Polymer International Polym Int 52:1382–1389 (2003)

DOI: 10.1002/pi.1232

Properties of natural rubber composites

reinforced with silica or carbon black:
influence of cure accelerator content and
filler dispersion
Sung-Seen Choi,1∗ Changwoon Nah2 and Byung-Wook Jo3
1 Research Institute of Advanced Materials, Chungnam National University, 220 Gung-dong, Yuseong-gu, Daejeon 305-764, Korea
2 Department of Polymer Science and Technology, Chonbuk National University, Chonju 561-756, Korea
3 Faculty of Chemical and Polymer Science and Engineering, Chosun University, Gwangju 501-759, Korea

Abstract: Filler dispersion is a critical factor in determining the properties of filled rubber composites.
Silica has a high density of silanol groups on the surface, which lead to strong filler–filler interactions
and a poor filler dispersions. A cure accelerator, N-tert-butyl-2-benzothiazole sulfenamide (TBBS), was
found to improve filler dispersion in silica-filled natural rubber (NR) compounds. For the silica-filled
NR compounds without the silane coupling agent, the reversion ratio generally increased with increase
in TBBS content, whereas those of the silica-filled NR compounds containing the silane coupling agent
and carbon black-filled NR compounds decreased linearly. The tensile strength of the silica-filled NR
vulcanizate without the silane coupling agent increased as the TBBS content increased, whereas carbon
black-filled samples did not show a specific trend. The experimental results were explained by TBBS
adsorption on the silica surface and the improvement of silica dispersion with the aid of TBBS.
 2003 Society of Chemical Industry

Keywords: rubber composite; silica; carbon back; cure accelerator; filler dispersion

INTRODUCTION surface and a siloxane bond is then formed. The silane

Silica and carbon black have been used as the
main reinforcing agents in rubber compounds1 – 3 but
their surface chemistries are very different. Silica
has a number of hydroxyl groups on the surface,
which result in strong filler–filler interactions and
adsorption of polar materials by hydrogen bonds.1,4
The polar surface of silica makes hydrogen bonds
with polar materials in rubber compounds. Since
the silica surface is acidic, it especially forms a
strong hydrogen bond with basic materials. N-
tert-Butyl-2-benzothiazole sulfenamide (TBBS) and
N−cyclohexylbenzothiazole sulfenamide (CBS) are
generally used as cure accelerators for rubbers. Since
they have basic functional groups such as amide
(=NH), they are well adsorbed on the silica surface.
The adsorption of curatives on silica results in
a delay of the scorch time and reduction of the
cross-link density in silica-filled rubber compounds.
In general, silane coupling agents such as bis[3-
(triethoxysilyl)propyl]tetrasulfide (TESPT) are used
to improve the filler dispersion and to prevent
adsorption of curatives on the silica surface.5 – 7 The
silane coupling agent reacts with silanol on the silica
molecule is bound to the silica surface.
A cure accelerator based on sulfur in a rubber com-
pound increases cure rates and cross-link densities.8,9
In the present work, the influence of cure accelerator
content on the properties of silica-filled natural rubber
(NR) compounds with and without a silane coupling
agent was studied. TBBS was used as a cure acceler-
ator and TESPT was employed as a silane coupling
agent. The degree of silica dispersion, cure character-
istics and physical properties were investigated. The
silica-filled NR compounds were also compared with
the carbon black-filled compounds.
EXPERIMENTAL
Five silica-filled natural rubber (NR) compounds
without the silane coupling agent, five silica-filled NR
compounds containing the silane coupling agent and
five carbon black-filled NR compounds were prepared.
Z175 (pH = 6.9, Brunauer-Emmett-Teller (BET)
(adsorption isotherm) ((BET) = 175 m2 g−1 ) from
Kofran was used as the silica, Si69 from Degussa was
employed as a silane coupling agent and N220 (BET =
119 m2 g−1 , dibuthyl phthalate ((DBP) = 114 cm3 per

∗ Correspondence to: Sung-Seen Choi, Research Institute of Advanced Materials, Chungnam National University, 220 Gung-dong,
Yuseong-gu, Daejeon 305-764, Korea
E-mail: sschoi@korea.com
(Received 9 September 2002; revised version received 6 January 2003; accepted 27 January 2003)

 2003 Society of Chemical Industry. Polym Int 0959–8103/2003/$30.00 1382

 Natural rubber composites reinforced with Si or C black

Table 1. Formulations (phr)

Compound No

Component 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

SMR CV60a 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Z175b 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 0.0 0.0 0.0 0.0 0.0
Si69c 0.0 0.0 0.0 0.0 0.0 3.2 3.2 3.2 3.2 3.2 0.0 0.0 0.0 0.0 0.0
N220d 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 40.0 40.0 40.0 40.0 40.0
Stearic acid 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
ZnO 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0
HPPDe 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Wax 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
TBBSf 1.0 1.4 1.8 2.2 2.6 1.0 1.4 1.8 2.2 2.6 1.0 1.4 1.8 2.2 2.6
Sulfur 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4
a standard Malaysian rubber with constant viscosity of 60 MU.
b Silica from Kofran.
c Bis[3-(triethoxysilyl)propyl]tetrasulfide (TESPT) from Degussa.
d Carbon black from Cabot.
e N-Phenyl-N -(1,3-dimethylbutyl)-p-phenylenediamine.
f N-tert-Butyl-2-benzothiazole sulfenamide from Monsanto.

100 g) from Cabot was used as the carbon black.
Formulations and given in Table 1. Mixing of
compounds was performed in a Banbury-type mixer
at rotor speeds of 40 and 30 rpm for the master batch
(MB) and final mixing (FM) stages, respectively. The
initial temperatures of the mixer were 110 and 80 ◦ C
for MB and FM stages, respectively. The silica-filled
MB compounds were prepared as follows. (1) The
rubber was loaded into the mixer and premixed for
0.5 min. (2) The silica (and silane coupling agent) was
compounded into the rubbers for 2.0 min. (3) The
cure activators (zinc oxide and stearic acid) and
antidegradants (HPPD and wax) were mixed for
2.0 min and the compounds were discharged. The
carbon black-filled MB compounds were prepared as
follows. (1) The rubber was loaded into the mixer
and premixed for 0.5 min. (2) The carbon black was
compounded into the rubbers for 1.0 min. (3) The
cure activators (zinc oxide and stearic acid) and
antidegradants (HPPD and wax) were mixed for
2.0 min and the compounds were discharged. FM
compounds were prepared by mixing curatives with
the MB compounds for 2.0 min.
Cure characteristics were obtained using a Flexsys
rheometer (MDR 2000) at 160 ◦ C. Viscosities and
Mooney cure times of the compounds were measured
at 100 and 125 ◦ C, respectively, using a Mooney MV
2000 of Alpha Technologies. The vulcanizates were
prepared by curing at 160 ◦ C for 30 min. Physical
properties of the vulcanizates were measured with a
Universal Testing Machine (Instron 6021). Tan δ
values of the vulcanizates were measured according to
the procedure in ASTM D2231-87 with a Qualimeter
Eplexor 150N (Gabo).
RESULTS AND DISCUSSION
Dispersion of silica
In order to investigate the influence of TBBS con-
tent on the dispersion of silica, the degree of
dispersion of silica was observed using scanning
electron microscopy (SEM). Figure 1 shows SEM
photographs of the cut-off surface of silica-filled
NR vulcanizates. The filler dispersion of silica-filled
NR vulcanizates without the silane coupling agent
(Fig 1(a) and 1(b)) was poorer than that of the silica-
filled NR vulcanizates containing TESPT (Fig 1(c)
and 1(d)). This is due to the modification of the sil-
ica surface by TESPT. The silane coupling agent,
(C2 H5 O)3 Si—(CH2 )3 —Sx —(CH2 )3 —Si(OC2 H5 )3 ,
has a sulfidic linkage between triethoxysilylpropyl
groups. The ethoxy group of the coupling agent reacts
with the silanol group of the silica to form a siloxane
bond, for example silica ≡Si—O—Si(OC2 H5 )2 —
(CH2 )3 —Sx —(CH2 )3 —Si(OC2 H5 )3 . The bound
silane on the silica surface can make the filler–filler
interaction of silica weak and prevent the silica from
agglomerating.
Figure 1(a) and 1(c) are SEM photographs of the
compounds containing TBBS of 1.0 phr and Fig 1(b)
and 1(d) are those of the compounds containing TBBS
of 2.2 phr. The compounds with higher TBBS content
show better filler dispersion than those with a lower
content. This implies that the cure accelerator, TBBS,
can act as a dispersing agent in silica-filled rubber
composites. Since the silica surface is dense with
silanol groups (Si—OH) and is acidic, it forms a
strong hydrogen bond with TBBS, which is basic.
The TBBS adsorbed on the silica surface will prevent
agglomeration of silica. It is possible that the adsorbed
TBBS reacts with the silanol group. If so, the
chemically bonded residues of TBBS also prevent
the silica aggregates from agglomerating. The silane
coupling agent was mixed in the MB stage and the cure
accelerator, TBBS, was compounded in the FM stage.
Thus, the number of silane coupling agent, TESPT,
molecules that react with the silanol or adsorb on the
silica surface will be larger for the compounds without
the silane coupling agent than for those containing the

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S-S Choi, C Nah, B-W Jo

Figure 1. SEM photographs (×1000) of cut-off surfaces of vulcanizates 1 (a), 4 (b), 6 (c) and 9 (d).

silane coupling agent. The contents of TBBS in the Cure characteristics

compounds were measured by gas chromatography
after extraction of TBBS with acetonitrile at 90 ◦ C
for 4 h. The results are summarized in Table 2. The
amounts of TBBS extracted from the silica-filled
compounds were much smaller than those from the
carbon black-filled compounds. For the silica-filled
compounds, the amounts of TBBS extracted from
the compounds without the silane coupling agent
were much lower than those from the compounds
containing the silane coupling agent.
Figures 2, 3 and 4 show variations of rheocurves
with the TBBS content for the silica-filled NR
compounds without TESPT, the silica-filled NR
compounds containing TESPT and the carbon black-
filled compounds, respectively. For the silica-filled
NR compounds without the silane coupling agent, the
maximum torque (Tmax ) increases and the degree of

Table 2. Amounts of TBBS extracted from compounds (wt%)

Initial content of TBBS (phr)a

Compounds 1.0 1.4 1.8 2.2 2.6

Silica-filled 0.02 0.09 0.16 0.19 0.20

compounds without
the silane coupling
agent
Silica-filled 0.11 0.15 0.19 0.34 0.40
compounds
containing the silane
coupling agent
Carbon black-filled 0.37 0.61 0.78 0.84 0.95 Figure 2. Rheocurves of silica-filled NR compounds without silane
compounds coupling agent with TBBS content at 160 ◦ C. Squares, circles,
up-triangles, down-triangles and diamonds indicate TBBS contents of
a Parts per 100 rubber. 1.0, 1.4, 1.8, 2.2, and 2.6 phr, respectively.

1384 Polym Int 52:1382–1389 (2003)


Figure 3. Rheocurves of the silica-filled NR compounds containing
the silane coupling agent with TBBS content at 160 ◦ C. Squares,
circles, up-triangles, down-triangles and diamonds indicate TBBS
contents of 1.0, 1.4, 1.8, 2.2, and 2.6 phr, respectively.
Figure 4. Rheocurves of carbon black-filled NR compounds with
TBBS content at 160 ◦ C. the measurement temperature was 160 ◦ C.
Squares, circles, up-triangles, down-triangles and diamonds indicate
TBBS contents of 1.0, 1.4, 1.8, 2.2, and 2.6 phr, respectively.
the cure reversion also increases as the TBBS content
increases. Reversion is speculated to occur when the
desulfurization reaction is faster than the cross-linking
reaction during vulcanization. A severe reversion tends
to occur in NR compounds.10,11 In the case of
both silica-filled NR compounds containing the silane
coupling agent and carbon black-filled compounds,
Tmax also increases with increase in the TBBS content
but no remarkable reversion occurs.
Figure 5 shows the variation of Mooney viscosity
with the TBBS content. The Mooney viscosity was
obtained using a large rotor 4 min after preheating
for 1 min, which is denoted ML1+4. The viscosity, in
general, decreases with increase in the TBBS content
for all the compounds. This seems to be mainly due
to a peptizing effect of TBBS. The rubber chain is
dissociated by shear force during mixing, and this can
cause a decrease in molecular weight distributions.12,13
The viscosities of rubbers or rubber compounds with
higher molecular weight distributions are higher than
those with lower distributions.12 – 15 Polymer radicals
formed from the chain scission by shear force during
Polym Int 52:1382–1389 (2003)
Natural rubber composites reinforced with Si or C black
Figure 5. Variation Mooney viscosity at 100 ◦ C with TBBS content.
Squares, circles and triangles indicate the silica-filled NR compounds
without silane coupling agent, silica-filled NR compounds containing
silane coupling agent and carbon black-filled NR compounds,
respectively.
mixing recombine or react with other molecules or
other radicals to form a shorter chain. The S—N
bond of TBBS is relatively unstable and it is easily
dissociated by heat. Thus, TBBS will react with the
polymer radicals, which leads to a decrease in the
molecular weight distribution. The viscosities of the
silica-filled compounds without the silane coupling
agent are much higher than those of the other
compounds. This was due to a poorer filler dispersion
for the silica-filled compounds without the silane
coupling agent compared with the other compounds.
Figure 6 gives variations of the Mooney cure times
with the TBBS content. The t5 (Mooney scorch time)
and t (cure rate index) values were measured at
125 ◦ C; t5 means the time taken for the viscosity
to reach from the minimum point to increase of 5
Mooney units (MU) and it was used as the starting
point of vulcanizing reaction, t is the difference
between t35 and t5 and t35 means the time taken
for the viscosity to reach from the minimum point an
increase of 35 MU. t is used as a cure rate index:
the larger is t, the slower is the cure rate. For silica-
filled compounds containing the silane coupling agent
and the carbon black-filled compounds, t5 and t, in
general, become faster and faster as the TBBS content
increases. These are normal phenomena because a
cure accelerator such as TBBS generally accelerates
the vulcanizing reaction, leading to a faster cure. For
the silica-filled compounds without the silane coupling
agent, however, the variations of t5 and t show
anomalous behavior. This may be due to the excessive
adsorption of TBBS on the silica surface.
1385
S-S Choi, C Nah, B-W Jo
Figure 6. Variation Mooney cure times at 125 ◦ C with TBBS content.
Squares, circles and triangles indicate the silica-filled NR compounds
without silane coupling agent, silica-filled NR compounds containing
silane coupling agent, and carbon black-filled NR compounds,
respectively. Solid and open symbols stand for t5 and cure rate index
(t), respectively.
In the rheocurve of vulcanization time versus
torque, the torque increases after the minimum point
(minimum torque, Tmin ) by cross-linking reaction to
the maximum torque (Tmax ) and then decreases if
reversion occurs. The vulcanization reactions produce
several different cross-link structures including mono-,
di- and polysulfidic linkages. Polysulfidic linkages are
changed into mono- or disulfidic linkages as the
vulcanization proceeds. Reversion is observed when
the desulfurization reaction is faster than the cross-
linking reaction during vulcanization. The reversion
ratio was determined by dividing the difference
between the maximum torque and the torque at
2tmax by the delta torque; tmax means the time
at the maximum torque. The delta torque is the
difference between the maximum and minimum
torques (Tmax − Tmin ). For the silica-filled compounds
containing the silane coupling agent and the carbon
black-filled compounds, the reversion ratio decreases
linearly with increase in the TBBS content, as shown
in Figure 7. The slopes obtained from curve fitting
are about −5.3 and −4.7 %/phr, respectively. This
means that the reversion ratio decreases by about
5.3 and 4.7 % per 1.0 phr increase in TBBS. This
is because polysulfides decrease and the mono- and
disulfides increase as the cure accelerator content
increases.16,17 The silica-filled compounds without the
silane coupling agent did not show this trend. This is
an unexpected result. It seems that the unreacted
TBBS adsorbed on the silica surface and the TBBS
residues bonded to the silica participate in dissociation
reactions of the existing polysulfides.
1386
Figure 7. Variation in reversion ratio at t2 max with the TBBS content.
The measurement temperature was 160 ◦ C. Squares, circles and
triangles indicate the silica-filled NR compounds without silane
coupling agent, silica-filled NR compounds containing silane coupling
agent, and carbon black-filled NR compounds, respectively.
Delta torque is the difference between the maximum
and minimum torques. Since the torque in the
rheograph starts to increase by formation of cross-
links, delta torque is very closely related to the
cross-link density:16,18,19 the larger the delta torque,
the higher is the cross-link density. The delta
torque increased linearly with increase in the TBBS
content irrespective of the kind of compounds. The
straight lines in Fig 8 were obtained by curve fitting
and the correlation coefficients were >0.99. The
slopes are about 0.85, 0.75 and 0.51 for silica-
filled compounds without TESPT the silica-filled
compounds containing TESPT, and the carbon black-
filled compounds, respectively. This indicated that
the properties of the silica-filled compounds were
more affected by TBBS than the carbon black-filled
compounds. This was due to the adsorption of TBBS
on the silica surface. Since the silane coupling agent
prevents TBBS molecules from adsorption on the silica
surface to some extent for the silica-filled compounds
containing TESPT, the level of increased delta torque
is lower for the silica-filled compounds containing
TESPT than for the silica-filled compounds without
TESPT. The delta torques of the carbon black-
filled compounds are higher than those of the silica-
filled compounds. This can be also explained by the
adsorption of TBBS on the silica surface. Since the
silane coupling agent isolates some sulfur and makes
the formation of cross-links between rubber and silica,
the cross-link density of the silica-filled compound
containing the silane coupling agent is higher than
that of the silica-filled compound without the silane
coupling agent. The silane coupling agent Si69 has
Polym Int 52:1382–1389 (2003)
 Natural rubber composites reinforced with Si or C black

Figure 8. Variation of delta torque with TBBS content. The
measurement temperature was 160 ◦ C. Squares, circles and triangles
indicate silica-filled NR compounds without silane coupling agent,
silica-filled NR compounds containing silane coupling agent, and
carbon black-filled NR compounds, respectively.
Figure 9. Variation of the modulus with TBBS content. Squares,
circles and triangles indicate silica-filled NR vulcanizates without
silane coupling agent, silica-filled NR vulcanizates containing silane
coupling agent, and carbon black-filled NR vulcanizates, respectively.
Solid and open symbols stand for moduli at strain ratios of 100 and
300 %, respectively.

a sulfidic linkage of di- to octasulfides and the average

number of —Sx —is about 3.8.6 The sulfur content
of the silane is about 20 wt%. Elemental sulfur (S8 ) is
formed by heating the silane coupling agent.20

Physical properties
The modulus of a rubber vulcanizate is a property
proportional to the degree of cross-link density.16,17
The modulus of a rubber vulcanizate with a
higher cross-link density is higher than that of a
rubber vulcanizate with a lower density. The moduli
of the vulcanizates increase with increase in the
TBBS content (Fig 9). Especially for the silica-
filled vulcanizates containing TESPT and the carbon
black-filled vulcanizates, the increased moduli with
the TBBS content show linear relations (correlation
coefficients >0.99). The increments for the silica-
filled vulcanizates are larger than those for the carbon
black-filled vulcanizates. The 100 % moduli increase
by about 9 and 7 kg cm−2 per 1.0 phr increase in TBBS
for the silica-filled vulcanizates containing TESPT and
the carbon black-filled vulcanizates, respectively, and
the 300 % moduli increase by about 45 and 33 kg cm−2 Figure 10. Variation of tensile strength with TBBS content. Squares,
per 1.0 phr increase in TBBS, respectively. This is circles and triangles indicate silica-filled NR vulcanizates without
because the degree of increased delta torque for silica- silane coupling agent, silica-filled NR vulcanizates containing silane
filled compounds is larger than that for the carbon coupling agent, and carbon black-filled NR vulcanizates, respectively.

black-filled ones, as discussed previously.

Figure 10 shows variations of the tensile strength
with the TBBS content. The tensile strength of a
rubber vulcanizate increases and then decreases as the
cross-link density increases.16,17 For the carbon black-
filled vulcanizates, the tensile strength, in general,
decreases slightly with increase in the TBBS content.
The tensile strength of the silica-filled vulcanizate
containing TESPT at first increases notably and
then remains almost constant. The tensile strength of
the silica-filled vulcanizate without TESPT increases

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S-S Choi, C Nah, B-W Jo

continuously as the TBBS content increases. This

is due to the relatively lower cross-link density and
improvement of the silica dispersion with the aid of
TBBS.
Figure 11 shows variations of the elongation at
break with the TBBS content. For the silica-filled
vulcanizates containing TESPT and the carbon black-
filled vulcanizates, the elongation at break decreases
with increase in the TBBS content. This is due to the
increased cross-link density. In general, elongation at
break of a vulcanizate with higher cross-link density is
shorter than that of a vulcanizate with a lower density
since elongation at break is inversely proportional
to the cross-link density.16,17 For the silica-filled
vulcanizates without the silane coupling agent, the
elongation at break increases and then decreases as the
TBBS content increases. The increased elongation at
break is surprising. This may be due to improvement
of the filler dispersion. The silica-filled compounds
without the silane coupling agent have very poor
filler dispersion. TBBS will greatly largely the silica
dispersion. The improved filler dispersion makes the
elongation at break improve. Figure 12. Variation of tanδ at 0 ◦ C with TBBS content. Squares,
Figures 12 and 13 show variations of the tanδ values circles and triangles indicate silica-filled NR vulcanizates without
at 0 and 60 ◦ C with the TBBS content, respectively. silane coupling agent, silica-filled NR vulcanizates containing silane
Tanδ values at 0 and 60 ◦ C reflect the wet traction coupling agent and carbon black-filled NR vulcanizates, respectively.

and the rolling resistance, respectively. The larger

the tanδ value at 0 ◦ C, the better is the wet traction
property of a vulcanizate, and the smaller the tanδ
value at 60 ◦ C, the better is the wear property of a
vulcanizate. Variations of tanδ at 0 ◦ C of the silica-
filled vulcanizates without TESPT and the carbon

Figure 13. Variation of tanδ at 60 ◦ C with TBBS content. Squares,

circles and triangles indicate silica-filled NR vulcanizates without
silane coupling agent, silica-filled NR vulcanizates containing silane
coupling agent, and carbon black-filled NR vulcanizates, respectively.

black-filled vulcanizates show opposite trends. For the

Figure 11. Variation of the elongation at break with TBBS content.
Squares, circles and triangles indicate silica-filled NR vulcanizates
without silane coupling agent, silica-filled NR vulcanizates containing
silane coupling agent, and carbon black-filled NR vulcanizates,
respectively.
silica-filled vulcanizates without TESPT, tanδ at 0 ◦ C
at first increases notably and then remains almost
constant near 0.101 as the TBBS content increases,
whereas that of the carbon black-filled vulcanizates
at first decreases and then remains almost constant

1388 Polym Int 52:1382–1389 (2003)


near 0.125. This may be due to the improved silica
dispersion by TBBS. Tanδ at 60 ◦ C decreases with
increase in the TBBS content, irrespective of kind of
vulcanizate. This is due to the increased cross-link
density by TBBS.
CONCLUSIONS
TBBS improves silica dispersion. For silica-filled
compounds, adsorption of TBBS on the silica surface
and reactions of TBBS with the silanol groups
lead to different cure characteristics to the carbon
black-filled compounds. Especially the silica-filled
compounds without the silane coupling agent show
anomalous behavior. The reversion ratio of the silica-
filled compounds without TESPT increases with
increase in TBBS content, whereas those of the other
compounds decrease. The silica-filled vulcanizates
without the silane coupling agent show different
physical properties from the other vulcanizates. By
increasing the TBBS content (increase in cross-link
density), for the silica-filled vulcanizates without the
silane coupling agent, the tensile strength increases
and the elongation at break does not decrease. These
anomalous behaviors of the silica-filled compounds
without the silane coupling agent may result from poor
filler dispersion and excessive adsorption of TBBS on
the silica surface.
Polym Int 52:1382–1389 (2003)
Natural rubber composites reinforced with Si or C black
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