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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.
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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,
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.
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]:
(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]:
Low moisture absorption and high bulk density; they should preserve their properties
during storage prior to compounding.
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.
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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
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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
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
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.
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.
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Particulate Fillers and Fibre Reinforcements
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.
Fibre has an AR of > 10, high strength, dimensional stability, heat resistance and chemical
resistance.
Limestone
Marble
Dolomite
Alumina
Magnesium
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Handbook of Polymer Blends and Composites
These have good electrical and/or thermal conductivity or magnetic properties, they reduce
friction, and they are expensive.
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).
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
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.
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Handbook of Polymer Blends and 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
Glass spheres are used as fillers in both thermoplastics and thermosetting compounds.
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.
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Handbook of Polymer Blends and Composites
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Particulate Fillers and Fibre Reinforcements
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).
In the analysis and specification of fillers, several properties are of particular importance:
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]
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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,
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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.
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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).
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.
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Particulate Fillers and Fibre Reinforcements
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%.
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:
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Handbook of Polymer Blends and Composites
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.
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.
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
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Particulate Fillers and Fibre Reinforcements
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Handbook of Polymer Blends and Composites
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.
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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 basic commercial form of continuous glass fibres is a strand that is a collection of
parallel filaments, numbering 204 or more.
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].
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]:
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 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:
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Particulate Fillers and Fibre Reinforcements
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
67
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.
Some of the properties of the alumina fibres are listed in Table 2.8.
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:
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.
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].
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.
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.
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.
70
Particulate Fillers and Fibre Reinforcements
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.
Carbon fibres are produced by heat treatment of organic precursors such as rayon [218,
219-224], polyacrylonitrile (PAN) and pitch.
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.
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].
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].
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
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.
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.
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.
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].
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].
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Handbook of Polymer Blends and Composites
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.
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
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.
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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Particulate Fillers and Fibre Reinforcements
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Handbook of Polymer Blends and Composites
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Particulate Fillers and Fibre Reinforcements
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178. K. Joseph, S.Thomas and C. Pavithran, Polymer, 1996, 37, 23, 5139.
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186. A. Paul, K. Joseph and S. Thomas, Composites Science & Technology, 1996, 56,
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187. J. Gassan and T. Bledzki, GAK Gummi Fasern Kunststoffe, 1996, 50, 5, 360.
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192. K. P. Mieck, T. Reussmann and Ch. Hauspurg, GAK Gummi Fasern Kunststoffe,
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204. E. K. Tschegg and N. Finger, Composites Science & Technology, 1996, 56, 8, 947.
206. T. Stern, A. Teishev and G. Morom, Composites Science & Technology, 1997, 57,
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213. T. Masuda, Y. Horii and T. Iwama, inventor; Toray Industries Ltd., assignee; GB
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215. R. Gilat and J. Aboudi, Composite Structures, 1995, 32, 1-4, 81.
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,
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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.
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.
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.
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229. S. Singh and I, TUT Textiles a Usages Techniques, 1996, 19, 13. K. Partridge,
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231. H. Hamada and S. Ramakrishna, Composites Sciences & Technology, 1995, 55,
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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.
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.
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,
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246. E. Leblanc, C. Piuna, P. Sigety and I. Vincon, Composites Sciences & Technology,
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253. K. E. Atkinson and C. Kiely, Composites Science & Technology, 1998, 58, 12,
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254. T. Nojima and T. Kusaka, JSME International Journal, Series A: Mechanics and
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260. J. Raghovan and M. Meshii, Composites Science & Technology, 1997, 57, 4,
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263. J-M. Ting and M. L. Lake, inventors; Applied Sciences Inc, assignee; US
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266. S. C. Khatri and M. J. Koczak, Composites Science & Technology, 1996, 56, 6,
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270. S. C. Khatri and M. J. Koczak, Composites Science & Technology, 1996, 56, 4,
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280. H. van der Werff and M. H. Hoffman, Chemical Fibres International, 1996, 46,
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283. R. Neuert and H. Jung, inventors; Hoechst AG, assignee; EP 0688743, 1995.
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288. S. W. Shalaby and M. Deng, inventors; Smith & Nephew Richards, Inc., assignee;
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293. S. Shalom, H. Harel and G. Marom, Composites Science & Technology, 1997,
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296. B. J. Field and R. Soar, inventors; Pacific Safety Products Inc., assignee; US
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