CHAPTER I

I INTRODUCTION

The importance of fillers in the rubber compounds is

well known. Fillers are widely used to enhance the
performance of rubbers and other polymeric materials.
Filler characteristics such as size and shape of particles
and aggregates, chemical nature and porosity of surface,
dispersibility and tendency to agglomerate and form
secondary filler networks determine its effect on rubber
compounds.

Fillers can be classified into black and non-black.

Soon after carbon black was discovered to be an active
filler in rubber, at the beginning of this century, it
became one of the most important components in the
manufacture of rubber products, with a consumption second
only to rubber itself.

The total Indian consumption of black and non-black

fillers by the rubber industry during 1995-95 is estimated
at about 3,30,000 metric tonnes corresponding to an
average loading of 50 phr. The consumption of carbon
black was more than that of non-black fillers and amounts
to about 2 lakhs metric tonnes during 1995-96.
 The results of many studies have been published
describing one aspect or another of the behaviour of
fillers and these are still appearing. Some excellent
review papers and books, survey and analyse the available
information such as those by Studebaker [ 1 ], Kraus [ 2,3 ],

Donnet and Voet [4], and Medalia [5]. However,

publications on the use of metallic powders as filler and
its effect on mechanical and electrical properties of
elastomers are only few in number [6,7]. In the following
pages, a detailed account of the work done to study the
effect of fillers on rubber compounds and vulcanisates is
presented.

1.1 Types of Carbon Blacks

Carbon blacks are classified into furnace blacks,

channel blacks, thermal blacks, lamp black and acetylene
black, etc. based on their method of manufacture. Among
these, the furnace type blacks account for a lions share
of the total black consumed by the rubber industry.

The main reason for the predominant use of furnace

type carbon blacks, in elastomers, is the reinforcement
they impart to the vulcanisates [1,2,8], Incorporation of
carbon blacks into rubber gives enhanced modulus, improved
fatigue and abrasion resistance and better overall
performance. A simple classification of rubber grade
furnace type carbon black is based on surface area and
aggregate morphology measured by dibutyl phthalate
absorption (Table 1.1).

Table 1.1 Properties of furnace blacks

Black Surf ace Average DBP

Name particle ab o r p t i o n
ASTM Type s i z e (nm) S
( c /g)

NllO SAF Super abrasion furnace 140 20-25

N220 ISAF Intermediate super

abrasion furnace 120 24-33

N330 HAF High abrasion furnace 80 28- 36

N550 FEF Fast extrusion furnace 45 39-55

N660 GPF General purpose furnace 37 50 - 60

N774 SRF Semi-reinforcing furnace 28 70-96

1.2 Types of Non-black Fillers

Non-black fillers are classified as

a) Fillers used mainly to reduce cost
b) Semi-reinforcing fillers
c) Reinforcing fillers used to achieve high
performance in non-black products.

Non-black fillers such as ground limestone, barytes,

clay, kaolin, etc. were used in order to extend and
cheapen the compound since it was found that in natural
rubber quite a bit of these fillers could be added without
detracting too much from the final vulcanisate properties.
These inorganic fillers are in the non to low reinforcing
range and have high specific gravities compared to the
carbon blacks or synthetic silicas and silicates.
Recently, new technical developments show promise of
closing the wide performance gap between the carbon blacks
and inorganic fillers. These included the use of silane
coupling agents [9-111, pretreatment of filler surface
with silanes and the surface grafting of reactive
polymers.

Zinc oxide was the standard reinforcing filler for

many years until it was replaced by carbon black during
the period of 1917-1929. Today there are hundreds of
commercial inorganic fillers providing a performance range
from non-reinforcing to highly reinforcing, giving the
rubber compounder a wide choice of cost benefit options.
Table 1.2 gives a simple classification of non-black
fillers.
Table 1.2 Classification and properties of non-black
fillers

Product types Averaqe Surface Specific Volume Oil

and grades particle area gravity specific pH absorption
size (nr) (r2&) surface (9/100 q)
area
( r2/cr3

Silica
precipitated, hydrated 16-100 40-170 1.93-2.05 77-332 5.7-9.5 160-240

Silica
anhydrous, f umed 8-15 200-380 2.10 420-798 3.9-4 .O 150-200

Aluminium silicate
precipitated, hydrated 25 130 2.10 273 10.0 140

Clays 300-1500 8-22 2.60-2.68 21-58 4 .I-7.0 29-52

Calcium carbonate
precipitated 50-700 8-74 2.42-2.71 22-179 9.4 28.60

1.3 Reinforcement of Elastomers by Fillers

A reinforcing filler improves the modulus and failure

properties of the final vulcanisate. A practical
definition of reinforcement is the improveinent in service
life of a rubber article. The reinforcement of elastomers
by particulate fillers, to a large extent depends on
polymer properties, filler characteristics and processing
methods. The primary filler factors influencing elastomer
reinforcement are:
 a) The particle size or surface area which together
with filler loading, determines the effective
contact area between the filler and the polymer
matrix.
b) The structure or the degree of irregularity of
the filler unit which plays an essential role in
the restrictive motion of elastomer chains under
strain.
c) The surface activity which is the predominant
factor with regard to filler-filler and filler-
polymer interaction.

I.3.1 Effect of Particle Size of the Filler on

Reinforcement

The most important parameter influencing

reinforcement i s primary particle size [ 2 ] . Coarse blacks
consist of aggregates of simple particles.

The more reinforcing blacks have much smaller primary

particles, fused together to form primary aggregates. The
size of the primary particles determines the surface area
of aggregates since the area used up by fusion of
particles is relatively low. These primary aggregates are
the units, determining most of the properties the black
will impart to the rubber compound.
 The total surface area of a particulate solid is
directly related to its particle size. If all particles
are spheres of the same size, the surface area fAsf per
gram of the filler is given by the Equation 1.1.

where d is the diameter and p is the density. In reality

there is always a distribution of sizes that can be
averaged in various ways [12] and particles are usually
far from round [13].

Particle size or surface area is a factor of greater

importance in reinforcement because it vary over a wide
range. Coarse inorganic fillers have surface areas of
about 1 m2/g, fine silicas upto 400 m2/cg, and in the case
of rubber grade carbon blacks, there is a variation from
6 m2/g for medium thermal blacks (N991) to 250 m2/g for

conductive blacks. So there is a factor of 40 between the

highest and lowest surface area. No other factor in
reinforcement varies over such a wide range,

The use of the same particle size description for

silicas and carbon blacks does not imply the same
reinforcement. This difference essentially disappears
when coupling agents are used with the silicas. Then the
silica and carbon black of similar size provide equivalent
reinforcement, as measured by modulus, tensile strength
and tire-tread wear. So given equivalent surface
activity, particle size does relate to reinforcement in
the same way for the two types of fillers. Among various
types of silicas and silicates, majority are confined to
the smaller size classes (c50 nm) and minority in the size
classes larger than 50 nm.

Carbon black particles with pores and cracks have

surface area greater than blacks of similar size without
such features. This leads to an increased number of
particles per unit weight. Thus porous black gives
decreased resilience and increased electrical conductivity
when compared with equal weight loadings of non-porous
blacks.

1.3.2 E f f e c t of S t r u c t u r e of the Filler on Reinforcement

Structure of carbon black aggregates is important in

understanding the role of carbon blacks in reinforcement
and its influence on properties such as modulus, viscosity
and die swell which are known to be shape dependent.
Aggregate shape or \structure8 increases with greater
aggregate complexity and larger number of particles per
aggregate. Highly structured aggregates typically have
branches that form voids between them, where polymer can
be occluded, which results in higher effective loading of
the carbon black in an elastomeric ' compound.
Skeletonisation method has been used for the first
quantitative and direct measurement of branching in carbon
black aggregates [14].

Carbon black aggregates are classified into four

different shape categories that included (a) spheroidal,
(b) ellipsoidal, (c) linear, and (d) branched [15]. Non-
spherical particles have a volume packing which is less
dense than that of spheres, leaving a greater volume of
voids between the particles.

Filler aggregates in elastomer matrix have a tendency

to form agglomerates, especially at high loadings leading
to chain-like filler structures or clusters. These are
generally termed secondary structure or filler network,
even though they are not comparable to the continuous
polymer network. Such a structure has a significant
effect on the properties of filled rubber. Filler
networking is determined by the attractive potential \Sft
between aggregates in rubber as well as by their distance.
Wang et al. [16] studied the role of the distance between
filler aggregates in the dynamic properties of filled
vulcanisates, using fillers with different attractive
potential values. This study demonstrated that, at the
same interaggregate distance, lower Sf of the filler leads
to weaker filler network which is readily brokeh down and
reconstituted.

The most common method of determining the \structuret

of carbon black is based on the measurement of the
combined intra and interaggregate void volume by oil
absorption (DBPA, ASTM D-2414). The internal void volume
may also be measured by the compressibility of the carbon
black at high pressures [17]. High structured carbon
blacks have high oil absorption and lower compressibility
for a given weight of carbon black. Work has been
done extensively for carbon black morphological
characterisation [18,19]. Tables 1.3 and 1.4 show in
detail the effects of decreasing particle size and
increasing structure on the vulcanisate properties and
rheological behaviour of unvulcanised compounds
respectively [20].

Table 1.3 Effect of particle size and structure on

vulcanisate properties

Decreasing Increasing
Vulcanisate properties particle size structure

Rate of cure Decreases Little

Tensile strength Increases Decreases
Modulus Increases to Increases
maximum and
' then decreases
Hardness Increases II
 , .\ - \.
. .>..! .
.\>.'',$
Elongation Decreases to Dec.-&ses- - -.
-. .
.
. . -.
minimum and .-
--. . ----.-.:
then increases
Abrasion resistance Increases Increases
Tear resistance II
Little
Cut growth resistance Decreases
Flex resistance II

Resilience Decreases Little

Heat build up Increases Increases
slightly
Compression set Little Little
Electrical conductivity Increases Little

Table 1.4 Effect of particle size and structure on

processing characteristics

Decreasing Increasing
Processing properties particle size structure

Loading capacity Decreases Decreases

Incorporation time Increases Increases
Oil extension potential Little Increases
Dispersability Decreases Increases
Mill bagging Increases
Viscosity 11

Scorch time Decreases Decreases

Extrusion shrinkage 11 11

Extrusion smoothness Increases Increases

Extrusion rate Decreases Little
I.3.3 Effect of Polymer-Filler Interaction on
Reinforcement

When carbon black is mixed into the rubber in

conventional equipment, the first step is penetration of
rubber into the void space replacing the trapped air and
eliminating loose black. This occurs before the black is
randomly dispersed. If at this stage considerable rubber-
black interaction occurs, subsequent dispersion is
rendered more difficult as bound rubber cements many
primary aggregates together. For this reason, low
structure, higher surface area blacks are difficult to
disperse; their small void space and dense packing lead to
high local black concentration and their large surfaces
provide ample opportunity for early interaction with
polymer. At the same time such blacks are quite rapidly
incorporated. High structured blacks are more slowly
incorporated but more easily attain a satisfactory degree
of dispersion.

Continued mixing decreases the number of

interaggregate contacts and increases the ayerage distance
of separation of the aggregate from each other. Electron
microscopic studies have shown the breakdown of aggregates
to two-third of their original size, with the extent of
breakdown increasing with increased structure and
increased polymer-filler interaction [21]. Even in good
dispersions, there exist many interaggregate physical
contacts.

Mechanical processing of carbon blacks by a novel

pressure milling technique [ 2 2 ] provides a controlled
breakdown of primary carbon black aggregates. In rubber
vulcanisates, the pressure milled carbon blacks give about
the same vulcanisate properties as normal carbon blacks
with the same void volume or DBP absortion value.

The surface interaction between fillers and rubber

molecules or network segments involves a range of bond
energies from relatively weak Van der Waals force to very
strong chemical bonds [23]. The number of each kind of
interaction is unknown [24]. In all cases, physical
adsorption undoubtedly occurs to varying degrees depending
on the particular surface and molecular segments.
Evidence for chemical bonding at the interface is also
conclusive for some systems [25]. The relative
contributions of physical and chemical interactions to
reinforcement, differ both with the nature of the filler
and the elastomer. When physical interaction is high,
such as that for carbon black in hydrocarbon rubbers,
there is little added contribution to reinforcement from
the chemical bonding, although this may contribute to
other desirable properties. Chemical interaction improves
interfacial wetting and adhesion, improves dispersion and
prevents reflocculation of dispersed particles: Another
effect of chemical interaction is actual bridging of the
particle surface to the elastomeric network 126,271.

The adsorption of polymer segments on the filler

surface leads to some loss of mobility of the chains.
Studies of proton magnetic resonance in carbon black-
reinforced rubbers have shown that there is a loss in
segmental mobility, but severe restriction of motion is
confined to a layer of 5 A thick at the surface, i .e., a
distance of few carbon lengths along the polymer chain
1281. On the other hand, the chains of bound rubber
extend far into the polymer matrix where they freely
intermix with unadsorbed rubber molecules. On
vulcanisation, they become part of the network,
undistinguishable from free rubber.

1.3.4 Surface A c t i v i t y

The surface activity is related to different chemical

groups on the surface, such as carboxyl, quinone, phenol
and lactone. Unlike white fillers whose ihemical groups
(hydroxyl and/or metal oxide groups) play an important
role in their reinforcing ability for elastomers, the
surface chemistry of carbon black has a significant effect
on the vulcanisation of compounds. Surface energy of
blacks is of much greater importance than their chemical
nature with regard to the mechanical propert'ies of the
filled elastomers, particularly when general purpose
hydrocarbon rubbers are concerned. Surface energies of a
series of carbon blacks and the interaction between
carbon blacks and elastomers were estimated by Wang and
Wolff [29]. Inverse Gas Chromatography (IGC) is one of
the most sensitive methods for the investigation of filler
surface energies 130-321.

I.3.5 Effect of Bound Rubber on Reinforcement

Bound rubber [ 33-35 ] has been used to characterise

filler-rubber interaction. Without the formation of bound
rubber, carbon black acts as an inert filler, lowering
modulus and tensile strength [36]. The bound rubber in a
compound generally depends upon the surface area, with a
weaker dependence on the structure, as was found for a
series of compounds 1331. Wolff et al. 1371 conducted a
study on bound rubber content in SBR compounds with 1 7
carbon blacks covering a whole range of rubber grades and
tested for bound-rubber content. It was. found that the
bound rubber content of a polymer at high loadings is
higher for large surface area carbon blacks. In compounds
using silica as the filler, the bound rubber can be
greatly altered by chemically modifying the surface using
the active hydroxyl sites on the surface to graft blocking
agents or coupling agents.
 In a series of compounds using fumed and precipitated
silicas, Donnet [38] used a short chain alcohol, methanol,
and a long chain alcohol, hexadecanol to modify the silica
surface. The surface modification effectively prevented
the formation of bound rubber with either SBR or NR. The
reinforcement of the compound decreased substantially with
surface modification.

I. 3 - 6 Role o f Coupling Agents

Owing to the hydrophilic character, silicas as such

are incompatiable with the rubber matrix and thus lack in
full rubber reinforcing ability. In the presence of a
coupling agent, which chemically binds silica with rubber,
marked increase in reinforcement is observed in silica-
filled rubber vulcanisates. In this respect, silanes with
appropriate functionality (alkoxy silyl groups) have been
successfully employed as coupling agents [9-11,391.
It has been reported [40] that bis(diisopropy1)
thiophosphoryl disulfide, an entirely new class of
compound can also react with both silica and rubber during
vulcanisation.

Wang and Wolff [41] showed that silane modified

silica increase its compatibility with hydrocarbon
elastomers, hence improves filler dispersion, compound
processability and certain vulcanisate properties.
Titanate coupling agents are used for fillers, extenders
and reinforcing agents in thermosetting and thermoplastic
polymer systems [42].

The influence of fumed silica on the reinforcement

properties of silicone rubber was studied by Cochrane and
Lin [43]. The network in the vulcanisate is held together
by silica-silica interactions and silica-polymer-silica
bridge bonds between the silica aggregates. Increasing
the silica loading, surface area and structure level
increase the number of interactions and hence the network
strength. Wang et al. [44] conducted a study to
characterise the reinforcement of in situ precipitated
silica in polydimethyl siloxane (PDMS) elastomers in shear
and in biaxial extension and the results indicated that
PDMS networks filled by the in situ precipitated silica
have good mechanical properties, not only in uniaxial
elongation but in shear and biaxial extension as well.
The performance of silicas in polar elastomers is
studied [45] using a series of silica and carbon black
loaded acrylonitrile butadiene (NBR) compounds with
different acrylonitrile contents. The study shows that
the changes in viscoelastic properties of the silica-
filled compounds can be attributed to improved polymer
filler interactions relative to the interaction involved
in carbon black-filled compounds.
1.4 Effect of Filler on Viscosity of the Rubber Compound

The flow of filled rubber compounds in the

unvulcanised state is of obvious technological importance.
The melt viscosity of rubber mixes increases with
decreasing particle size and with increasing structure.
The melt viscosity of the unfilled polymers is strongly
dependent on their molecular weight distribution and the
presence or absence of long chain branching [46]. The
reason why carbon black imparts so much greater viscosity
to the rubber are (a) occlusion of rubber within and
between the carbon aggregates [47], (b) immobilisation of
a layer of elastomer at the filler surface [481. Changes
in viscosity of filled rubbers is attributed to an
entanglement/bound rubber model/for a series of SBR and NR
compounds [49,50]. Physical properties of silica were
reported to affect the viscosity of reinforced rubbers.
Hewitt [51] reported that compound viscosity is directly
related to silica surface area. It is also observed that
highly developed filler networks of silicas give rise to
high viscosities of the filled compounds [52].

Silicas and silicates generally produce higher Mooney

viscosity in rubber mixes than other fillers of comparable
particle size. This difference between types of filler
became less pronounced as the average filler particle size
increased [53]. At small size (-20 nm) HS-200 silica
produced a significantly higher viscosity than carbon
blacks of comparable size [54]. At large particle size
(- 40 nm) the silica and black produced similar
viscosities [53]. In view of the greater increase in
viscosity with small particle size, the primary emphasis
on improving viscosity was on the more reinforcing
silicas. One such study [55] was conducted using similar
silicas with average ultimate particle size in the
18-22 nm range. The use of silane coupling agents was
also an effective means of reducing viscosity in some
elastomers, when silica was the filler [56].

With rare exception, the viscosity of high molecular

weight rubbers is shear rate dependent. The presence of
filler always increases the shear dependence; i.e., the
increase in viscosity caused by the filler is the greatest
at low shear rates. The viscosity at vanishing low shear
rates becomes effectively infinite. The phenomenon is the
result of secondary filler agglomeration, leading to the
establishment of a weak filler network held together by
Van der Waals forces. This network is. progressively
disrupted by increasing shearing stresses.

It has been shown that higher shear rates reduced the

difference between types of fillers [57-591, so that
silicas and carbon blacks have similar viscosities in high
shear rate processes, such as extrusion and injection
moulding.
1.5 Effect of Filler on Crosslinking Process and
Cure Characteristics

Since a large proportion of natural rubber consumed

in manufactured goods is compounded with carbon black as a
reinforcing filler, it is important to understand the
influence of individual carbon blacks upon the reactions
taking place during sulphur vulcanisation. The possible
influence of carbon black fillers on the total
concentration of chemical crosslinks and on the
proportions of mono-, di- and polysulphidic crosslinks is
regarded as of particular relevance in view of the
importance of these factors in determining vulcanisate
properties [60,61].

The change in concentration of the effective chains

of a rubber network caused by the presence of the filler
in vulcanised rubbers has been investigated upto the
present by means of the equilibrium swelling method [62-
651 with use of Flory equation [66,67] as well as by
determination of the equilibrium modulus [68]. Kraus [63]
determined the crosslink density of a large series of
vulcanisates, filled with carbon black and unfilled. From
the increase in crosslink density in the filled
vulcanisates, he deduced the number of polymer-filler
bonds formed during mixing and vulcanisation as well as
the number of those that are formed by the catalytic
effect of the filler in course of the crosslinking
reaction. Kraus [63] proved further that the filler in a
,
vulcanised rubber, crosslinked with sulphur has no
influence on the content of bound sulphur, but influences
the number and character of the bonds formed in the
system.

Janacek [69] has studied the influence of fillers on

the degree of crosslinking of natural rubber and found
that the crosslink density increased proportionally with
the concentration of the carbon black by volume. Work by
Cotton [70] has shown that the chemistry of carbon black
surface plays an important part in the initial steps
preceeding the actual crosslinking reaction as well as the
crosslinking rate itself. Oscillating disc rheometer [71-
731 can be used to study the effect of fillers on rate of

cure and crosslinking. The rheometer curve (Fig. 11.2)

taken at curing temperature indicates the induction
period, the course of the crosslinking reaction, the
occurrence of a plateau or reversal and the time at which
optimum cure is reached. The time required to achieve 90%
of the maximum increase in torque (MH) over the minimum
(ML) has been set as the time for optimum cure. MH will
also indicate the characteristic effects of the filler.

Bhowmick and De [74] have studied the effect of

addition of HAF black on the kinetics of vulcanisation and
the changes in the network structure of natural rubber
mixes with a DTDM based accelerator system at 1 5 0 ' ~and
1 8 0 " ~ . Results showed that addition of HAF black enhanced

the polysulphidic crosslinks as well as total crosslinks.

They have observed that in the gum vulcanisate the
polysulphidic crosslinks decrease continuously with cure
time. Loo [75] and Mukhopadhyay and De [76] also made
similar observations. In the filled system, however, the
polysulphidic crosslinking passes through a maximum which
shows that HAF black takes part in the actual sulphuration
processes.

Previously, Porter [77] reported that HAF black

influences the chemistry of sulphuration of the
conventional system and has little effect on the EV system
of NR. However, Bhowmick and De [74] showed that HAF
black has a pronounced effect on the EV system as well.
Previously [78] the increased crosslink density in the
filled system has been attributed to the increased
polymer-filler attachment which gives rise to restricted
swelling in solvents. The recent observations [74] point
out that the filler surface may catalyse the sulphuration
processes and the observed increase in crosslink density
may be due to increase in covalent crosslinks and not
merely due to polymer-filler attachment.

Duchacek [79] has studied the effect of HAF carbon

black on the course of the tetramethylthiuram disulphide
accelerated sulphur vulcanisation of natural -rubber at
to~ 1 4 0 ~ ~ .Results show that HAF
temperatures from 1 0 0 ~
black does not alter the mechanism of the thiuram
accelerated sulphur cure. The rate constants of
vulcanisation rise considerably when HAF black is used and
is dependent on the HAF black content of the rubber
compound. The activation energies of vulcanisation are
same as in carbon black-free mixture.

The effect of zinc oxide concentration on the course

of tetramethylthiuram disulphide accelerated sulphur
vulcanisation of natural rubber has been investigated by
Duchacek [80] and found that the concentration of zinc
oxide has practically no influence on the rate of thiuram
accelerated sulphur cure. The values of the ultimate
extents of crosslinking increase with increasing zinc
oxide content in the rubber compound upto a certain limit
corresponding to the theoretical amount of zinc oxide,
which is necessary for the formation of zinc
dimethyldithiocarbamate from tetramethylthiuram disulphide
and zinc oxide during the vulcanisation reaction.

Effect of aerosil [81] on the course of thiuram

accelerated sulphur vulcanisation of natural rubber from
100°C to 145°C shows that aerosil speeds up the course of

the vulcanisation upto the value corresponding to the rate

of zinc dimethyldithiocarbamate accelerated sulphur cure.
 Hema Acharya [82] conducted a systematic study by
selecting two carbon blacks namely, HAF and ISAF and
changing their dosage to see their effect on the reaction
kinetics for NR and polybutadiene rubber. She reported
that the vulcanisation reaction seems to be of first order
where k value depends on temperature and not on dosage of
carbon black.

1.6 Effect of Filler on Vulcanisate Properties

The effect of fillers on the mechanical properties of

elastomers is primarily of great interest because fillers
can be used very effectively to enhance the ultimate
properties. At the same time, however, fillers also
affect the viscoelastic properties at small and
intermediate strains.

I Effect on Modulus

Carbon black raises the modulus of rubber by

geometrical constraints which perturb the force field
[83], these constraints are magnified by'the convoluted
shape of carbon black aggregates, within which the
occluded rubber is partially shielded from stresses in the
matrix [84]. The modulus of filled elastomers rises
according to Payne [85] from several contributing factors
which can be classified as follows:
 a) A pure gum contribution which does not depend
much on the kind of elastomer but on the
crosslink density.
b) The hydrodynamic effect or strain amplification
effect which is based on the concept that the
local strain in between the filler particles is
amplified over the externally applied
macroscopic strain because the particles can be
considered rigid compared to the soft rubbery
matrix material and thus do not participate in
deformation.
c) Elastomer-carbon black bonds are believed to
increase the number of crosslinks per unit
volume and thus increase the modulus [I].
d) The carbon structure is believed to be
responsible for increase in the dynamic [86] as
well as static modulus [87] at strains below 1%.
Paynets classification of contributions to
filler reinforcement does not include possible
effects on - t h e formation of structure
entanglements. This effect could be playing a
role, since entanglements have been shown to
influence the modulus of elastomers markedly
[88-901.

Compared to the carbon blacks, inorganic fillers have

low levels of polymer-filler bonding and larger particle
size varieties consists of individual, non-aggregated
particles which cannot immobilise or occlude significant
amounts of rubber phase. The smaller particle size
hydrated silicas are aggregated and form transient
structures, but their low level of surface activity for
polymer bonding results in small amounts of effectively
immobilised rubber. Because of these factors, mineral-
filled vulcanisates have considerably lower modulus values
compared to carbon black-filled vulcanisates at equivalent
hardness.

I.6.2 Effect on Tensile Strength

Tensile strength may be regarded as catastrophic

tearing at the tip of a chance flaw [91]. For an
elastomeric material with a flaw corresponding to a cut of
depth \Ct,the stress at break (tensile strength) is given
by
ub = (TcE/nC)f .... (1.2)

and the elongation at break, by

eb = (Tc/nCE)f

where Tc is the fracture energy and E is the Youngts

modulus [91]. Once the cut starts to grow, the stress
required for further growth decreases progressively in
accordance with Equation 1.2, accounting for the
catastrophic nature of the rupture.

Since modulus enters in the numerator of Equation

1.2, a filler such as carbon black which increases the
modulus will also tend to increase the tensile strength.
This increase may be counteracted to some extent by a
tendency toward larger flaw size in the presence of carbon
black and this will depend considerably on the quality of
dispersion attained during mixing. Larger flaw size leads
to reduced elongation at break as well as reduced tensile
strength.

Vulcanisates containing coarser black at high

elongation give lower tensile strength [92] than that
containing finer particle size blacks. This difference in
tensile strength between blacks of widely different
particle size is not tremendous. NllO and N765 blacks at
50 phr in SBR-1500 give tensile strengths of 32.3 and
22.7 MPa, respectively [93] i.e., a ratio of 1.42 whereas
the blacks differ by a ratio of 4.83 in particle size.

The effects of structure and loading have been

studied by Kraus [94] using blacks of approximately the
same surface area (100 m2/g). Results confirmed that with
reinforcing blacks, the net effect of loading on tensile
strength is that of carbon black plus the occluded rubber.
In accordance with Kraus' results, it is known that [93]
at a fixed loading (50 phr), a low structure black gives
higher tensile strength and higher elongation than a high
structure black of the same surface area, since at this
loading, low structure blacks are near the maximum of both
properties while high structure blacks are to the right of
the maximum. The loading at which the tensile strength is
a maximum increases somewhat with increasing particle size
[95], perhaps due to lower effectiveness of the occluded
rubber with the coarser blacks at high elongations.

The increase in ultimate properties with increased

effective loading upto the maximum is presumably due to
the increased tear deviation [96]. Carbon blacks lead to
tear deviation by creating barriers in the path of the
tear. In non-crystallising rubber, it appears that the
barriers can be formed by alignment of carbon black
aggregates and their linkage, into chains or strands [97].
Evidence for the formation of these strands comes most
directly from a large increase in electrical conductivity
in the direction of stretching [98]. . The positive
dependence of tensile strength on the surface area of
carbon black may be ascribed to the increased number of
strands with blacks of higher surface area. In order to
be effective, this tear deviation must act during the
initial stages of growth of the random flaws, delaying the
onset of catastrophic tearing.
 The decrease in tensile strength beyond the maximum
loading contrary to the increase which would be expected
from an increase in modulus, according to Mullins [99], is
due to "serious physical interference between neighbouring
particles as the concentration gets sufficiently high."
Developing this concept higher, at high loadings the
carbon black aggregates may be unable to rearrange into
strands during the time of stretching.

Silicas and silicates give tensile strength of

similar magnitude as that expected from carbon black of
comparable size. Colloidal silica is a good reinforcing
agent, imparting high tensile strength and excellent
resistance to tearing.

I-6-3 Effect on Abrasion and Wear

The most important effect observed upon introduction

of carbon black into rubber was the vast improvement in
abrasion resistance. Carbon black contributes strength
and abrasion resistance to non-crystallising rubbers,
while maintaining to a large extent their desirable
elastic properties.

The mechanism of abrasion has been studied, amongst

others, by Shallamach [loo] who had shown that it is a
complicated process of repeated straining of small volumes
at the surface resulting finally in tear and their
separation from the bulk of the rubber. Hence after a
number of cycles of prestress, abrasion loss is the result
of a high speed tensile process (Ecker) [loll. Kraus [3]
has analysed the effect of the addition of carbon black on
abrasion and wear in his excellent review. The abraded
volume falls with carbon black loading.

Westlinning [102] compared the abrasion resistance at

the same modulus of two series of compounds, one in which
the modulus was obtained by the use of sulphur and
curatives, the other by the addition of carbon black to a
simple base compound. He found that while the abrasion
resistance of the latter increased upto a certain maximum,
the resistance of the former fell continuously and
rapidly. Also abrasion resistance is known to fall
rapidly with increased modulus as a result of the use of
non-reinforcing fillers.

It is now well established that wear of rubber is not

a purely mechanical process in that it contains a
contribution due to thermal-oxidative Leakdown of the
polymer [103-1051. Still under severe conditions, which
apply to all accelerated laboratory tests as well as to
many situations encountered in tire wear, abrasion is
dominated by tearing process.
 - ',,'<,\,
',
. _\.
"u.
The strain rates and temperatures pr&~d&-$.i,ng
.. in
abrasion are very different from those used in routine
laboratory testing of tensile or tear strength. Because
of friction, local temperatures may far exceed those of
the test track or of the bulk of the rubber [106,107].
Even at small sliding velocities the effective strain rate
is very large, as small volume elements of rubber are
deformed repeatedly at high strains by the many surface
asperities of the track. Grosch and Schallamach [I081
estimate strain rate E = 100 sec'l for rubber sliding with
a velocity of 1 cm/sec over silicon carbide paper.
Ecker [loll has shown that laboratory abrasion loss data
may be related to tensile strength measured at 1 0 0 and
~ ~
= 150 sec-l.

Irrespective of the shortcomings of laboratory

hbrasion tests, Equation 1.4.

A/P C/Ub
where,
A - volume abraded
P - coefficient of sliding friction
C - proportionality constant

Ub - the work input at break

accounts for some important aspects of the dependence of

roadwear on carbon black properties under severe
conditions.
 The coefficient of friction p is not particularly
sensitive to carbon black addition at normal loadings
[101,108] and is essentially independent of particle size
and structure for carbon blacks used in tire treads. Thus
abrasion loss should be inversely related to Ub; the work
input at break. The highest values of Ub are generally
realised with small particle blacks. Also structure in
carbon black leads to increased tensile strength and Ub at
elevated temperatures.

The response of roadwear to carbon black particle

size is generally decreased wear with smaller particle
size [log-1111. But the predicted beneficial effect of
structure is revealed clearly only at severe conditions,
where the mechanism of abrasion is tearing [112]. Normal

.
usage of tire always involves some service under severe
conditions of wear, so that the use of medium to high
structure, blacks is favoured. Detailed quantitative
correlations of wear with carbon black particle size and
structure are not easily established because of the
fundamental difficulty in characterising the morphology of
carbon black in quantitative terms. Surface oxidation of
carbon blacks generally leads to increased rates of wear
with highly unsaturated hydrocarbon rubbers [113,114],
but the opposite is observed with butyl rubber. This
behaviour has been ascribed to differences in .interfacial
adhesion.

During abrasion, small particles of rubber of about

1 to 5 pm in size are removed from the surface, leaving

pits behind [115]. Eventually, as a result of continued

erosion of the rubber surface, large pieces of rubber, of
the order of 100 pm in size, are torn away. Most of the
loss in weight is due to these larger pieces; they
comprise as much as 95% of the total [115,116]. And yet
it is detachment of the smaller particles that constitutes
the basic abrasion process. If they are not removed, then
cumulative erosion of the surface, followed by detachment
of larger particles, will not occur.

A new theoretical treatment has been shown to account

for observed rates of wear in terms of the resistance of
compounds to crack growth under repeatedly-applied tensile
stresses [117,118]. A hypothetical mechanism for
detachment of small particles of rubber under the action
of frictional force is put forward by Gent [119].

1.7 Specific Properties Imparted by Fillers

1.7.1 Effect on flare resistance

Fillers are used satisfactorily in many applications

requiring certain specific properties. Elastomers with
inherent flame resistance, such as polychloroprene
rubber (CR), chlorinated polyethylene rubber (CPE),
chlorosulphonated polyethylene rubber (CSPE),
fluoroelastomers and silicones are readily selectable for
flame resistant applications, but other elastomers which
are not inhereqtly flame resistant have been treated
successfully by various methods to increase their fire
retardancy. One approach to flame-retard rubbers is
dilution of the polymer with filler having strongly
endothermic transitions. The prominent examples of energy
absorbing fillers are hydrates in particular alumina
trihydrate (ATH). Alumina trihydrate has exhibited both
smoke suppressant and flame retardant effect in a wide
variety of elastomers when used at relatively high
loadings [120]. At high loadings (>20 wt%) mass dilution
and/or endothermal dehydration are thought to slow the
build up of heat, favouring char forming processes and
Eeducing the flammability and smoke generation in
polydienes [121]. The effect is predominantly physical,
but evidence has been found for catalytic activity as well
Chalabi, Cullis and Hirschler [122-1241 have also reported
that, at less than 20 phr, pyrogenic silica is superior to
Al(OH)3 for smoke suppression in polystyrene.

Calcium carbonate, a very frequently used filler in

all types of polymers, tend to lower the oxygen index (01)
of cured polychloroprene gum compound slightly [125]. The
effect is more pronounced with carbonate of small particle
size and is probably due to partial absorption'of hydrogen
chloride by filler. A similar effect was found with zinc
oxide [126]. Inert fillers such as clay raise the oxygen
index (01) by dilution of combustiable matter in the
rubber compound [125-1273. The effept of a variety of
commonly used fillers.and flame retardant additives was
examined by Bolibar [128]. Among inorganic fillers
alumina and kaolin were found to make the largest
contribution to flame retardance.

The flammability of black-filled compounds, and

unfilled compounds with equivalent formulations were
evaluated by Trexler [129]. The flammability ratings of
the black and unfilled compounds were the same, except for
two polymers, neoprene and hypalon, which were rated as
self-extinguishable in the black-filled compounds and
combustable in the unfilled compounds.

Mosesman and Ingham [I301 investigated two hydrated

fillers,' alumina trihydrate and magnesium hydroxide
together with calcium carbonate and soft clay in an EPDM
rubber. It was shown that hydrated fillers delayed smoke
emission compared with other fillers; which was attributed
to endothermic dehydration. In the flame mode, magnesium
hydroxide was the most efffective smoke suppressant.
Application of magnesium hydroxide as a flame retardant
and smoke suppressant in two EVA copolymers was' studied by
Holloway [131].

1.7.2 Effect on Electrical Insulation/Conductance

Elastomers are insulators to which conductivity is

imparted by addition of conductive fillers. The
electrical conductivity of carbon black rubber compounds
is augmented by promotion of interaggregate contacts and
this is achieved by employing high concentrations of high
structure filler and by using porous conductive blacks
[132,133]. Carbon blacks of small particle size or a high
degree of permanent particle structure generally gives
lower values of resistivity [134-1361. The good
mechanical properties combined with either low or high
electrical resistivity has enabled their use in electrical
devices such as high quality communications cables, low
loss conventional power apparatus, optical fibers, cable
jackets, etc. Enhanced electrical conductivity has also
been realised in rubber blends by means of a nonuniform
distribution of the carbon black [137,138],

With regard to the physical processes involved in the

conduction of electricity, various authors have proposed
different mechanisms [139,140]. It is known that
deformation, while initially reducing the electrical
conductivity of carbon black reinforced rubber, induces at
higher strains, an enormous increase in the conductivity
of many filled elastomers [141-1431. Higher conductivity
can eventually be realised in the double network rubber
[144].

Recently, flakes and fibers of aluminiun, exfoliated

graphite, nickel flakes, graphite and carbon fibers and
aluminium-coated glass fiber are being employed in making
conductive polymer composites [145-1491. The use of a
combination of carbon fiber and particulate carbon black
has also been reported [150,151]. Ferrites have been used
to improve magnetic and electrical conductivity of
polymers [152,153]. Mica-thermoset resin composites are
well known electrical insulators. Epoxy-mica composite
has been shown to have enhanced voltage endurance
characteristics. Mica, silane and silane-treated mica
increases the ambient dielectric properties of vulcanised
styrene-butadiene rubber [154].

I.7.3 Effect of Filler on Heat Resistance of Elastomers

The presence of high level of unsaturation in a

natural rubber molecule makes it highly susceptible to
attack by oxygen. Heat accelerates the oxidation process.
During service, a number of rubber products are subjected
to varying levels of heat, generated as result of either
cyclic mechanical strain as in the case of a running tyre
or high ambient temperature. Prolonged exposure to heat
causes thermo-oxidative degradation of rubber and results
in the deterioration of its desirable properties,
eventually leading to premature failure. Thermo-oxidative
ageing of rubber is believed to occur in two ways either
via main chain scission or crosslink scission. It is
reported that carbon black accelerates main chain scission
and crosslink scission by surface catalysis [155].

Heat resistant compounds used in seals, gaskets often

contain magnesium oxide. Natural mica, washed and ground
to pass 200-300 mesh, provides a filler of linear type,
imparting resistance to heat and lower permeability of
gases.

1.7.4 Effect of Filler on Chemical Resistance of

El ast o m s

Elastomers find applications in many chemical

industries as a protective lining to various metallic
vessels, which carry chemicals at different temperatures
[156]. Oxygen, ozone, heat, solvents and chemicals are
the most common agents which cause degradation of
elastomers. In this event, elastomers having a relatively
inert backbone structure should be chosen. Fillers also
contribute to impart resistance to various chemicals under
the service conditions e.g., precipitated barium sulphate
is useful under acid immersion conditions.
 It has also been reported [157] that a pronounced
decrease in matrix swelling due to liquid penetration
occurs with increased filler loading and the decrease is a
linear function of loading when it is done with carbon
black. For loading with inorganic fillers the presence of
water soluble constituents in the filler may act as water
pools and as a consequence the above pattern of swelling
may get altered [158].

1.8 Effect of Filler on Thermal Conductivity of

Rubber Compounds

Heat is the most important processing agent both in

the manufacture of raw elastomers and processing them to
finished products. The rate at which heat can get into
and out of rubber i.e., its thermal conductivity controls
many applications, affects the design of processing
machinery and controls the speed of mixing, extruding and
moulding operations.

The basic Fourier equation for the unsteady state

conduction of heat in one dimension is

where
t - temperature
8 - time
 k - thermal conductivity
c - specific heat
p - density
x - distance from one surface.

The expression k/cf is called \a8 the thermal diffusivity

which is a measure of the rate of temperature movement
through a body. k t the thermal conductivity can be taken
as a measure of the rate of flow of heat through a body.
In comparison with other substances, rubber has a very low
thermal diffusivity. In the extensive list of Ingersoll
et al. [I591 rubber has the lowest value of \a8 of all
substances quoted which include metals, insulating
materials, soils, woods, liquids and gases. This low
value of 'a0 means that a given article made of any of the
other materials mentioned can be heated faster than the
one made of rubber.

Studies on thermal conductivity of rubber compounds

with various fillers are scanty. A large dependence of
conductivity on the type of carbon black .was reported by
Kainradl [160]. His observations can be summarised as
follows:

a) Furnace blacks give higher thermal conductivity

than channel blacks.
 b) Thermal conductivity increased almost linearly
with black content in the range 10-50 phr black.
c) Acetylene black imparted the highest thermal
conductivity; at 50 phr, conductivity was about
twice that with a channel black. Conductivity
ranking for various types of black was acetylene
black > RF > FEF > HAF > HMF > SRF > HPC > MPC.
d) Mineral fillers gave conductivities intermediate
between the highest and lowest values secured
with carbon blacks, zinc oxide giving the
highest conductivity on a volume basis.

Hands and Horsfall [161] observed high thermal

conductivity for N990 than for N110, N220 or N550. They
showed that both the diffusivity and conductivity of black
loaded natural rubber compounds decrease with increasing
temperature. The decrease over the temperature range from
room temperature to 200°c, can be as much as 45%. They
observed that the thermal conductivity of black loaded NR
samples cut from different parts of the same compression
moulded vulcanised sheet could differ by upto 25% at room
temperature. The difference could be caused by variation
in carbon black dispersion across the sheets. Particle
size and structure of carbon black seem to affect values
erratically, although the trend is towards higher values
with larger particle size and higher structure [162]. A
linear relationship of thermal conductivity Vs volume
concentration of carbon blacks and other fillers is
observed except at a very high concentration.

Schilling [163] carried out thermal conductivity

determination for NR, butyl rubber, NBR and SBR with a
series of loadings of HAF black and silica gel. Oikov [7]
investigated the thermophysical properties of NR
vulcanisates filled with aluminium. He studied the
dependence of coefficient of thermal conductivity and
thermal diffusivity of NR vulcanisates on the content of
aluminium. Various methods for measuring thermal
conductivity are well documented in the literature
[162,164-1661 including the widely accepted ASTM
procedures [167].

1.9 Heat Transfer and Vulcanisation of Thick Articles

During the mixing and moulding stage, the

thermoplastic nature of rubber is such that viscosity and
other physical characteristics are temperature sensitive.
In the vulcanisation of a rubber article in contact with
an efficient heating medium, the period during which the
temperature within the rubber is rising, is the period of
unsteady state heat conduction. If the article is thin
this period is short and for most of the cure, the
temperature is steady. If the article is thick, the
temperature in the interier may never reach the
temperature of the heating medium and unsteady state
conduction occurs during the whole cure. In the former
case calculation of the degree of cure at the coolest
point in the article is not so simple. The terms thick
and thin as employed here are relative to time. If the
total cure is say three minutes, anything over 5 mm may
well be called thick. Bearing in mind that the economies
of production tend to force the cure time down to the
minimum, unsteady state conduction applies through the
curing cycle of most articles of thickness greater than
6 to 8 mm.

Rubber is a bad conductor of heat, so cure time is

controlled by the length of time required to heat the
centre of the article on the one hand and on the other by
the amount of overcure which can be accepted on the
surface while obtaining full cure in the centre of the
product. Some increase in the conductivity is possible by
the incorporation of 'suitable filling materials having
inherent high conductivity.

In the case of thick articles, if 'the surface is

close to its optimum cure state, the centre may well be
badly undercured causing the article to be too prone to
heat build up under rapid cyclic deformation and readily
get destroyed. If the centre is adequately cured the
surface may be badly overcured resulting in reduced ageing
resistance. At the same time the thicker the article, the
slower will its inside cool after the article has been
removed from the curing environment. Almost exact
equivalence of cure of the outside and base of treads has
been reported for tyres when they are removed from the
mould with the tread base cured only about half as much as
the outer surface [168].

In order to make a balance between the uneven state

of cure of the surface of a thick article and its core and
to ensure adequate processing safety, cure retarders [I691
are used in rubber compounds. Retarders prolong the
induction period before the onset of vulcanisation. An
efficient retarder should influence the induction period,
without affecting the actual curing time or the extent of
vulcanisation.

Vulcanisation with a high ratio of accelerator to

sulphur (an EV system) reduces the reversion of the
exterior of a large article during the long period
required to cure the interior. EV system gives a network
which is thermally more stable than that obtained from a
conventional high sulphur formulation [170]. The greater
stability is attributed to the formation of high
proportion of relatively unreactive monosulphidic [I711
crosslinks.
 According to Cuthbert [I721 the problem of
vulcanisation of thick articles can be solved by the
application of unsteady state heat conduction theory, in
addition to a certain amount of practical experience of
minimum and maximum cure the compound can withstand
without deterioration in physical properties or ageing
resistance.

In simple cures of modertately thick articles, the

rough practice of adding 81ag time8 to the cure has
evidently served for many practical purposes to achieve
adequate cure at the centre [173,174]. Conant et a l .
[I731 published a nomogram for estimating the additional
curing time for various sizes of slabs, blocks, bars,
cylinders, cubes and spheres. The additional time was
assumed to be independent of the impressed temperature and
the error on this account was estimated not to exceed 5%
for a resonable range of curing temperatures. Mackae and
Zapp [I751 made a study of the thermal diffusivity of
butyl rubber compounds and time temperature relations at
the midplane of rubber slab in connection with their
vulcanisation.

Another interesting observation made by Edmondson

[I761 on thick articles is that if a small amount of
surface is ground away, volumes of maximum over cure can
be readily removed.
 One way of improving the heat transfer is tb increase
the thermal conductivity of the compound by adding
suitable thermally conductive fillers.

1.10 Scope of the Work

A close examination of the detailed literature survey

presented in the foregoing pages reveals that most
of the work on use of filler in rubber compounds
were concentrated on studying the factors affecting
processing characteristics, reinforcement, polymer-filler
interaction, vulcanisate properties, etc. Fillers
examined in rubber compounding were mostly carbon blacks
and silica, even though other particulate fillers such as
calcium carbonate, clay, mica powder [177], rice husk ash
[178], etc. and short fibres such as nylon, aramid, sisal,
jute, silk, etc. were also studied in different elastomers
[179-1831. Role of 'fillers in imparting special
requirements such as electrical resistance/conductance
[132], chemical resistance [157], flame resistance [129],
heat resistance [155], etc. were also examined by several
research groups. However, use of metal powders as filler
in rubber compounds was examined only to a very limited
extent. For example, use of brass powder [184] in rubber
compounds has been reported to give better bonding of the
compound with metals. High loadings of lead powder was
found to be useful to impart X-ray resistance.
 India is the fourth largest producer of natural
rubber in the world, with an annual production of 5,06,910
metric tonnes [185]. We also produce 5,80,000 metric
tonnes of aluminium per annum [186,187]. Even though
other metals such as copper, iron, manganese, etc. are
known to be pro-oxidants for NR, aluminium is
comparatively neutral in its action towards natural rubber
and hence aluminium vessels are widely used for processing
NR latex by the plantation industry. NR is having
excellent technological properties but its resistance to
oxidation and thermal ageing is very poor. Since NR is a
poor conductor of heat, it requires a very long time for
vulcanising thick articles such as retread compounds, roll
covers, rice polishers, dock fenders, solid tyres, etc.
This leads to overcuring at the surface and thermal
degradation of the polymer when it is used for such
applications. Aluminium is available in powder form,
having particle size ranging from 127 to 200 nm. Its
thermal and electrical conductance is also very good. At
the same time it is not a pro-oxidant for NR. Its
specific gravity is 2.69 which is in the range that for
fillers such as china clay (2.6), whiting (2.7), calcium
carbonate ( 2.65) , talc ( 2.8 ) , etc. and is much lower than
that for zinc oxide (5.60), titanium dioxide (3.9),

magnesium oxide (3.6), barytes (4.45), etc. Hence it is

worth to take up a detailed study on the use of aluminium
powder as a filler in natural rubber compounds.
1.11 Objectives of the Work

Incorporation of filler in rubber compounds brings

about a lot of changes in processing characteristics, flow
behaviour and vulcanisation kinetics, besides the
vulcanisate properties. The main objective of the present
study is to examine the possibility of using aluminium
powder as a filler in natural rubber compounds, with a
view to improving the thermal conductivity. Hence in this
work, the changes in the following properties of compounds
with different loadings of aluminium powder have been
examined in detail. In all the cases, high abrasion
furnace black (HAF) and acetylene black which are known to
provide good reinforcement and thermal conductivity
respectively were also included for comparison.

a) Cure Characteristics, vulcanisation kinetics and

extent of crosslinking of aluminium powder-filled NR
compounds

Ideally, fillers should not affect the cure

characteristics, vulcanisation kinetics +and extent of
crosslinking of rubber compounds. But acidic fillers and
those which can adsorb the accelerators are known to
retard the cure, resulting in extension of the
vulcanisation time. Very fine particle size furnace
blacks are difficult to get incorporated in the rubber
compound and generate high temperature during mixing,
leading to scorching problems. Increase in vulcanisation
time affects productivity and scorching makes the compound
difficult to process further. If the filler affects the
extent of crosslinking, the vulcanisate properties will be
affected adversely. Thus a detailed study of all these
parameters is essential to assess the suitability of
aluminium powder as a filler for rubber compounds.

b) Melt flow characteristics of aluminium powder-filled

NR compounds

For making a product the rubber compound is to be

subjected to any of the processes such as moulding,
extrusion or calendering. All such processes involve flow
of the compound under high pressure and temperature. Most
of the rubber compounds have pseudoplastic flow
characteristics so that their viscosity decreases with
increase in rate of shear. But incorporation of fillers
normally increases the viscosity. Hence to standardise
the processing conditions of rubber compounds containing
aluminium powder, knowledge on its viscosity at different
temperatures and rates of shear is essential.

c) Vulcanisate properties of aluminium powder-filled NR

compounds

Fillers are incorporated in rubber compounds either

to enhance the vulcanisate properties or to reduce the
 50

cost. Reinforcing fillers when used in rubber compounds

at appropriate loadings, enhance properties such as
tensile and tear strengths, abrasion resistance, flex
resistance, hardness, etc. whereas, the non-reinforcing
ones help to reduce the cost of the compound. Aluminium
powder which costs about Rs. 150 per kg cannot be
considered as a cheap filler. Hence a detailed study on
its effect in different vulcanisate properties is
necessary to optimise the quantity of filler for achieving
the desired level of improvement in a particular property.

d) Thermal conductivity of aluminium powder-filled NR

compounds

Natural rubber is a poor conductor of heat and

electricity. Fillers such as carbon blacks help to
improve these to a certain extent only. Hence it takes a
very long time to vulcanise thick articles. One of the
important properties of aluminium is its good thermal and
electrical conductance. Incorporation of aluminium powder
is expected to increase the thermal conductivity of NR
compounds. To assess the extent of enhancement in thermal
conductivity achieved by adding a definite volume of
aluminium powder and to study the effect of temperature on
thermal conductivity of aluminium powder-filled NR
compounds, a detailed experiment was carried out.
e) Ageing characteristics of aluminium powder-filled NR
compounds

Rubber vulcanisates are being subjected to the attack

of various degrading agents such as oxygen, ozone, light
heat, radiation, etc. during service. ~ependingon the
basic structure of the polymer, its resistance to these
degrading agents varies. Natural rubber is having very
active double bonds in its main chain and hence is highly
susceptible to the attack of these agents. Many metals
such as copper, iron, manganese, etc. are pro-oxidants for
natural rubber. Even though aluminium is neutral under
normal conditions, it is necessary to study its effect on
the resistance of NR compounds under the influence of the
above degrading agents, so as to get an idea about the
long term performance of the aluminium powder-filled NR
vulcanisates.

f) Properties of retread compounds containing aluminium

powder

There are several rubber products such as retreads,

rice polishers, rubber rolls, solid tyres, dock fenders,
etc. which take a very long time for vulcanisation. Due
to their thick cross-section, extra time is needed for the
heat reach the centre portion. This leads to uneven cure
and a very badly overcured outer surface for the product
which adversely affects its performance. Long cure time
affects productivity also. Among such products, retread
compound is the one which is produced in large quantities
in this country. In this era of energy shortage, it will
be a welcome step if the vulcanisation time can be reduced
by increasing its thermal conductivity. Hence in the
present work an attempt is made in this line also.
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