Composites Science and Technology 60 (2000) 17371751

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Morphology and melt rheological behaviour of

short-sisal-bre-reinforced SBR composites
R. Prasantha Kumar a, K.C. Manikandan Nair a, Sabu Thomas a,*, S.C. Schit b,
K. Ramamurthy b
a
School of Chemical Sciences, Mahatma Gandhi University, Priyadarshini Hills PO, Kottayam-686 560, Kerala State, India
b
Central Institute for Plastics Engineering and Technology, Guindy, Chennai, India

Received 9 February 1999; received in revised form 6 January 2000; accepted 1 March 2000

Abstract
The melt-ow behaviour of untreated and treated short-sisal-bre-reinforced styrenebutadiene rubber (SBR) composites were
analysed by using an Instron capillary rheometer. The eects of bre breakage, length, concentration and shear-rate/stress on melt
viscosity have been studied. The bre breakage was analysed before and after extrusion and the polydispersity index(PDI) was
estimated. It was found that these composites behave as pseudo-plastic materials. At low shear rates, the short bres increase the
viscosity much more than at high shear rates. There was an increase in viscosity upon chemical treatments owing to the strong
interfacial adhesion between the bre and the rubber matrix. The dependence of melt viscosity on temperature, ow behaviour
index, n0 , melt elasticity, extrudate distortion and deformation of these composites were analysed. Finally, die-swell measurements
were carried out to understand the elastic eects. The extruded samples were analysed by optical and electron microscopy in order
to study the surface morphology and extrudate deformation of these composites. # 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Sisal bre; Styrenebutadiene rubber; Composites; Rheology; Bonding agent; Interfacial adhesion

1. Introduction the rheological and extrusion behaviour of short-bre-

The ease of processability of a rubber compound is
essential for the fabrication of an end product, since it
undergoes dierent types of shear during every stage of
processing [1]. The need for rheological studies is essen-
tial in making a logical choice of the polymer and its
processing conditions [2]. The modern theories of
rheology of elastomers have been related to the proces-
sing characteristics of rubber and molecular structure
[35]. The study of the rheological behaviour of polymer
composites is very important for fabrication of end
products. It is seen that at higher shear rates, bre
orientation takes place because of the convergent,
divergent and shear ows. The bres orient along the
ow direction during convergent ow and at 90 to the
direction in a divergent ow [6].
Setua et al. [7] and Murthy et al. [8] have observed that
short-bre-reinforced elastomer composites behave as
pseudoplastic materials. Goettler et al. [9] have reported
* Corresponding author. Tel.: +91-481-598015/598303; fax: +91-
481-561190.
E-mail address: sabut@md4.vsnl.net.in (S. Thomas).
0266-3538/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S0266-3538(00)00057-9
reinforced rubber compounds. Kutty et al. [10] have
found the dependence of temperature on the shear visc-
osity of short-bre-lled composites.
Melt elastic parameters like die swell ratio were found
to increase with increasing shear rate and decrease with
bre loading [11]. This is due to the irreversible orien-
tation of the bres in the matrix during extrusion.
Goettler [12] has found that the bres raise the viscosity
of the composite due to the higher pseudoplasticity
induced by the bres. Czarnecki et al. [13] have worked
on the shear ow rheological properties, bre damage,
and mastication characteristics of short-bre-reinforced
polystyrene melts.
Recently, Thomas and co-workers have extensively
studied the eect of short bres on the rheological
behaviour of composites of natural rubber [1415] and PS
(polystyrene) [16] respectively. Recently, the authors have
reported on the mechanical [1719], processing [20],
electrical [21] and transport [22] behaviour of short-
sisal-bre reinforced styrenebutadiene (SBR) compo-
sites. However, there seems to be no previous studies
made on the rheological and extrusion behaviour of short-
sisal-bre-reinforced SBR composites. In this paper, we
1738 R. Prasantha Kumar et al. / Composites Science and Technology 60 (2000) 17371751
report our observations found on the rheological and
extrusion behaviour of untreated, treated and bonding
agent added short-sisal-bre-reinforced SBR composites
with special reference to the eect of bre breakage and
bre distribution, bre length and bre concentration
on shear viscosity.
2. Experimental
2.1. Materials
Synthetics and chemicals, Bareilly, Uttar Pradesh
State, India supplied Synaprene (SBR-1502). Sisal-bre
(Agave sisalana) was obtained from a local processing
unit situated in the state of Tamil Nadu. The chemical
constituents of sisal-bre are reported in Fig. 1 [23]. It
was reported that the density [24] and the average dia-
meter of the bre are 1.45 g/cm3 and 0.1212 mm
respectively. All other chemicals such as hexamethylene
tetramine and resorcinol used were of laboratory
reagent grade.
2.2. Methods
2.2.1. Fibre distribution analysis
The mixes were dissolved in toluene and the length of
the extracted bres was measured under the optical
microscope. The variation of average bre length with
the volume loading of bre and the changes in the
average bre length before and after extrusion at dier-
ent shear rates was analysed.
Fig. 1. Chemical constituents of sisal bre.
2.2.2. Treatment of bres
2.2.2.1. Water treatment. Fibres of length 6 mm were
immersed in water at 28 C for 1 h. These bres were
then washed several times with water and were later
dried in an air oven at 70 C for 2 days and kept in
polyethene bags. These bres were designated and used
as untreated bres.
2.2.2.2. Acetylation. Fibres were immersed in 18%
NaOH solution at 28 C for 1 h . These bres were
washed several times with water and 0.1 N HCl. The
bres were then soaked in glacial acetic acid for 1 h at
the same temperature. Later they were soaked again in
acetic anhydride containing Con.H2SO4. The resulting
bres were washed and dried in an air oven.
2.2.2.3. Benzoylation. The mercerised bres were agi-
tated with 10% NaOH and 50 ml benzoyl chloride for
15 min. The dried bres were then soaked in ethanol for
1 h, washed and dried in an air oven at 70 C.
2.2.3. Preparation of composites
Mixes were prepared in a two-roll laboratory open
mixing mill (150300 mm), at a nip gap of 1.25 mm.
These mixes were compounded according to the basic
formulation given in Table 1. All the ingredients were
added in the mix according to the mixing sequence [17].
2.2.4. Rheological measurements
The rheological studies of untreated and treated
short-sisal-bre-reinforced SBR composites were car-
ried out using an Instron Capillary Rheometer Model
 R. Prasantha Kumar et al. / Composites Science and Technology 60 (2000) 17371751 1739

Table 1
Formulation of mixes (from A to H2)

Ingredients Mixes

A B C D E E1 E2 E3 E4 F1 F2 G1 G2 H1 H2

Synaprene 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
Sulphur 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2
Stearic acid 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
Zinc oxide 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5
Silica (Pptd) 1 1.5 3 5
Hexaa 2 2.5 1.5 2.5 2.5 2.5 2.5 2.5
Resorcinol 2.5 5 3 5 5 5 5 5
CBSb 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
TDQc 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
Sisal bre
1. Untreated 20 20 20 5 10 15 15
2. Acetylated 5 10 15 20
3. Benzoylated 5 15
a
Hexamethylene tetramine.
b
N-cyclo hexyl benzothiazole sulphenamide.
c
2,2,4-Trimethyl 1,2-dihydroxy quinoline polymerized.

3211 [25]. A capillary of L/D ratio 20 and an angle of : 3n0 1 8V

entry 90 were used in all experiments. All studies were w;a 5
4n0 dc
done in the shear range of 3.681226.9 s1, and a tem-
perature range of 90130 C due to the instrument lim-
itations. The factor 3n0 1=4n0 is the Rabinowes correction
The shear stress, w , increases linearly with distances, applied to calculate the true shear rate.
r, from the centre line and is given by:

P dlnw
w r 1 But; n0 6
2lc dln a

:
where P is the pressure drop across the length, lc , of i.e. n0 is the slope of the graph of ln w vs ln w;a . Thus
capillary tube. The true wall shear stress was calculated wall shear rate for pseudoplastic materials is, therefore:
by,

F : 2 3n0 1 VXH db2

w 2 w;a 7
4Ap lc =dc 15 4n0 dc3

where F is the force on the plunger (N), Ap cross- Thus, apparent viscosity, a is calculated by,
sectional area of the plunger (mm2), and lc (mm) and dc
(mm) the length and diameter of the capillary respectively. :
na w =
w;a 8
The apparent shear rate was calculated by using the
equation:
2.2.5. Die swell and extrudate morphology
:

w;a 8V=dc 3 The extrudates diameters were measured at dierent
times and were kept for 24 h to attain equilibrium
VXH db2 before nal readings were recorded, using a travelling
But; V 4
60 dc3 microscope. The die swell ratio can be calculated from
the formula,
where V is the mean velocity of the liquid owing de
through the capillary, VXH , the cross head speed in Die swell ratio 9
dc
cm/min, db , the diameter of the barrel, dc , the diameter
of the capillary. The correct wall shear rate may be where de and dc are the diameter of the extrudate and
found by using the Rabinowes correction: the capillary, respectively.
1740 R. Prasantha Kumar et al. / Composites Science and Technology 60 (2000) 17371751
For SEM, the peripheral and cross-sectional surfaces
of the extrudates were sputter-coated with gold within
24 h of testing.
3. Results and discussion
The calculations of melt viscosity and the shear rate
of a pseudoplastic material depends on several assump-
tions: (i) uid ow is parallel to the axis, (ii)velocity of
any uid element is a function of radius only, (iii) uid
is incompressible, (iv) velocity of the uid is zero at the
wall, (v) uid ow is isothermal and (vi) all energy is
consumed within the capillary itself.
3.1. Fibre breakage
Fibre breakage was analysed from the bre length
distribution curve and from the polydispersity index
(PDI). Fig. 2 shows the bre length distribution for
compound G2 before and after milling. The short sisal
bres have not undergone severe breakage, although
high shear forces were generated during the time of
mixing. The initial 6 mm length of the bres is con-
verted to varying sizes. It can be observed that the
maximum breakage is seen between 5 and 6 mm in
length. During extrusion, the bre again undergoes
breakage and the percentage of bre of less than 5 mm
length increases considerably.
It is clear from Fig. 3(a) that the maximum in the
range 56 mm bre length before extrusion is shifted to
01 mm after extrusion at a shear rate of 1226.9 s1.
The increase in the breakage of bres is due to the result
of the nal break-up of kinked bres during extrusion.
n 10
As the shear force increases, the percentage of breakage
increases dramatically, and at a shear rate of 1226.9 s1
more than 40% of the bres are of less than 2 mm
length. The increase of PDI value as shown in Table 2
with the increase of shear rate also revealed the bre
breakage. On analysing Fig. 3(b) it is seen that the most
probable length of the bre in composite decreases with
shear rate.
3.2. Eect of bre length
The eect of bre length on the melt viscosity of SBR
composites at 120 C is shown in Fig. 4. A series of
mixes containing 20 phr short sisal bre of length 2, 6
and 10 mm were used to study the eect of bre length.
Generally, an increase in viscosity on increasing the
bre length is expected. It is seen that the melt viscosity
increases with bre length from 2 to 10 mm. The ow
behaviour of composites containing bres having a
length beyond 10 mm was dicult to study. The visc-
osity increases with bre length at low shear rates. But
at higher shear rates, the bre alignment and bre
distributions occur simultaneously and, therefore, increase
in viscosity is less predominant here.
It is dicult for bres having higher bre lengths to
become oriented in the direction of ow and the dis-
tribution or dispersion of bres also is poor at higher
bre length. This is due to the entanglement of bres at
higher bre content. Thus bres having shorter length
can be more easily aligned and dispersed than those
having higher lengths along the direction of ow, i.e.
SBR composites containing short sisal bres having
shorter length show low viscosity than having higher
length. This fact is clearly shown in the Fig. 5. As the
bre length increases the dispersion of the bre becomes
poor and it will cause agglomeration of short sisal bres
in the SBR matrix. This increases the melt viscosity of
the composite.
3.3. Eect of shear stress and bre loading on melt
viscosity
The variation of melt viscosity of sisal-SBR compo-
sites with shear stress at dierent bre loading at 120 C
is shown in the Fig. 6. Like all other bre reinforced
elastomer composites, the melt viscosity of SBR com-
posites reduces with the increase in shear stress. The
increase in viscosity with increasing shear stress is
attributed with the orientation of the polymer molecules
and the bres in the direction of shear.
These curves are typical of pseudoplastic materials,
which show a decrease in viscosity with increasing shear
stress. All the mixes have been modelled using the
power-law equation [26],
:
 K
where n is the power law index and k the consistency
index. The power-law model was found to be the most
suitable equation to model this behaviour. The slight
non-linearity from the power-law model is due to the
variation in the extent of bre orientation in the matrix
and also due to wall slip [27]. For a given stress, the
viscosity of SBR composites was found to increase with
bre loading. The increase in viscosity of the composites
with increasing bre loading is due to the interaction
between brebre and brematrix.
3.4. Eect of chemical modication of bres
Several researchers [2832] have proved that strong
interfacial bonding at the interface can be obtained by
dierent chemical treatments.
3.4.1. Acetylation
The cellulosic hydroxyl groups in the lignocellulosic
sisal bre are not so reactive, since they form strong
hydrogen bonds. The addition of 18% caustic soda
 R. Prasantha Kumar et al. / Composites Science and Technology 60 (2000) 17371751 1741

solution treatment destroys the hydrogen bonding in 3.4.2. Benzoylation

cellulosic hydroxyl groups and cause partial removal of
lignin. This makes the OH groups more reactive
(Scheme 1). The hydrogen atom on acetyl carbon atom
becomes more reactive due to the presence of a carbonyl
group. This reacts with active sites on SBR to form
chemical links, thereby improving adhesion between
bre and rubber matrix. The hypothetical mechanism
showing the acetylation reaction on the bre is shown in
Scheme 2. The mechanism of acetylation has been
explained by Chand et al. [33].
The hypothetical mechanism showing the benzoyla-
tion reaction on the alkali treated bre is shown in
Scheme 3. The OH group of the lignocellulosic sisal
bre reacts with benzoyl chloride. The extractable
materials such as lignin, waxes, etc. were removed by
the addition of 18% caustic soda solution. Considerable
attention has been paid to see that the bres do not lose
their physical properties and brous nature during this
treatment. The reaction proceeds through any hydroxyl
group attached to the cellulose backbone, since the
oxygen linkage is a hydrolysable one. As per the IR
studies made on the bre after benzoylation, it is
observed that as a result of esterication of the hydroxyl
group, the hydroxyl vibration absorption at 3400 cm1
is found to be decreased. The absorption bands at 1950,
1600 and 710 cm1 indicate the presence of aromatic
rings. The ester group is identied by the presence of
peaks at 1725 and 1300 cm1.

Table 2
Fibre length distribution index of sisal bres before and after extrusion

Shear rate s1 Ln Lw Ln/Lw

Before extrusion

4.68 5.08 1.08

After extrusion

12.269 3.72 4.3 1.15

122.69 2.5 3.58 1.43
Fig. 2. Eect of bre length distribution before and after milling of 1226.91 2.32 3.38 1.45
SBR composites.

Fig. 3. (a) Eect of bre length distribution of sisal bres after extrusion. (b) Eect of bre length on increasing shear rates at 120 C.
1742 R. Prasantha Kumar et al. / Composites Science and Technology 60 (2000) 17371751
Fig. 4. Eect of shear rate on melt viscosity at dierent bre lengths.
Fig. 5. Eect of bre length on melt viscosity at dierent shear rates at
120 C.
3.5. Viscosity of chemically modied composites
The eects of chemical treatments on the melt viscos-
ity of treated SBR composites at a temperature of 120 C
are discussed in the Fig. 7. The gure shows the eect of
hydration, acetylation and benzoylation on the melt
viscosity of the composites. On analysing the gure, it is
seen that the benzoylated bre containing mix H2 has
Fig. 6. Eect of shear stress on melt viscosity of mixes A, E2, E3 and
E4 at 120 C.
the maximum viscosity followed by acetylated bre
containing mix G1 and it decreases on increasing shear
rate. The increase in viscosity is due to the better bond-
ing with the bre and rubber due to chemical modica-
tion. The better interfacial adhesion between the
bezoylated sisal bre and SBR matrix is shown in
Scheme 3. Schematic models of the interfaces after
acetylation and benzoylation treatments are shown in
Fig. 8(a) and (b).
3.6. Eect of temperature
During processing, the elastomers undergo consider-
able change due to the eect of temperature. At all bre
loading, the melt viscosity of the composites decreases
on increase of temperature. This is due to several factors
such as (a) accelerated molecular motion due to thea-
vailability of greater free volume and the decrease of
entanglement density, (b) weak intermolecular interac-
tions.
In the Arrhenius expression, () is related to absolute
temperature (T) by the following equation [34].
 AeD E=RT 11
where A is a constant characteristic of the polymer,
E
is the activation energy for viscous ow, and R is the
universal gas constant. The eect of temperature on
melt viscosity of the SBR composites at dierent load-
ing of bres at four dierent temperatures at a shear
rate of 36.807 s1 is shown in Fig. 9. These plots are
treated as the semi logarithmic Arrhenius plots, i.e. log 
vs 1=T at xed shear rate of 368.07 s1. From the slopes
of these linear plots,
E values were estimated. The
E
 R. Prasantha Kumar et al. / Composites Science and Technology 60 (2000) 17371751 1743

Scheme 1.

Scheme 2.

Scheme 3.

values provide valuable information on the sensitivity of

the material towards the changes in temperatures. The

E of the composite melt increases with increase in the
bre concentration, indicating that the melt viscosity of
the composite is greater temperature sensitive than that
of the gum compound. The estimated
E values pre-
sented in Table 3 support this fact. Thomas et al. [14,15]
have already reported similar behaviour for sisal/coir
bre reinforced NR composites.
Fig. 10 shows the eect of melt viscosity with tem-
perature on dierent chemically modied bre rein-
forced composites at a shear rate of 368.07 s1. Among
the treated mixes, the benzoylated bre containing mix
H2 showed highest slope value showing the higher acti-
vation energy, and it indicates that it has greater sensi-
tivity to temperature among all other mixes (Table 4).

3.7. Eect of relative viscosity

In the case of polymer composites, the relative visc-

osity is calculated as the ratio of the shear viscosity of
Fig. 7. Eect of shear rate on melt viscosity of sisal/SBR composites the lled compounds to that of unlled compounds. The
containing chemically modied bres at a temperature of 120 C. variation of relative viscosity with volume fraction of
1744 R. Prasantha Kumar et al. / Composites Science and Technology 60 (2000) 17371751

Fig. 8. (a) Schematic model of the interface after acetylation treatment. (b) Schematic model of the interface after benzoylation treatment.

bres at a shear rate of 3.68 s1 is shown in Fig. 11.
When the temperature is increased from 90 to 120 C,
the relative viscosity of the composite decreases. For the
dierent temperatures studied, it can be seen that the
relative viscosity increases with bre loading. But the
magnitude of the increase show a decreasing trend as
the temperature is elevated with bre loading.
At 110 and 120 C, the rate of change of relative visc-
osity is uniform over the entire range of bre loading
whereas at 90 and 100 C the rate of change shows a
sharp increase. At higher bre loadings and at higher
temperatures, the scorch eect causes the bres to be
less oriented as compared with their behaviour at a
lower temperature. This decreases the relative viscosities
of composites containing the same level of bre loading,
as the temperature is increased.
3.8. Flow behaviour index (FBI)
The pseudoplastic materials have n0 values less than unity
and a high value of n0 indicates a low shear thinning nature.
The eect of bre length on the ow behaviour index of the
composites is presented in Fig. 12. No remarkable eect
was noticed upon the increase of bre length.
Fig. 13 shows the eect of volume percentage of bres
on the ow behaviour index of sisal-SBR composites.
From the gure, it is seen that the ow behaviour index
of sisal/SBR composites was found to be less than unity,
indicating the pseudoplastic nature of the system. It is
also noted that the n0 values decrease upon increasing
the bre content in the system. The increase of pseudo-
plasticity arises due to the orientation of bres during
its ow through the capillary.
 R. Prasantha Kumar et al. / Composites Science and Technology 60 (2000) 17371751 1745

3.9. Die swell and extrudate distortion

Die swell measurements at 120 C for three dierent

Fig. 9. Eect of temperature on melt viscosity of mixes A, E1, E3 and
E4 at a shear rate of 36.807 s1.
shear rates were made and shown in Table 5. The die
swell increases slightly with increase of temperature and
shear rate in the case of bre reinforced rubber com-
pounds. But the die swell is greatly reduced by the
addition of bre and the eect is negligible beyond
10phr loading. These results are agreement with earlier
observations made by Chan et al. [35]. At the same bre
loading, the die swell ratio increases with shear rate and
it is observed that the chemical treatment on the bres
does not show much remarkable change in the die-swell.
Optical photograph of the SBR composites extruded
at 120 C at three dierent shear rates is shown in Fig.
14. The presence of bre reduced the extrudate distor-
tion at high shear rates and at 15 phr loading, the dis-
tortion is remarkably low. It has been also observed
that the distortion is negligible at 90110 C. It is evi-
denced from the optical photograph that the presence of
bre reduced the extrudate distortion at high shear rates
and at higher loading of bres (mixes E4, G1 and H2).

Table 3
Activation energy of sisal/SBR composites at dierent bre loading at Table 4
a shear rate of 36.807 s1 Activation energy of treated sisal/SBR composites at same bre load-
ing at a shear rate of 368.07 s1
Mixes Volume of bres (% ) Activation energy (kJ/ K/mol)
Mixes Type of chemical treatment Activation energy (kJ/ K/mol)
E 0 2.707
E1 5 4.841 E4 Untreated 2.734
E2 10 5.867 G1 Acetylated 2.872
E3 15 7.973 H2 Benzoylated 3.063

Fig. 10. Eect of temperature on melt viscosity of treated mixes at a Fig. 11. Eect of volume of bres (%) on relative viscosity of SBR
shear rate of 36.807 s1. composites at a shear rate of 3.68 s1.
1746 R. Prasantha Kumar et al. / Composites Science and Technology 60 (2000) 17371751

Fig. 12. Eect of bre length on ow behaviour index of SBR composites.

Fig. 13. Eect of bre loading on ow behaviour index of SBR composites.

Table 5
Variation of die swell ratio (de/dc) of SBR composites for dierent shear rates at 120 C

Samples Shear rate (s1)

3.6807 3.6807 3.6807 1226.91

A 1.45 1.49 1.52 1.61

E 1.46 1.47 1.51 1.58
E1 1.40 1.42 1.48 1.55
E2 1.38 1.39 1.39 1.40
E3 1.15 1.16 1.16 1.15
E4 1.14 1.14 1.13 1.13
G1 1.06 1.08 1.08 1.07
G2 1.05 1.06 1.07 1.06
H2 1.05 1.06 1.07 1.06

extrudates E, F1 and G1 at dierent shear rates 36.807,

3.9.1. SEM studies on extrudate morphology
The extrudates show smooth surfaces and uniform
diameter at low shear rate. But on increasing shear
rates, the extrudates exhibit surface irregularity. Fig.
15(a), (b) and (c) shows the SEM micrographs of
368.07 and 1226.91 s1 respectively. The surface mor-
phology of these composites extruded at dierent shear
rates show an increase in the surface discontinuity with
increasing shear rates. The irregularity at the periphery
of the mixes increases as the shear rate increases. The
 R. Prasantha Kumar et al. / Composites Science and Technology 60 (2000) 17371751 1747

Fig. 14. Optical photograph showing the extruded distortion of mixes

A, E1, E2, E3, E4, G1, G2, H1 and H2.

surface discontinuity is associated with the migration of

bre towards the periphery of the extrudates.
Fig. 16(a) and (b) shows the cross-sectional view of
the extrudates E2, and E3 at a constant shear rate of
368.07 s1 containing 10 and 15 phr loading of bres. It
is observed that the bres are well oriented along the
direction of extrusion. At low shear rate the bres are
mainly concentrated at the periphery, whereas at med-
ium shear rates they form a uniform dispersion Fig. 15. SEM of the surface morphology of dierent extrudates at
throughout the matrix. The unequal retroactive forces dierent shear rates 36.807, 368.07 and 1226.91 s1 respectively: (a) E-
experienced by the components in the composite result gum; (b) F1 (5 phr); (c) G1 (15 phr).
in the redistribution of the bre and its consequent
migration to the periphery of the extrudate [35]. It is
observed that short sisal bres, which are dispersed
uniformly at medium shear rate, are concentrated at the is extruded at a shear rate of 1226.1 s1. In the case of
core region along the direction of capillary ow. When G2, the bres are concentrated at the periphery while in
the shear rate is increased from 36.807 to 368.07 s1, the the case of G1, the bres are concentrated at the core of
redistribution of short bres takes place and more and the extrudate.
more bres were concentrated at the core of the extru-
dates (E2 and E3). 3.10. Theoretical modelling
It is also clear from these gures that dispersion of
short bres increased with treated bre concentration. Guth et al. [36] has proposed the following equation
Micrographs, Fig. 17(a) and (b), of composites con- to explain the viscosity of the oriented composite:
taining treated bres show increased orientation of
short bres due to the increased brerubber interac-

tions. G2 is extruded at a shear rate of 36.8 s1 while G1 c un 1 0:6fc 1:62f 2 c2 12
1748 R. Prasantha Kumar et al. / Composites Science and Technology 60 (2000) 17371751
Fig. 16. SEM of the cross-sectional view of the extrudates at a shear
rate 368.07 s1: (a) E2-10 phr; (b) E3-15 phr.
where f is the ratio of longest to the shortest diameter of
the bre, c, the volume fraction of the bre, un , the
viscosity of the unlled mix, and c , the viscosity of the
composite.
The theoretical and experimental viscosity of sisal/
SBR composites at 100 and 120 C at dierent shear
rates are shown in Fig. 18(a) and (b). Fig. 18(a) shows
that at 100 C, the experimental values are higher than
the theoretical value in all loading. On increasing the
concentration of bres, the bre-matrix interaction
increases and thereby diculty arises in the better
alignment and orientation of bres. Therefore, the
experimental viscosity is higher than the predictions.
Fig. 18(b) also shows that the experimental viscosities
are higher than the theoretical values at all bre load-
ing. On increasing temperature, the viscosity is governed
by brematrix interactions and misalignment of bres
in bre distribution, which lead to higher viscosity than
the theoretically predicted one.
Fig. 19 shows the comparison of experimental and
theoretical relative viscosities at dierent volume frac-
tion of bres and dierent temperatures at a shear rate
of 36.807 s1. The relative viscosity increases upon the
increase of the volume fraction of bres. It is also seen
that the experimental relative viscosity is higher than the
theoretical one. This is due to the increased interfacial
adhesion between the bre and matrix, i.e. the better
Fig. 17. SEM of cross-sectional view of the extrudates of treated
composites at shear rates 36.807 and 1226.91 respectively: (a) G2-20
phr; (b) G1-15 phr.
bonding occurred in the interface, if not, it could be due
to the entanglement of bres in the composite.
According to Kamal et al. [37], the relative viscosity
and concentration relations represent semi-empirical
extensions of dilute suspension theories through the
inclusion of 2v .
r 1 v kv 2 13
where r is the relative viscosity of the suspension and
v is the term for the rst order interactions among
bres. Thus the variation of relative viscosity of com-
posites with bre loading at dierent temperature and
shear rate can be tted into a second-degree polynomial
type of equation [38], i.e.
f =g 1 K1 Vf K2 V2f 14
where K1 and K2 are functions of rate of shear and
temperature, f and g , the viscosities of the lled and
the gum compound respectively and Vf , the volume
fraction of the bre in the composite. The relative visc-
osities of sisal/SBR composites have been tted into the
 R. Prasantha Kumar et al. / Composites Science and Technology 60 (2000) 17371751 1749

Fig. 18. (a) Comparison of experimental and theoretical melt viscosities at dierent shear rates of mix H2 (a) 100 C; (b) 120 C.

Fig. 19. Comparison of experimental and theoretical relative viscosities at dierent volume fraction of bre and dierent temperatures (shear rate
36.807 s1).

Table 6
Comparison of theoretical and experimental viscosity of mix H2

Shear rate (s1) Temperature ( C)

90 100 110 120

K1 K2 K1 K2 K1 K2 K1 K2

3.6807 5.9384 12.741 0.6109 29.59 0.1350 26.84 5.536 133.3

36.807 2.6537 0.0857 0.5726 23.62 16.871 381.26 5.863 10.80
368.07 0.1196 1.5170 8.4956 68.80 0.0390 106.98 0.034 99.37

second-degree polynomial equation and the values of K1 4. Conclusions

and K2 at dierent shear rate and temperature are given
in Table 6. Some K1 values are negative, which are The rheological behaviour of short-sisal-bre-
attributed to the wall slip occurred during extrusion. reinforced SBR composite has been studied. The eects
1750 R. Prasantha Kumar et al. / Composites Science and Technology 60 (2000) 17371751
of shear rate, bre loading, temperature and the extent
of interface bonding on the viscosity of the system have
been examined in detail. The sisal bres undergo severe
breakdown during extrusion. All the system showed
pseudoplastic behaviour showing the decrease of visc-
osity with increasing shear rate.
The incorporation of treated bres increased melt
viscosity and the viscosity enhancement was due to the
increased interfacial adhesion between the bre and
matrix due to the chemical treatments. Of the various
chemical treatments, benzoylated bre reinforced com-
posites showed maximum viscosity among all mixes.
The ow behaviour index of the composites was found
to decrease and attain a steady value on increasing the
concentration of treated bres. The relative viscosity of
the composites was also found to increase with increase
of bre loading.
The extrudate distortion and die swell behaviour of
SBR composites were reduced by the addition of short
sisal bres. Short bres present in the matrix prevent the
shape distortion of the extrudates and the increase in
bre content decreased the shape distortion. Die swell
values decreased substantially with the incorporation of
short bres. SEM photographs indicated that the
increase of short bres creates discontinuity in the
polymer matrix. The bres were found to be con-
centrated more on the periphery at low shear rates and
on the core at high shear rates.
On comparison of theoretical melt viscosity with the
experimental values, it is seen that the experimental
viscosity is greater than the theoretical value as a result
of better interfacial adhesion and misalignment of the
bres. Moreover, the variation of relative viscosity of
composites with bre loading at dierent temperatures
and shear rates has been tted into a second-degree
polynomial type equation.
Acknowledgements
One of the authors (R.P.K.) would like to thank the
Council of Scientic and Industrial Research (CSIR),
New Delhi for the nancial assistance awarded in the
form of a research fellowship. His thanks are also due to
Mr. Murukesan, Technical Assistant, Rheological
laboratory, CIPET, Guindy, Chennai. Finally the
authors thank the referee for the valuable comments.
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