decrease shrinkage during curing add opacity and colour, and improve
other general processing and performance parameters. Silane (epoxysilane) treated fillers
(quartz, silicate, wollastonite) provide improvements in flexural strength and complete
retention of electrical properties after extensive water immersion.

The physical properties improvements result from the use of epoxy functional and
aminofunctional treated metals (aluminium needles and powder, iron powder), while
wollastonite in epoxy composites improves flexural strength with complete retention
after boiling test. Hydrated alumina is commonly added to cycloaliphatic epoxy resins
used for outdoor, high voltage insulation, largely as replacement for porcelain.

Phenolic and other condensation resins are typically used filled with alumina (abrasive
grit for grinding wheels), foundry sand (for shell moulding), glass spheres, silicon carbide
granules or treated with very low amounts of silane.

Thermoset composites such as diallyl phthalic moulding compounds commonly contain


silane treated chopped glass and high loads of silica or silicate-type fillers. The thermoset
polybutadiene, such as the Ricon resins, with very good electrical properties, are
generally silica-filled.

56
Particulate Fillers and Fibre Reinforcements

In high performance composites of polyimide and polybenzimidazole, thermally stable silanes


are needed as aminophenyl or as a mixed alkylaryl amino or chloromethylphenyl silanes.

2.3.3.2 Elastomers

In addition to the use of some 1000 kilo tonnes of carbon black, the elastomers industry
consumes about 800 kilo tonnes of nonblack particulate fillers (~ 1300 kilo tonnes)
largely dominated by carbonates, clays, silica, titania and zinc oxide. The reinforcement
provided by many of these fillers is considerable, but their overall performance properties
are limited and, generally, are significantly lower than those obtained with carbon black
reinforcement. The use of silane coupling agents that are rubber-reactive and which will
through couple to the non-black filler surface, provides properties that are useful under
very severe end-use conditions. Unsaturated silanes in peroxide cured ethylene-propylene-
rubber (EPR) and EPDM wire and cable compounds give significant improvements to
high-voltage cable formulations. Silane-treated clays are used in considerable volume by
wire and cable and speciality goods as solid golf ball formulations, providing
improvements in resiliency, hysteresis and rebound. The use of mercaptofunctional and
aminofunctional silanes in sulphur-curing elastomers provides improvement in modulus,
compression and tensile strength. The use of these silanes in tyre compounds is also of
considerable value in improving heat build-up, abrasion resistance, etc. In many non-
black systems, combinations of TiO2 and mineral filler (as hydrous clay) are used. Specialty
elastomers such as polychloroprene, epichlorohydrin and nitrile are filled with silane
treated-silica. Modulus increases by 150-300%, compression is reduced by 30-40% and
abrasion resistance is improved by 55-70%.

2.3.3.3 New Developments in Particulate Fillers

Some new developments in particulate fillers are given in Table 2.3.

SMC are thin sheets made of fibres precompounded with a thermoset resin, being used
primarily in compression moulding processes. The various types of SMC in current use are:

1. SMC R, containing randomly oriented discontinuous fibres;


2. SMC CR, containing a layer of unidirectional continuous fibres;
3. XMC, containing continuous fibres arranged in an X pattern.

BMC can be prepared using different techniques such as compression or injection


moulding, depending on the type of fibrous material and matrix material employed.

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Handbook of Polymer Blends and Composites

Table 2.3 New developments in particulate fillers [44]


Company Product Improvement and examples of
applications
J M Huber Mineral solutions Al(OH)3, Mg(OH)2 for flame
Corporation retardance and electrical
Engineering Minerals properties; CaCO3 for improved
Division surface of SMC in automotive
applications. Kaolin clay for
improved reinforcement impact
and processability
R J Marshall Company Spraylite filler systems
ECC International, CaCO3, polymer coated For thermoset polyesters (SMC),
Atlanta Polarite 420 G(W) BMC, low profile action, allowing
Polarite 423 G(B) reduced shrinkage and phase
separation, reduced porosity.
Surface smoothness, gloss,
weathering characteristics and
porosity for BMC parts is superior.
Carbon black is added
Pfizer Mineral HiThix 3388 CaCO3, formulated with proprietary
Specialty Mineral SuperThix 3434 surface coating. Ground limestone
Group of Easton, Pa Ultrafix 3397 for silicone sealant. Surface coated
CaCO3, for PU sealants. Surface
coated precipitated CaCO3 for PVC
plastisols
TAC Division of Amical-brand surface
Franklin Limestone coated CaCO3,
Co Dalton Al(OH)3 and flame
retarded CaSO4
Franklin Limestone 20 100 mesh mica For reinforced reaction injection
MICA-TER Mineral Polymica moulding (RRIM) metallised and
Industrial Commodities pigmented mica
of America
Dry Branch Kaolin Co Polyfil WC, WC-426 New surface modified electrical
Kaolin grades for wire and cable
applications
J M Huber Corp Clay Nylok 100 Filled Nylon
Division of Macon

58
Particulate Fillers and Fibre Reinforcements

Table 2.3 New developments in particulate fillers [44] continued


Company Product Improvement and examples of
applications
Cyprus International Talc Cimflex High aspect ratio large particle
Minerals Co of size, talc powder RIM
Englewood Colo.
Pfizer Ultratalc 408 High impact and flexural modulus
for PO
Montana Talc Co. Nicron 610
ECC International Ecco-Tal 325 P and
4ooP
PQ Corp Valley Microspheres High-strength hallow borosilicate
Forge, Pa Q-CEL 640 and 650 microspheres for high pressure
applications for SMC, BMC and
thermosets
Potters Industries Inc. Spherical 11098
N.J,
Bekaert Fibre Conductive fillers For PS and PO. For high
Technologies Marietta Stainless-steel fibres performance/high temperature
Ga Beki-Shield GR engineering thermoplastics PES,
75/C10; 90/C24 PEI, PEEK
Hoechst Celanese MA-g-PP Compatibiliser, increases tensile
Hostaprime HC5 strength in GF PP and other materials
BASF Elastolit R 4500 Fillers for RRIM process
polyurea/amide + filler and
reinforcement
Composition Plasti-Grit XH, H Thermoset melamine
Materials Co. Inc. formaldehyde and thermoset urea
Fairfield Conn formaldehyde with alpha-cellulose.
For electrical boxes, brake linings,
various automotive components
Nyco of Wilsboro, Wollastonite: New RIM. Polyurea/polyurethane body
NY chemically surface- panels and fascias. Nylon RRIM
modified grades for with superior hydrolytic stability
reinforced nylon
RRIM Wollastokup
10013; RRIM
Wollastokup 20417

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Handbook of Polymer Blends and Composites

Table 2.3 New developments in particulate fillers [44] continued


Company Product Improvement and examples of
applications
PPG Industries Inc GF roving Spray For thermoset liquid composites
Veil 5555; 5553; 5528 for SMC
Manville Corp. Star Rov 504 GF For filament winding, pultrusion
Toledo, Ohio Star Stan 702 and weaving for polyester, vinyl
ester and epoxy resin. Chopped
strands for PA, PC, SMA, PBT
Fibre Glass Industries Textrand 110 and GF bulked and entangled textures
Inc. Amsterdam, NY 55LYPP
Zoltek Corp, St Louis Panex Carbon yarn and chopped GF.
Mo Hybrid carbon fibre/woven aramid
reinforcement
The Carborund Co, Fibrefrax Ceramic fibres for epoxy,
Niagara Falls NY phenolic, melamine, PU, PA
GFPP: glass fibre reinforced polypropylene
SMA: styrene-maleic anhydride
PES: polyether sulphones
GF: glass fibre
RIM: reaction injection moulding
PU: polyurethane
PEI: polyether imides

There is a movement towards the development of multifunctional fillers, which will


make a useful contribution to performance.

2.4 Reinforcements
In the field of reinforcements, the new developments are in long fibre and high performance
fibres (such as aramids, carbon or polyethylene fibres), for injection moulding products,
and in the improvement of surface treatments developing new coupling agents.

The cellulose granules derived from a woody growing ring or corncobs are introduced as
extenders in plastics. They are environmentally inert and biodegradable, non-dusting
and absorb a high quantity of water (95%) retaining the free-flowing characteristics.
They are compatible with a wide range of active agents.

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Particulate Fillers and Fibre Reinforcements

Recently, the E-CR glass (corrosion-resistant E-glass) was developed, being particularly
designed for reinforcement of plastics submitted to acidic environment. Vetrotex
Certain Teed has developed Twintex, a commingled reinforcement of unidirectional
fibre roving and PP filaments. Glass reinforcement offering superior mechanical
properties in compounding PP, is M Star Stran from Schuller Mats and Reinforcements.

In addition to glass, the principal composite reinforcements are carbon (or graphite)
filaments, alumina whiskers, and filaments of high-strength metal such as boron.
These fibres will be less sensitive to water than glass is, because they are less
hygroscopic.

When particulate fillers are used in polymer composites, it is important to decrease


the free energy of the filler surface to reduce agglomeration, so they are often modified
with coupling agents.

The interest in fillers and reinforcements has risen considerably since 1974, due to
the increase of the raw materials cost and the industry search for materials with
good mechanical properties and lower densities as those of metals.

The predominant fibres used for reinforcement are made of glass or carbon (graphite).
Polymeric and metal fibres are used for specialised circumstances. Mineral fibre usage
is low and declining because of health concerns and lower performance, although
these materials were once of considerable commercial importance. Natural fibres
have yet to demonstrate their performance level to justify their usage in any but non-
demanding applications. Although they provide improvement in stiffness and impact
resistance, their use is severely limited by their relatively low resistance strength loss
sets around 124 C, while thermal degradation begins around 163 C, so they impart
a dark coloration to the composite, tend to degrade quickly on exposure to sunlight
and microbial attack and absorb water and oils with diminished mechanical and
dielectric properties.

2.4.1 Inorganic Fibres

Inorganic fibres are of interest for advanced composite materials because of their thermal
resistance and their compatibility with metal and ceramic matrices. Inorganic fibres of
commercial interest are based on silica, alumina, boron, silicon carbide and high melting
temperature metal fibres (steel or alloys of molybdenum, nickel, titanium and tungsten, etc).

Table 2.4 presents the chemical composition of inorganic fibres and Tables 2.5 and 2.6
list the representative properties.

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Handbook of Polymer Blends and Composites

Table 2.4 Chemical Composition of Inorganic Oxide Fibres [45-51]


Components (%)
Material SiO2 Al2O3 Fe2O3 CaO MgO Na2O B2O3
+ K2O
A-glass 72.0 <2.5 0.5 5-10 0.4-4.0 <15.0 0.5
C-glass 60-66 <6.0 <0.3 14.0 <3.0 8-15 2-7
D-glass 72-75 <0.5 0.2 - 0.2 1.3 22
E-glass 50-56 12-16 0 .3 16-25 <6.0 <2.0 6-13
R-glass 60 25 0.3 6-9 6-9 0.4 -
S-glass 65 22-25 0.2 <8.81 10-18 <1.1 <8.81
Quartz >99.95
C- 1 (Nextel 312) 24 62 14
C- 2 (Nextel 448) 28 78 2
Al-1 15 85
Al-2 (Soffil) 3 97
Al-3 (Fibre FP) >99
A-glass belongs to the group of alkaline-limestone glass (A-alkaline); C-glass belongs
to the group of alkaline-limestone glass, but it has a higher proportion of boron
trioxide (C-chemical corrosion endurance);
D-glass is a technical glass rich in silicon dioxide (D-dielectric properties);
E-glass has aluminium trioxide apart from silicon dioxide and boron trioxide
(E-electrical applications);
ECR-glass, in addition to silicon dioxide and calcium oxide, has as main component
aluminium trioxide (ECR electro chemical resistance);
R-glass, apart from the standard main components of aluminium trioxide and silicon
dioxide, has additions of calcium and magnesium oxides (R-resistance to fatigue,
thermal shock and moisture);
S-glass belongs to the group of aluminosilicate glass (S-stiffness, for mechanical
requirements);
C-1, ceramic 1 fibre;
C-2, ceramic 2 fibre;
Al-1, alumina 1 fibre;
Al-2, alumina 2 fibre;
Al-3, alumina 3 fibre.

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Particulate Fillers and Fibre Reinforcements

Table 2.5 Representative properties of some inorganic oxide fibres [45-51]


Properties Quartz C-1 C-2 Al-1 Al-2 Al-3
Specific gravity, g/cm3 2.2 2.7 3.10 3.25 3.3 3.95
Filament diameter, m 10 8-12 8-12 17 3 20
Range of available tow
counts, thousands filaments / 0.3 0.39 0.39 1 0.21
strand
100-
Price range, 1990 $/kg 180 440 760 440
400
Tensile modulus, GPa 69 152 220 200 300 377
Tensile strength, GPa 0.9 1.5 1.7 1.5 2 1.4
Tensile elongation, % 1.3 1 0.8 0.8 0.67 0.36
Toughness, MPa 5.9 7.7 6.6 5.6 13.3 2.5
Dielectric constant, 10 Hz 4.5 4.7 9.5
Melt temperature, C 1650 1800 >2000 2045
Maximum applied
900 1200 1600
temperature, C
90% tensile strength
1100 1400 1250 1100
retention temperature, C

Table 2.6 Representative properties of some glass fibres [45-51]


Properties A-glass C-glass D-glass E-glass R-glass S-glass
2.48- 2.54-
Specific gravity, g/cm3 2.49 2.16 2.5 2.49
2.50 2.60
Tensile modulus, GPa 45.5 70 55 72-75 88 87
Tensile strength, GPa 2.9 3 2.5 3.5 4.7 4.6
Maximum applied 600-
785 749 763 928 760
temperature, C 846
Dielectric constant, 10 Hz 6.3 6.9 6.5 5.1 5.8 5.2
Thermal expansion,
8.6 7.5 6.8 8.2 5.6 5.6
10-6 m/m.K

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Handbook of Polymer Blends and Composites

2.4.1.1 Glass Fibres

Glass fibres are the most common of all reinforcing fibres for polymeric (plastic) matrix
composites (PMC). The main advantages of glass fibres are: low cost, highly crosslinked
polymer, high tensile strength, high chemical resistance, and excellent insulating properties.
The disadvantages are: low tensile modulus, relatively high specific gravity among the
commercial fibres (2.62 g/cm3), sensitivity to abrasion with handling (which frequently
decreases in tensile strength), relatively low fatigue resistance, and high hardness (which
causes excessive wear on moulding dies and cutting tools).

After melt spinning, glass fibres are sized to protect their surface, to bind fibres together,
to improve interfacial bonding and antistatic properties. Necessary constituents of the
sizing are: a film-forming polymer to provide protection, e.g., polyvinyl acetate, a lubricant
and a coupling agent, e.g., organosilane.

The two types of glass fibres commonly used in the fibre-reinforced plastics (FRP) industry
are E-glass and S-glass.

E-glass is used in electronic boards because of its good electrical and weathering properties,
dimensional stability, good strength and stiffness, moisture resistance and lower cost
[51-53].

S-glass, originally developed for aircraft components and missile casings, has the highest
strength and modulus, high temperature resistance among all fibres in use [54, 55].
However, the compositional difference and higher manufacturing cost make it more
expensive than the E-glass. A lower cost version of S-glass, called S-2-glass, has become
available in recent years. S-glass is used in advanced composites where cost-performance
benefits can be justified.

Alkali-containing (eventually boron, too) grade A-glass is used in articles not excessively
subjected to stress and exposed neither to the action of weathering nor to moisture.
Grade C-glass is a chemical glass suitable for application requiring higher resistance to
acids but with a low strength, while dielectric grade D-glass is limited to electrical insulating
materials.

For special applications, AR, M and R grades are indicated for products subjected to
extremely high stress, for products with high strength and with good thermal and radiation
stability, respectively. AR-glass contains an increased addition of zirconium oxide and
is particularly alkali-proof. M-glass contains beryllium and is characterised by a high
modulus. R-glass is used in applications requiring radiation protection. These special
types are very expensive.

64
Particulate Fillers and Fibre Reinforcements

Oxides, such as B2O3 and Al2O3, are added to modify the network structures of SiO2, as
well as to improve its processability, while the Na2O and K2O content in E- and S-glass
fibres is quite low, which gives them a better corrosion resistance to water as well as
higher surface resistivity.

The internal structure of glass fibres is a three-dimensional, long network of silicon,


oxygen and other atoms arranged in random fashion. Thus, glass fibres are amorphous
(non-crystalline) and isotropic (equal properties in all directions).

The basic commercial form of continuous glass fibres is a strand that is a collection of
parallel filaments, numbering 204 or more.

A roving is a group of untwisted parallel strands wound in a cylindrical forming package.

Chopped strands are produced by cutting continuous strands into short lengths from 3.2
to 12.7 mm.

Milled glass fibres are produced by grinding continuous strands in a hammer mill into
lengths ranging from 0.79 to 3.2 mm.

Glass fibres are also available in woven form, such as woven roving or woven cloth. All
these forms of glass fibres are suitable for hand lay-up mouldings.

The average tensile strength of freshly drawn glass fibres may exceed 3.45 GPa. However,
surface damage produced by abrasion, either by rubbing against each other or by contact
with the processing equipment, reduces it to a value that is in the range of 1.72 2.07
GPa. The tensile strength of glass fibres is reduced in the presence of water or under
sustained loads (static fatigue) due to existence of alkaline soluble oxides and other
alkaline impurities.

In recent years, numerous investigations have been devoted to the multiple aspects of
glass fibres utilisation in composites, as: obtaining fibres [56-65] and composites [66-
92]; investigation methods [93-112]; properties of reinforcing fibres and of the composites
[113-127]; economic aspects [128-134].

2.4.1.2 Ceramic Fibres

Silicon carbide (SiC) and aluminium oxide (Al2O3) fibres are examples of ceramic fibres
notable for their high-temperature applications in metal and ceramic matrix composites.
Their melting points are 2830 C and 2045 C, respectively. Silicon carbide retains its
strength well above 650 C, and aluminium oxide up to about 1370 C. Both fibres are

65
Handbook of Polymer Blends and Composites

suitable for reinforcing metal matrices in which carbon and boron fibres exhibit adverse
reactivities [46, 135-137].

Silicon carbide fibres are available in three different forms [47, 50, 51]:

1. Monofilaments with the average fibre diameter of 140 m obtained by chemical


vapour deposition [138, 139];

2. Multifilament yarn produced by melt spinning of a polymeric precursor, such as


polycarbosilane at 350 C in nitrogen. The average fibre diameter in the yarn is 14.5
m and a commercial yarn contains 500 fibres. Yarn has a considerably lower strength
than the monofilaments [140-142];

3. Whiskers, which are 0.1-1 m in diameter and around 50 m in length, have been
initially produced from man-made rice hulls, which contains 10-20 wt% SiO2. The
silicon carbide whiskers contain 10 wt % SiO2 and up to 10 wt% Si3N4. The tensile
strength and modulus of these whiskers are reported as 13 and 700 GPa, respectively,
[143-145].

It is known that high thermal and mechanical resistance require strong chemical bonds. In
ceramic fibres, such a requirement is met through three-dimensional covalent bonds. Thus,
a perfect crystal, of a perfect geometry in a network, is represented by silicon carbide.

In a simple crystal of the whisker-type, a perfect alignment is present exclusively along


the fibres axis while, in the case of commercial fibres, a polycrystalline (crystalline-
amorphous) structure may be noticed. In the other extremity, an amorphous structure,
having no special spatial organisation of its elements exists.

In the case of silicon carbide, the geometry of the chemical bonds is simple, as both the
carbon and the silica are tetracovalent elements, permitting regulated tetrahedral networks.
The oxide-type fibres have much more complicated networks, as a result of the elements
different valencies. The Nicalon fibre (of the silicon carbide-type) shows ultrafine -
silicon carbide crystals, while the Fibre FP alumina fibre has a polycrystalline structure
of the -Al2O3 type, with a particle size of about 0.5 m. The most representative properties
of SiC fibres are presented in Table 2.7.

Out of the most recent achievements recorded in the field of silicon carbide fibres and of
their corresponding composites, special mention should be made of:

silicon carbide fibre-reinforced carbon composites [146-149];


studies on the micromechanical push-out test [150, 151];
microstructural characterisation of interface in silicon carbide fibre [152-154];

66
Particulate Fillers and Fibre Reinforcements

Table 2.7 Representative properties of silicon carbide fibres


[47, 50, 51, 135-145]
Properties Chemical vapour Pyrolysis (Nicalon-
deposition CVD multifilament supplied by
(monofilament supplied Nippon Carbon Co./
by Avco) Dow Corning)
Specific gravity, g/cm3 3.08 2.55
Filament diameter, m 140 10-20
Range of available tow Not applicable 0.5
counts, thousands
filaments/strand
Tensile modulus, GPa 430 190
Tensile strength, GPa 2.4 2
Tensile elongation, % 0.56 1.1
Toughness, MPa 13 11
Electrical resistivity, /m 0.1
Longitudinal coefficient of 3.1
thermal expansion,
10-6 m /(m.K)
Melt temperature, C 2700 2700
Maximum use 1150
temperature, C
90% tensile strength 800 300
retention temperature, C

new fibre made by UBE Industries with trade mark Tyranno [155, 156];
ceramic fibre tow reinforced metal matrix composite [157, 158];
microstructure control for optimising properties of ceramic composites[159-163];
honeycomb structure of thermostrucural composite material [164-170].

Continuous multifilament aluminium oxide yarn is available under the trade name Fibre
FP [45, 137, 171]. It is a high-purity (>99%) polycrystalline -Al2O3 fibre, dry spun
from a slurry mix of alumina and proprietary spinning additives. The filament diameter
is 20 m, and there are 210 filaments in the yarn. Fibre FP retains almost 100% of its

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Handbook of Polymer Blends and Composites

room temperature tensile strength after 300 hours of exposure in air at 1000 C. Fibre
FP has remarkably high compressive strength estimated to be about 6.9 GPa.

Another ceramic fibre, containing approximately equal parts of Al2O3 and silica (SiO2),
is available as staple under the trade name Fibrefrax (3M, USA) [137, 172]. The fibre
diameter is 2-12 m and the fibre aspect ratio is greater than 200. It is manufactured
either by melt blowing or by melt spinning processes.

Composites were fabricated by impregnating discontinuous alumina fibre (Soffil ICI,


UK) with Al-Cu-Mg-Ag alloys at two different magnesium levels [135].

Some of the properties of the alumina fibres are listed in Table 2.8.

Table 2.8 Properties of selected commercial reinforcing alumina fibres


[137, 161, 172]
Fibre Diameter, Specific Tensile Tensile
m gravity, g/cm3 modulus, GPa strength, GPa
Al2O3, Fibre FP 20 3.95 379 1.90
Al2O3, Fibrefrax 2-12 2.73 103 1.03-1.72

2.4.1.3 Boron Fibres

Boron fibres have an extremely high tensile modulus: 379-414 GPa and with their relatively
large diameter, they offer excellent resistance to buckling, which in its turn contributes
to high compressive strength for composites. The main disadvantage of boron is its high
cost, which is even higher than that of many forms of carbon fibres. For this reason, its
use is at present restricted to aerospace applications [49, 147, 157].

Boron fibres are manufactured by chemical vapour deposition (CVD) of boron onto a
heated substrate (either a tungsten wire or a carbon monofilament [137]). Boron vapour
is produced by the reaction of boron chloride with hydrogen:

2BCl3 + 3H2 = 2B + 6HCl

Deposition temperature is 1100-1300 C. The resulting fibre diameter is controlled by


varying the speed of pulling as well as the deposition temperature. Currently, commercial
boron fibres are produced in diameters of 0.1, 0.142 and 0.203 mm that are much larger
than those of other reinforcing fibres [156].

68
Particulate Fillers and Fibre Reinforcements

Boron fibres are used in epoxy, aluminium or titanium matrices. The resulting composites
have high strength-to-weight ratio, and good compressive strength [162].

Some of the main properties of boron fibres are presented in Table 2.9.

Table 2.9 Properties of boron fibres


Property Value
Diameter 140 m
Specific gravity 2.7 g/cm3
Tensile modulus 393 GPa
Tensile strength 3.1 GPa
Strain 0.79%
Coefficient of thermal expansion 5 x 10-6 C
Poissons ratio 0.2

By CVD of silicon carbide on boron fibres, borsic fibres are produced [137, 144]. Borsic
fibre loses 50% of its room-temperature tensile strength after only one hour of exposure
to air at 500 C [137].

2.4.1.4 Asbestos Fibres

The commercial term asbestos includes a large number of fibrous hydrated magnesium
and sodium silicate minerals of different composition, crystalline state, strength, flexibility
and length. There are six kinds of asbestos from the chrysolite and amphibole group,
which are either fibres or prismatic crystals. The colour varies from white, green and
brown; Mohs hardness 2.5 to 6; fibre diameter of 20 to 90 nm and length up to 500 nm,
mean strength; service temperature limit of 1510 C.

The long-fibre types are used as fibres and yarns, while the short-fibre ones are used as
fillers, extenders, and viscosity adjusting aids.

Asbestos fibres differ from glass fibres in that they have an unusually large surface, the
stiffness is twice as high at a similar level of tensile strength; also they are more compactly
bundled, have stronger interfibrillary bonds, and exhibit a higher degree of felting. All these
characteristics induce a significant improvement in the isotropy of the reinforcing effect.

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Handbook of Polymer Blends and Composites

Asbestos fibres have been used in the past, but their use has ceased following discoveries
of the health hazard they may induce.

2.4.2 Classical Fibres

For the manufacture of composites with lower technical performances classical fibres,
characterised by normal elasticity modulus and tenacity values, are still used.

Nevertheless, in several cases, attempts have been made to replace high modulus (HM)
fibres, known to be expensive and less accessible, by classical fibres, to obtain composites
with comparable qualitative characteristics. To this end, both natural and chemical fibres
are used.

2.4.2.1 Natural Fibres

Suitable natural fibres, e.g., cellulosic fibres, bonded together by means of modified binders
containing preservatives, are used to reinforce lightweight components used in the
construction of walls, ceilings and other structural items [50, 173, 174-195].

Natural fibres are undergoing a revolution that could see them replace composite materials,
plastics reinforced with glass or carbon fibres, in the future. Daimler Benz is a world leader
in using natural fibres in its vehicles and has been using flax fibres in the door panels of its
Mercedes G-Class cars since 1995. The real challenge though is to eliminate the oil derived
plastic and replace it with a renewable version [175, 176].

German car manufacturers are researching the use of naturally occurring materials to
replace synthetics. Mercedes-Benz is now using animal hair and fibres made from coconut,
cotton, flax and sisal in its cars and want to progress their use further. Currently, they are
investigating the potential to replace glass fibres in reinforced plastics with cellulosic fibre.
Current problems are processing and the poor heat resistance of natural fibres [51].

Originally, high performance composites were defined as being: carbon, aramid, ceramic
fibres (silica carbide and Al2O3), high molecular PE, aromatic polyester fibres (liquid crystal
polyester; LCP) and special glass fibres from R- and S-glass. However, over the last ten
years, natural fibres such as flax and hemp have been used in low performance composites
and the development in this field has lead to the assumption that natural fibres are set to
replace E-glass fibres in high performance composites [54, 177, 178].

Cotton fibres [176, 177, 191, 194], flax or hemp fibres [174, 177, 184, 185, 190, 192,
193], sisal fibres [175, 178, 179, 186-188], pineapple-leaf fibres [183], palm tree leaves
[173, 183, 195], bamboo fibres [181, 183] and jute fibres [182, 187, 188] have all been
used as reinforcing fibres.

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Particulate Fillers and Fibre Reinforcements

2.4.2.2 Man Made Fibres

Several carbocatenary and heterocatenary chemical fibres have been used as reinforcing
agents for composites [47, 50, 51]. Thus, special mention should be made here of both
carbocatenary and heterocatenary chemical fibres [196, 197].

Out of the carbocatenary fibres the following have been used: acrylic fibres [198-200],
Vinylon (PVA) fibres [201-202] and classical polyolefinic fibres [203-208].

Among the heterocatenary ones, the most representative are: polyester fibres [209-211]
utilised especially for the fabrication of nonwovens; polyamide fibres [212-214], mainly
employed in reinforcing car types; nylon based composites are claimed to reduce component
cost and weight when used instead of cast metal; elastic or polyurethanic fibres [215, 216].

Also, fibres based on both regenerated and modified cellulose have been successfully
used [217].

Synthetic fibre reinforced plastics have significantly lower moduli than glass reinforced
plastics in the direction of the fibre, but there is a higher resistance to damage by
distortion.

2.4.3 High Performance Fibres

2.4.3.1 Carbon Fibres

Carbon fibres are produced by heat treatment of organic precursors such as rayon [218,
219-224], polyacrylonitrile (PAN) and pitch.

Rayon-based carbon fibres can be obtained by the following method: stabilisation at


400 C in oxygen, depolymerisation and aromatisation; carbonisation at 400-700 C in
an inert atmosphere; stretch and graphitisation at 700-2800 C to improve orientation
and increase crystallinity by 30-50%.

PAN-based carbon fibres can be obtained by the following method: stabilisation at 200-
300 C in oxygen, depolymerisation and aromatisation, converting thermoplastic PAN
to a non-plastic cyclic or ladder compound; carbonisation at 1000-1500 C in an inert
atmosphere to get rid of non-carbon elements; stretch and graphitisation at > 1800 C.

Pitch-based carbon fibres may be obtained by the following method: heating at > 350 C,
condensation reaction, formation of mesophase (liquid crystal; LC); melt spinning into
pitch fibres; conversion into graphite fibres at 2000 C.

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Handbook of Polymer Blends and Composites

Carbon fibres have the highest modulus and strength of all reinforcing fibres at both
room and high temperatures, with a tensile modulus ranging from 207 GPa on the low
side to 1035 GPa on the high side. Low-modulus fibres have lower specific mass, lower
cost, higher tensile and compressive strength and higher tensile strain-to-failure than
high-modulus fibres [218].

Table 2.10 shows the typical mechanical properties of commercially available carbon fibres.

Table 2.10 Typical properties of commercially available carbon fibres


[47, 50, 51, 218]
Fibre Producer Precursor Density Tensile Strain, Coefficient
(g/cm3) strength/ % of thermal
modulus expansion
(GPa) (10-6/C)
AS-4 Hercules, Inc. PAN 1.78 4.0/231 1.65 - 0.6
AS-6 Hercules, Inc. PAN 1.82 4.5/245 1.32 2.9
IM-6 Hercules, Inc. PAN 1.74 4.8/296
T-300 Union Carbide /Toray PAN 1.75 3.31/228 1.4 5
T-500 Union Carbide /Toray PAN 1.78 3.65/234
T-700 Toray PAN 1.80 4.48/248 1.65 - 0.6
T -40 Toray PAN 1.74 4.5/296 1.8 - 075
Celion Celanese / Toho PAN 1.77 3.55/234
Celion ST Celanese / Toho PAN 1.78 4.34/234
XAS Grafil/Hysol PAN 1.84 3.45/234
HMS-4 Hercules, Inc PAN 1.78 3.10/338
PAN 50 Toray PAN 1.81 2.41/393
HMS Grafil/Hysol PAN 1.91 1.52/341
G 50 Celanese / Toho PAN 1.78 2.48/359
GY-70 Celanese PAN 1.96 1.52/483
P 55 Union Carbide Pitch 2.0 1.73/379 0.5 -13
P 75 Union Carbide Pitch 2.0 2.07/517
P 100 Union Carbide Pitch 2.15 2.24/724 0.32 -1.45
HMG-50 Hitcon/DCF Rayon 1 .9 2.07/345
Thornel 75 Union Carbide Rayon 1.9 2.52/517

72
Particulate Fillers and Fibre Reinforcements

The density is low, however, the performance:cost ratio limits their use to high
performance applications such as aerospace, where stiffness:weight ratio is the primary
concern [219-226].

Carbon fibres are electrically conductive, which require special care when using them
around electric motors and electronic controls [227].

Since carbon fibres are difficult to wet with resins, surface treatments are used to increase
the number of active chemical groups and harden the fibre surface [228].

In order to reduce fibre abrasion, to improve handling and to provide fibre-matrix


compatibility, it is common practice to impregnate carbon fibres with epoxy size prior to
shipment. These materials are called prepregs [229-232].

Structurally, carbon fibres contain a blend of amorphous and graphitic carbon. Their
high tensile modulus results from the graphitic form, in which carbon atoms are arranged
in crystallographically parallel planes of regular hexagons [47, 218]. The distance between
the planes (3.4 ) is larger than that between the adjacent atoms in a plane (1.42 ). The
planes are held together by weak van de Waals-type forces, and a strong covalent bond
exists between the carbon atoms in a plane. This results in highly anisotropic physical
and mechanical properties for the fibre [233-236].

Carbon fibres are commercially available in three basic forms:


continuous tow, bundle of 1000 to 160,000 parallel filaments;
chopped fibres (6-50 mm long);
milled fibres (30-3000 m long).

There are different types of carbon fibres reinforcements and recent achievements have
come from the three main types of composite materials:
carbon fibre reinforcing-polymer composites (CFRP) [229-232, 241-254];
carbon fibre reinforcing-metal composites (CFRM) [228, 235, 255-263];
carbon fibre reinforcing-carbon composites (CFRC) [234, 240, 264-276].

Among the aspects to which the literature of the field has been predominantly devoted,
one should note:
obtaining carbon fibre-based composites;
investigation of composite fibres properties considered as a whole and in their diversity,
including fibre degradation and compatibilisation;
applications based on strength and stiffness, thermophysical properties, chemical
inertness and corrosion resistance, specific rigidity and good damping, biological
inertness and x-ray permeability, electrical conductivity, fatigue resistance, etc.

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Handbook of Polymer Blends and Composites

2.4.3.2 Aramidic Fibres

Aramids are a group of highly crystalline aromatic polyamide fibres that have the lowest
specific gravity (1.47 g/cm3), the relatively high thermal and chemical resistance and the
highest tensile strength-to-weight ratio.

Aramidic fibres have numerous aromatic rings, constituted in rigid macromolecules,


showing strong interactions with the neighbouring macromolecules, both at the benzene
rings and through hydrogen bonds. In solution, the self-attractive macromolecules join
together, forming elongated liquid crystals with array and pleated system.

Some imperfections among crystals may be noticed, along with imperfections in crystals
packing and deviations from perfect orientation. These fibres have a sheath-core structure
with a porous skin region with arrays of needle-shaped voids aligned approximately
parallel to the fibre axis.

Perhaps the most widely known para-aramidic fibre is Kevlar (poly-para-phenylene


terephthalamide) produced by DuPont.

There are several versions of Kevlar used in textile structural composites, as shown in
Table 2.11.

The thermal treatment under tension improves structural perfection, less ordered forms,
with a smaller modulus, e.g., Kevlar 29, being present along with more ordered forms,
with a higher modulus, e.g., Kevlar 49 and 149.

Table 2.11 Properties of Kevlar fibres [47-48, 50-51]


Property Kevlar 29 Kevlar 49 Kevlar 149
(high toughness) (high modulus) (ultra-high
modulus)
Density, g/cm3 1.44 1.44 1.47
Filament diameter, m 12 12 12
Tensile modulus, GPa 83 131 186
Tensile strength, GPa 3.6 3.6-4.1 3.4
Tensile elongation, % 4. 0 2.8 2.0
Number of filaments 134-10,000 134-5,000 134-1,000
Coefficient of thermal -2.9 -2 -1.9
expansion (10-6/C)
Poissons ratio 0.37 0.35 0.30

74
Particulate Fillers and Fibre Reinforcements

Nomex, the meta-aramidic fibre, has a partially oriented structure, once the shape of
the poly-meta-phenylene terephthalamide prevents the formation of liquid crystals.
The structure of the Nomex fibre is closer to that of the synthetic polyamidic and
polyesteric fibres.

Other HM fibres made from liquid crystals are the Technora aramidic fibres, the Vectra(n)
aromatic polyesteric fibres and some new polymeric fibres with highly oriented structures,
which make them highly crystalline, such as the poly-p-phenylenebenzbisoxazole (PBO),
poly-2,5,(6)-benzoxazole (ABPBO), poly-p-phenylene benzobisthiozole (PBZT). Like
carbon fibres, they also have a negative coefficient of thermal expansion in the longitudinal
direction, which is utilised in designing low thermal expansion composites for printed
circuit boards. The major disadvantages of aramidic fibre for reinforced composites are
their low compressive strength, tendency to fibrillate, poor transverse properties,
susceptibility to abrasion and difficulty in cutting or machining them [47-48, 50-51].

Kevlar filaments are manufactured by extruding an acidic solution of a proprietary


precursor (a polycondensation product of terephthaloyol chloride and p-
phenylenediamine) from a spinneret [277-280]. During the filament drawing process,
Kevlar 49 molecules become highly oriented in the direction of the filament axis. The
resulting filament is highly anisotropic, with much better physical and mechanical
properties in the longitudinal direction than in the radial one [281].

Absorbed moisture seems to have very little effect on the tensile properties of Kevlar 49
fibres. However, at high moisture content, they tend to crack internally at the pre-existing
microvoids and produce longitudinal splitting.

A second-generation Kevlar fibre is Kevlar 149, which has the highest tensile modulus of
all commercially available aramid fibres. The tensile modulus of Kevlar 149 is 40%
higher than that of Kevlar 49; however, its strain-to-failure rate is lower. Kevlar 149 has
an equilibrium moisture content of 1.2% at 65% relative humidity and at 22 C, which
is nearly 70% lower than of the Kevlar 49 under similar conditions. Kevlar 149 also has
a lower creep rate than Kevlar 49.

Kevlar 149 fibres are commercially available as untwisted textured yarns with 134, 267,
768 and 1,000 filaments, roving with 3,072 and 5000 filaments, and woven and non-
woven fabrics [283, 284].

Although the tensile stress-strain behaviour of Kevlar 49 is linear, longitudinal


fragmentation, splitting, and even localised drawing usually precede fibre fracture. In
bending, Kevlar 49 fibres exhibit a high degree of yielding on the compression side. Such
a non-catastrophic failure mode is not observed in glass or carbon fibres, and gives
Kevlar 49 composites superior damage tolerance against impact or other dynamic loading.

75
Handbook of Polymer Blends and Composites

One interesting application of this characteristic of Kevlar 49 fibres is soft lightweight


body armours and helmets used for protecting police officers and military personnel
[284, 285].

Other properties of Kevlar 49 fibres are summarised as in Table 2.12.

Table 2.12 Some properties of Kevlar 49 fibres [283-285]


Property Values Effects
Melting point Do not melt Self extinguish
Carbonise 427 C Maximum long-term use
temperature recommended is
160 C
Thermal conductivity Very low
Vibration damping Very high coefficient
Chemical resistance Good except for a few
strong acids and alkalies
Ultraviolet light Sensitive Prolonged direct exposure to
sunlight causes discoloration and
significant loss in tensile strength.
The problem is less pronounced in
composite laminates in which the
fibres are covered with a matrix
Hygroscopicity Above 6% moisture at The equilibrium moisture content
100% relative humidity (maximum moisture absorption)
at 23 C is directly proportional to relative
humidity and is attained in
16-36 h)

2.4.3.3 High Modulus Polyethylene Fibres

An alternative to the previously mentioned structures is the utilisation of flexible


macromolecules with weak interactions, yet with very long, highly extended oriented,
and packed chains, with a high crystalline ordering, spinned from polymeric gel. These
are high modulus polyethylene fibres (HMPE) of the Dyneema and the Spectra types,
produced from PE with a very high molecular mass. The crystalline network includes
extended chains, with a high density of the covalent bonds along all planes, yet with very
weak van der Waals links between the chains.

76
Particulate Fillers and Fibre Reinforcements

Extended chain PE fibres, commercially available under the trade name Spectra, are
produced by solution spinning of a high molecular-weight PE. Solution spinning yields a
highly oriented fibrous structure with exceptionally high crystallinity (95-99%) [47, 48,
50, 286, 287].

Spectra PE fibres from the Allied Company have the highest strength-to-weight ratio of
all commercial fibres available to date. Two other outstanding features of Spectra fibres
are their low moisture absorption (1% compared to 5-6% for Kevlar 49) and high abrasion
resistance.

The melting point of Spectra fibres is low (147 C), and since they exhibit a high level of
creep above 100 C, their application temperature is limited to 80-90 C. Their poor
adhesion with resin matrices, can be partially improved by their surface modification
with gas-plasma treatment.

Spectra fibres provide high impact resistance for composite laminates even at low
temperatures and are finding increasing application in ballistic composites. However,
their use in high-performance aerospace composites is limited, unless they are used in
conjunction with stiffer carbon fibres to produce hybrid laminates with improved impact
damage [288-291].

Some of the physico-mechanical properties of the high performance PE fibres are presented
in Table 2.13.

Table 2.13 Properties of selected commercial extended-chain PE reinforcing


fibres [292-294]
Fibre Diameter, m Specific Tensile Strain, %
gravity, g/cm3 modulus/
strength, GPa
Spectra 900 38 0.97 117/2.59 3.5
Spectra 1000 27 0.97 172/3.00 2.7

Ultra-high oriented polyethylene fibre (UHMWPE) is used increasingly because of their


extremely high stiffness and strength. Relaxation and creep are mostly due to chain
motion in the vicinity of structural irregularities.

The structure and deformation behaviour of UHMWPE fibres and composites based on
them are explained, and advances in the development of self-reinforced composites are
predicted [295-300].

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Handbook of Polymer Blends and Composites

2.4.4 Perspectives, Costs, Marketing Aspects

The literature gives a survey on the development of reinforcing fibres used for polymeric
composites along with the description of the improvement of the properties of carbon
fibres. In addition, the status quo of the development of inorganic fibres for metallic and
ceramic matrices is presented. A cost rating of the different fibres is performed on the
basis of their production processes. Also, the market development for glass, carbon and
aramide fibres is described geographically and by application.

FRP continue to be used in new and innovative designs. Sales of advanced composite
components were exceeding 20,000 metric tons in 1995, yet, FRP users/suppliers need
to demonstrate their recyclability to maintain this market acceptance.

Most of the composites in existence today were originally developed for aerospace
applications. Although the results have been very successful, the cost factor has hindered
spreading of composites into other application areas and industries. Other factors that
prevent the faster growth of composite usage include capital investment, inspectability,
part consistency, lack of well-established manufacturing techniques and industry-wide
specifications.

With the end of the cold war, the composite research in aerospace and defence areas is
decreasing, which leaves transportation and construction as the biggest potential areas
for composite growth. As a result, due to different and probably less demanding
applications, new low cost composites need to be developed, for the utilisation in
mechanical, civil and structural engineering or in automotives and electronic applications.

The emphasis laid on smart or intelligent composites and materials has increased recently.
A smart or intelligent material may be defined as a material that possesses intrinsic
sensing, controlling and actuating capabilities. The growing use of composites in highly
sophisticated systems such as aerospace, may necessitate the development of smart or
intelligent composites. This, in turn, may require new developments in polymers, fibres
and other textile structures. Although some intelligent materials can be found in naturally
occurring biosystems, the development of synthetic intelligent materials is still in the
conceptual stage.

A comparison of the economics of several manufacturing processes for a composite


component in 40 years experience with composites is presented.

The future of advanced composites is reported, with the long-term status of the market
predicted for the next 20 years. The future looks good even if prospects may not look so
attractive in the short term. Four major sectors are identified as providing the bulk of the
future growth: infrastructure and constructions; transportation and alternate fuels for
transportation; marine structures; and industrial machinery [301].

78
Particulate Fillers and Fibre Reinforcements

The 21st century will usher in the need for repair retrofit and replacement of facilities,
which are deteriorating at a rapid rate. Composites will provide the material to resist
corrosion and maintain the safety of structures.

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Handbook of Polymer Blends and Composites

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Particulate Fillers and Fibre Reinforcements

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Handbook of Polymer Blends and Composites

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50. S. Adamur, Wellington Sears Handbook of Industrial Textiles, Technomic


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51. A. K. Dhingra and H. G. Lauterbach in Polymers: Fibres and Textiles, A


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52. Seong Sik Cheon, Jin Ho Choi and Dai Gil Lee, Composite Structures, 1995, 32,
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53. G. O. Shonaike and T. Maksuo, Composite Structures, 1995, 32, 1-4, 445.

54. M. Akay and D. F. ORegan, Plastics, Rubber and Composites Processing &
Applications, 1995, 24, 2, 97.

55. S. F. Bush, F. Yilmoz and P. F. Zhang, Plastics, Rubber and Composites


Processing & Applications, 1995, 24, 3,139.

56. M. L. Benzeggagh and S. Benmedakhene, Composites Science & Technology,


1995, 55, 1, 1.

57. J. P. Gasca and G. Tardy, inventors; Vetrotex France, assignee; US 5,470,658,


1995.

58. M. D. Gilchrist, A. J. Kinloch, F. L. Matthews and S. O. Osiyemi, Composites


Science & Technology, 1996, 56, 1, 37.

59. C. R. Key and Y. J. Shih, inventors; National Starch & Chemical Investment
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60. J. Gulino, inventor; Vetrotex France, assignee; US 5,520,984, 1996.

61. J. A. Fadell, inventor; Schuller International Inc., assignee; US 5,585,180, 1995.

62. M. W. Klett, inventor; PPG Industries, assignee; US 5,605,757, 1997.

82
Particulate Fillers and Fibre Reinforcements

63. E. M. Bullock, A. M. Steer and P. J. Tonge, inventors; Tenmat Ltd., assignee; GB


2,306,177 A, 1997.

64. P. L. Schell, inventor; PPG Industries, assignee; US 5,646,207, 1997.

65. C. R. Key and Y. J. Shih, inventors; National Starch & Chemical Investment
Holding Corporation, assignee; US 5,665,470, 1997.

66. S. K. De and J. R. White, Short Fibre-Polymer Composites, Woodhead Publishing


Limited, Cambridge, UK, 1996.

67. E. DeLuca, J. Prifti, W. Betheney and S. C. Chou, Composites Science &


Technology, 1998, 58, 9, 1453.

68. Advanced Composites Bulletin, 1998, 9, 5.

69. Advanced Composites Bulletin, 1995, 11, 2.

70. M. H. Abd Allah, E. M. Abdin, A. I. Selmy and U. A. Khashaba, Composites


Science & Technology, 1996, 56, 1, 23.

71. Non-wovens Report International, 1996, 299, 6.

72. Advanced Composites Bulletin, 1996, 3, 6.

73. G. J. Cook and A. Hughes, inventors; United Wire Ltd., assignee; E 0 697 921,
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74. Advanced Composites Bulletin, 1996, 4, 2.

75. P. Davoine and J-C. Berthier, inventors; Sarl ADN, assignee; EP 0703307, 1996.

76. F. Glover, inventor; Carrington Weldgrip Limited, assignee; GB 2,294,658, 1996.

77. Reinforced Plastics, 1996, 40, 5, 4.

78. Reinforced Plastics, 1996, 40, 5, 20.

79. H. Kimura, M. Maeda and T. Hirai, inventors; UBE - Nitto Kasei Co., assignee;
US 5,540,986, 1996.

80. H. T. Van de Grampel and Y. Hou, inventors; Azdel Inc., assignee; US 5,500,433,
1996.

83
Handbook of Polymer Blends and Composites

81. W. K. Tredway, C. W. Musson and O. Y. Chen, inventors; United Technologies


Corp., assignee; US 5,552,215, 1996.

82. S. Kichmeyer, inventor; Bayer AG, Bayer Antwerpen NV, assignee; E 0751100,
1997.

83. H. Daichon and Y. Yoshimoto, inventors; Koito Manufacturing Co., assignee; GB


2,303,631 A, 1997.

84. Reinforced Plastics, 1997, 41, 2, 4.

85. F. E. Penrose, inventor; Smith and Nephew plc, assignee; EP 0773800, 1997.

86. B. von Schlotheim, Chemische Industrie, 1986, 109, 9, 744

87. K. D. Beer, B. Anderson and R. A. Davis, inventors; PPG Industries Inc., assignee;
US 5,672,641, 1997.

88. Nissan Motor Corp. Ltd., assignee; GB 2,312,427, 1997.

89. M. Ushida and M. Ogata, inventors; Shin-Kobe Electric Machinery Co., assignee;
US 5,662,776, 1997.

90. J. P. Debalme and D. Loubinoux, inventors; Vetrotex France SA, assignee; E


0815307, 1997.

91. Reinforced Plastics, 1998, 42, 7, 27.

92. Reinforced Plastics, 1998, 42, 8, 6.

93. W. L. Hall, inventor; General Electric Company, assignee; US 5,468,437, 1995.

94. R. J. Brooks and G. J. Turvey, Composite Structures, 1995, 32, 1-4, 203.

95. T. Nishiwaki, A. Yokoyama, Z. Maekawa and H. Hamada, Composite


Structures, 1995, 32, 1-4, 635.

96. T. Katayama, T. Omiya, I. Amano, T. Tanaka, and K. Kuroda, Composite


Structures, 1995, 32, 1-4, 531.

97. Y. Katahara and T. Katayama, Composite Structures, 1995, 32, 1-4, 567.

98. M. R. Wisnom and M. I. Jones, Composite Structures, 1995, 32, 1-4, 615.

99. M. R. Wisnom, Composite Structures, 1995, 32, 1-4, 621.

84
Particulate Fillers and Fibre Reinforcements

100. Z-F. Li, D. T. Grubb and S. L. Phoenix, Composites Science & Technology, 1995,
54, 3, 251.

101. M. Pinfold and G. Calvert, Composite Structures, 1995, 32, 1-4, 549.

102. M. Carroll, F. Ellyin, D. Kujawski and A. S. Chin, Composites Science &


Technology, 1995, 54, 4, 391.

103. T. E. Tay, H. G. Ang and V. P. W. Shim, Composite Structures, 1995, 33, 4, 201.

104. A. G. Mamalis, D. E. Manolakos, G. A. Demosthenos and M. Ioannidis,


Composite Structures, 1995, 34, 1, 77.

105. X. Yuanming and W. Xing, Composites Science & Technology, 1996, 56, 2, 155.

106. M. L. Benzeggagh and M. Kenane, Composites Science & Technology, 1996, 56,
4, 439.

107. H. Leber and J. M. Lifshitz, Composites Science & Technology, 1996, 56, 4, 391.

108. Research Disclosure, 1996, 381, 30

109. A. S. Hadi and J. N. Ashton, Composite Structures, 1996, 34, 4, 381.

110. M. Salvia and L. Vincent, Composites Science & Technology, 1996, 56, 7, 797.

111. E. V. Pisanova and S. F. Zhandarov, Composites Science & Technology, 1997, 57,
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112. R. Park and J. Yang, Composites Science & Technology, 1998, 58, 6, 979.

113. D. C. Lee, J. J. Lee and S. J. Yun, Composite Structures, 1995, 32, 1-4, 39.

114. M. D. Robb, W. S. Arnold and I. H. Marshall, Composite Structures, 1995, 32,


1-4, 141.

115. B. Bompard and V. Veauville, TUT Textiles Usages Techniques, 1997, 23, 32.

116. B. Wulfhorst, R. Knein-Linz, K. U. Moll, P. Offermann and T. Pusch, Melliand


Textilberichte, 1995, 76, 9, 620.

117. J. Karger-Kocsis, T. Harmia and T. Czigany, Composites Science & Technology,


1996, 54, 3, 287.

118. G. Zhou, Composites Science & Technology, 1995, 54, 3, 273.

85
Handbook of Polymer Blends and Composites

119. A. P. Mouritz, Composites Science & Technology, 1995, 55, 4, 365.

120. High Performance Textiles, 1996, 4, 10.

121. X. Dirand, B. Hilaire, J. P. Soulier and M. Nardin, Composites Science &


Technology, 1996, 56, 5, 533.

122. L. Sodomka, Vlakna a Textil, 1996, 3, 1, 20.

123. J. P. Tancrez, J. Pabiot and F. Rietsch, Composites Science & Technology, 1996,
56, 7, 725.

124. G. Zhou, Composite Structures, 1996, 35, 2, 171.

125. M. D. Gilchrist, A. J. Kinloch and F. L. Matthews, Composites Science &


Technology, 1996, 56, 9, 1031.

126. E. Mader and K. Skop-Cardarella, Technical Textiles, 1998, 41, 1, 37.

127. A. Vasquez, M. Ambrustolo and S. M. Moschiar, Composites Science &


Technology, 1998, 58, 3-4, 549.

128. E. Mangenot, TUT Textiles Usages Techniques, 1995, 16, 12.

129. T. Bishop and T. W. Cowley, Tappi Journal, 1996, 79, 1, 137.

130. DuPont Magazine, 1996, 90, 1, 7.

131. Advanced Composites Bulletin, 1996, 3, 3.

132. Advanced Composites Bulletin, 1996, 3, 5.

133. A. Weaver, Technical Textiles International, 1996, 5, 6, 24.

134. Advanced Composites Bulletin, 1996, 7, 4.

135. J. M. ORourke, R. S. Bushby and V. D. Scott, Composites Science &


Technology, 1996, 56, 8, 957.

136. R. S. Bushby, J. M. ORourke and V. D. Scott, Composites Science & Technology,


1996, 56, 8, 967.

137. W. Bendkowska, Przeglad Wlokienniczy, 1997, 51, 1, 6.

138. F. Doreau, H. Maupas, D. Kervadec, P. Ruterana, J. Vicens and J. L. Chermant,


Journal of the European Ceramic Society, 1995, 15, 12, 1235.

86
Particulate Fillers and Fibre Reinforcements

139. Advanced Composites Bulletin, 1996, 12, 2.

140. J. F. Fromentin, K. Debray, Y. Le Petitcorps, E. Martin and J. M. Quenisset,


Composites Science & Technology, 1996, 56, 7, 767.

141. F. Lamouroux, M. Steen and J. L. Valles, Composites Science & Technology,


1996, 56, 7, 825.

142. M. K. Brun, K. L. Luthra and R. N. Singh, inventors; General Electric Co.,


assignee; US 5,552,352, 1996.

143. S. Kumar and R. N. Singh, Composites Science & Technology, 1996, 56, 11,
1271.

144. D. B. Gundel and F. E. Wawner, Composites Science & Technology, 1997, 57, 4,
471.

145. L. Zheng, Y. Jin and P. Li, Composites Science & Technology, 1997, 57, 4, 463.

146. U. Cocen, K. Onel and I. Ozdemir, Composites Science & Technology, 1997, 57,
7, 810.

147. S. G. Warrier and B. S.Majundar, Materials Science and Engineering A, 1997,


237, 2, 256.

148. Hua-Tay Liu and P. F. Becher in Thermal and Mechanical Test Methods and
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Dekker, New York, 1997, 128.

149. S. Lee and P. V. Mosher, inventors; SGL Carbon Composites Inc., assignee; US
5,759,688, 1998.

150. B. Guichet and J. C. Sangleboeuf, Composites Science & Technology, 1998, 58,
5, 665.

151. L. Geng, S. Ochiai, J. Q. Hu and C. K. Yao, Materials Science and Engineering A,


1998, 246, 302.

152. S. Q. Guo, Y. Kagawa, H. Saito and C. Masuda, Materials Science and


Engineering A, 1998, 246, 25.

153. A. Thionnet and J. Renard, Journal of the European Ceramic Society, 1995, 15,
12, 1235.

87
Handbook of Polymer Blends and Composites

154. M. Leparoux, H. Vandenbulcke, V. Serin, J. Sevely, S. Goujard and C. Robin-


Brosse, Journal European Ceramic Society, 1998, 18, 6, 715.

155. T. Ishikawa, K. Bansaku and N. Watanabe, Composites Science & Technology,


1998, 58, 1, 51.

156. P. W. Griffith, A. Wisbey and M. J. Wood, Diamond and Related Materials,


1998, 7, 7, 957.

157. J. Pan, J. H. Li and H. Fukunaga, Composites Science & Technology, 1997, 57,
3, 319.

158. Revista Delle Technologie Tessili, 58, 1, 51.

159. L. C. De Joughe, Advanced Composites Bulletin, 1996, 8, 3.

160. P. Colomban and N. Lapous, Composites Science & Technology, 1996, 56, 7, 739.

161. J. E. Goethe, L. R. Dharani and D. R. Caroll, Journal of Composites Technology


and Research, 1996, 18, 3, 194.

162. J. R. Carlberg, inventor; Caterpillar Inc., assignee, US 5,565,514, 1996.

163. L. R. Hwang, J. W. Fergus, H. P. Chen and B. Z. Jang, Composites Science &


Technology, 1996, 56, 12, 1341.

164. A. Delage, J. M. Georges and J. P. Maumus, inventors; Societe Europeenne de


Propulsion, assignee; US 5,514,445, 1996.

165. P. Breuet, F. Couchin, G. Fantozzi, P. Reynand and D. Rouby, Composites Science


& Technology, 1996, 56, 7, 817.

166. J. P. Solti, S. Mall and D. D. Robertson, Journal of Composites Technology and


Research, 1996, 18, 3, 167.

167. C. G. Cofer, J. Economy and Y. Xu, Composites Science & Technology, 1996, 56,
8, 967.

168. R. El Bouazzaoni, S. Baste and G. Camus, Composites Science & Technology,


1996, 56, 12, 1373.

169. R. Kahraman, Composites Science & Technology, 1996, 56, 12, 1453.

170. Advanced Composites Bulletin, 1997, 3, 4.

88
Particulate Fillers and Fibre Reinforcements

171. S. Q. Wu, H. Z. Wang and S. Tjong, Composites Science & Technology, 1996,
56, 11, 1261.

172. T. J. Hwang, M. R. Hendrick and H. Shao, Materials Science and Engineering A,


1998, 244, 1, 91.

173. S. K. Al-Oraimi and A. C. Seibi, Composite Structures, 1995, 32, 1-4, 165.

174. H. Burger, A. Koine, R. Maron and K. P. Miek, GAK Gummi Fasern Kunststoffe,
1995, 48, 7, 475.

175. R. P. Kumar and S. Thomas, Polymer International, 1995, 38, 2, 173.

176. G. Ahlblad, T. Reitberger, B. Stenberg and P. Danielsson, Polymer International,


1996, 39, 3, 261.

177. C. Joly, R. Gauthier and B. Chabert, Composites Science & Technology, 1996,
56, 7, 761.

178. K. Joseph, S.Thomas and C. Pavithran, Polymer, 1996, 37, 23, 5139.

179. K. P. Mieck, T. Reussmann and C. Bachmann, GAK Gummi Fasern Kunststoffe,


1996, 49, 8, 638.

180. S. Kakuk, inventor; no assignee, E 0751267, 1997.

181. N. Akiyama and S. Irie, inventors; ASK Corp., assignee; GB 2,202,152 A, 1997.

182. M. A. Khan, K. M. Ali Idriss, M. R. Al Imam and R. J. Mannan, Polymers


Plastics Technology and Engineering, 1997, 36, 1, 89.

183. S. Hill, New Scientist, 1997, 153, 2067, 36.

184. M. R. Vignon, D. Dupeyre and C. Garcia-Jaldon, Bioresource Technology, 1996,


58, 2, 203.

185. Reinforced Plastics, 1996, 40, 11, 16.

186. A. Paul, K. Joseph and S. Thomas, Composites Science & Technology, 1996, 56,
1, 25.

187. J. Gassan and T. Bledzki, GAK Gummi Fasern Kunststoffe, 1996, 50, 5, 360.

188. C. Sempio, Industria Cotoniera, 1997, 50, 4, 2297.

89
Handbook of Polymer Blends and Composites

189. R. Narayan and M. Kotnis, inventors; Evercorn, assignee; US 5,728,824, 1998.

190. S. Carpenter, Reinforced Plastics, 1997, 41, 11, 22.

191. F. Bergmann, inventor; Color Plastic Chemie, assignee; US 5,723,522, 1998.

192. K. P. Mieck, T. Reussmann and Ch. Hauspurg, GAK Gummi Fasern Kunststoffe,
1998, 52, 9, 740.

193. Reinforced Plastics, 1998, 42, 7, 26.

194. J. Gassan, I. Mildner and V. Bledzki, Technical Textiles, 1998, 41, 2, 74.

195. J. George, S. S. Bhagawan and S. Thomas, Composites Science & Technology,


1998, 58, 9, 1471.

196. H. Blumberg, Technical Textiles, 1997, 40, 1, 7.

197. H. Blumberg, Chemical Fibres International, 1997, 50, 4, 297.

198. High Performance Textiles, 1996, 1, 2.

199. T. Matsunase and T. Takada, inventors; Toray Industrie Inc., assignee; US


5,591,509, 1996.

200. G.M. Lorenz and W. Fester, inventors; Hoechst AG, assignee; US 5,591,509, 1997.

201. Advanced Composites Bulletin, 1995, 8, 2.

202. High Performance Textiles, 1996, 11, 8.

203. M. L. Allan and L. E. Kukacka, Waste Management, 1995, 15, 2, 171.

204. E. K. Tschegg and N. Finger, Composites Science & Technology, 1996, 56, 8, 947.

205. M. Elser, E. K. Tschegg and S. E. Stanzl-Tschegg, Composites Science &


Technology, 1996, 56, 8, 933.

206. T. Stern, A. Teishev and G. Morom, Composites Science & Technology, 1997, 57,
8, 1009.

207. Reinforced Plastics, 1998, 42, 1, 24.

208. J. M. Hofste, M. J. E. Kersten, J. Turnhout and A. J. Pennings, Journal of


Electrostatics, 1998, 45, 1, 69.

90
Particulate Fillers and Fibre Reinforcements

209. Non-wovens Report International, 1996, 289, 6.

210. High Performance Textiles, 1996, 2, 7.

211. F. Suhara, K. N. Kutty, G. B. Nando and A. K. Bhattacharya, Polymer Plastics


Technology and Engineering, 1998, 37, 1, 57.

212. F. Suhara, K. N. Kutty, G. B. Nando, Plastics, Rubber & Composites: Processing


& Applications, 1995, 24, 1, 37.

213. T. Masuda, Y. Horii and T. Iwama, inventor; Toray Industries Ltd., assignee; GB
2,292,385, 1996.

214. Advanced Composites Bulletin, 1996, 10, 5.

215. R. Gilat and J. Aboudi, Composite Structures, 1995, 32, 1-4, 81.

216. P. Lugez, TUT Textiles Usages Techniques, 1996, 20, 15.

217. G. Leumer and E. Gebauer, TUT Textiles Usages Techniques, 1996, 20, 59.

218. J-B. Donnet and R. C. Bansal, Carbon Fibres, Third Edition, Marcel Dekker Inc,
New York, USA, 1998.

219. J. Longhlan and M. Ata, Composite Structures, 1995, 32, 1-4, 13.

220. J. Eiblmeier and J. Longhlan, Composite Structures, 1995, 32, 1-4, 97.

221. M. S. Found and M. J. Friend, Composite Structures, 1995, 32, 1-4, 115.

222. H. Albertsen, J. Ivens, P. Peters, M. Wevers and I. Verpoest, Composites Science


& Technology, 1995, 54, 2, 133.

223. M. S. Found and C. I. Howard, Composite Structures, 1995, 32, 1-4, 159.

224. L. V. Smith and S. R. Swason, Composite Structures, 1995, 32, 1-4, 177.

225. M. Higashino, K. Takamura and T. J. Fujii, Composite Structures, 1995, 32,


1-4, 357.

226. K. S. Jeong, D. G. Lee and S. H. Oh, Composite Structures, 1995, 32, 1-4, 557.

227. Y. G. Kim, K. S. Jeong and D. G. Lee, Composite Structures, 1995, 32, 1-4, 575.

228. S. T. Mileiko, A. M. Rudnev and M. V. Gelachov, Composites Sciences &


Technology, 1995, 55, 3, 255.

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Handbook of Polymer Blends and Composites

229. S. Singh and I, TUT Textiles a Usages Techniques, 1996, 19, 13. K. Partridge,
Composites Sciences & Technology, 1995, 55, 4, 319.

230. J. Varga and J. Karger-Kosis, Polymer, 1995, 32, 25, 4877.

231. H. Hamada and S. Ramakrishna, Composites Sciences & Technology, 1995, 55,
3, 211.

232. J. A. Barnes and C. Newton, Composites Sciences & Technology, 1995, 55, 4, 287.

233. S. S. Cheon, J. H. Choi, D. G. Lee, Composite Structures, 1995, 32, 1-4, 491.

234. M. D. Gilchrist, A. J. Kinloch, F. L. Matthews and S. O. Osiyemi, Composites


Sciences & Technology, 1996, 56, 1, 37.

235. M. Yamanaka, S. Maegawa, Y. Nakamura and Y. Kimura, Seni Gakkaishi, 1996,


52, 1, 12.

236. B. Revzin, D. Fuks and J. Pelleg, Composites Sciences & Technology, 1996, 56, 1, 3.

237. L. V. Smith and S. R. Swanson, Composites Sciences & Technology, 1996, 56, 3, 359.

238. H. Tennent, R. W. Hausslein, N. Leventis and D. Moy, inventors; Hyperion


Catalysis International Inc, assignee; EP 0703858, 1996.

239. TUT Textiles Usages Techniques, 1996, 19, 13.

240. N. Chaud, J. V. Kaerzer and G. Hinrichsen, Journal of Scientific & Industrial


Research, 1996, 55, 4, 277.

241. J. Ivens, H. Albertsen, M. Wevers, I. Verpoest and P. Peters, Composites Sciences


& Technology, 1995, 55, 2, 147.

242. D. O. Ursenbach, R. Varziri and D. Delfosse, Composite Structures, 1995, 32, 1-


4, 197.

243. L. Caramaro and G. Vignie, TUT Textiles Usages Techniques, 1995, 16, 29.

244. L. Ye, K. Friedrich, J. Kastel and Y-W. Mai, Composites Sciences & Technology,
1995, 55, 4, 349.

245. M. Davenport, Reinforced Plastics, 1996, 40, 2, 26.

246. E. Leblanc, C. Piuna, P. Sigety and I. Vincon, Composites Sciences & Technology,
1996, 56, 7, 855.

92
Particulate Fillers and Fibre Reinforcements

247. A. Paollozzi and I. Peroni, Composite Structures, 1996, 35, 4, 435.

248. T. Muraki and M. Tokunon, inventors; Toray Industries Inc, assignee; US


5,599,612, 1997.

249. I. Yamamoto, A. Yoshiya and T. Nishimoto, inventors; Mitsubishi Chemical


Corporation, assignee; E 0761849, 1997.

250. J. K. Choi and D. G. Lee, Composite Structures, 1997, 37, 2, 241.

251. K. P. San, T. K. Chaki and D. Khastgir, Polymer, 1998, 39, 25, 6461.

252. M. Ahrens, Advanced Composites Bulletin, 1998, 8, 17.

253. K. E. Atkinson and C. Kiely, Composites Science & Technology, 1998, 58, 12,
1917.

254. T. Nojima and T. Kusaka, JSME International Journal, Series A: Mechanics and
Material Engineering, 1998, 41, 2, 225.

255. K. Gamble, M. Pilling and A. Wilson, Composite Structures, 1995, 32, 1-4, 265.

256. J. Longhlan, Composite Structures, 1996, 35, 1, 101.

257. D. R. Snyder and W. D. Thompson, inventors; Aircraft Braking Systems


Corporation, assignee; GB 2,298,611 A, 1996.

258. H. Kishi and N. Odagiri, inventors; Toray Industries Inc, assignee; US 5,557,831,
1996.

259. Advanced Composites Bulletin, 1996, 10, 6.

260. J. Raghovan and M. Meshii, Composites Science & Technology, 1997, 57, 4,
375.

261. P. S. Winckler, inventor; General Motors Corporation, assignee; US 5,662,993,


1997.

262. J. S. Bradley, Advanced Composites Bulletin, 1998, 6, 8.

263. J-M. Ting and M. L. Lake, inventors; Applied Sciences Inc, assignee; US
5,814,408, 1998.

264. J. L. Corden, inventor; Hexcel Corporation, assignee; EP 0670776, 1995.

93
Handbook of Polymer Blends and Composites

265. P. Rerat, TUT Textiles Usages Tecniques, 1996, 19, 46.

266. S. C. Khatri and M. J. Koczak, Composites Science & Technology, 1996, 56, 6,
181.

267. Advanced Composites Bulletin, 1996, 4, 2.

268. Reinforced Plastics, 1996, 40, 2, 36.

269. A. J. Mullender and L. J. Rodgers, inventors; Rolls-Royce plc, assignee; GB


2,294,709 A, 1996.

270. S. C. Khatri and M. J. Koczak, Composites Science & Technology, 1996, 56, 4,
473.

271. C. Adrian, TUT Textiles Usages Techniques, 1996, 20, 55.

272. D. Leveque, M. H. Auvray, Composites Science & Technology, 1996, 56, 7, 749.

273. D. Tingley, High Performance Textiles, 1996, 9, 11.

274. X. Gu and R. J. Young, Textile Research Journal, 1997, 67, 2, 93.

275. B.Y. Park, S. C. Kim and B. Jung, Polymers for Advanced Technologies, 1997, 8,
6, 371.

276. V. Bianchi, P. Goursat and W. Sinkler, Journal European Ceramic Society, 1997,
17, 12, 1485.

277. P. Heidel, Man-Made Fibre Year Book (CTI), 1989, 24.

278. G. Christoph, Man-Made Fibre Year Book (CTI), 1989, 29.

279. F. Schultze-Gebhardt, Technische Textilien, 1993, 36, 10, T194.

280. H. van der Werff and M. H. Hoffman, Chemical Fibres International, 1996, 46,
12, 435.

281. E. Peter, Advanced Composites Bulletin, 1997, 5, 2.

282. H. Stumpf, P. Schwartz, M. Lienkamp and K. Schulte, Composites Science &


Technology, 1995, 54, 2, 211.

283. R. Neuert and H. Jung, inventors; Hoechst AG, assignee; EP 0688743, 1995.

94
Particulate Fillers and Fibre Reinforcements

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