Iranian Polymer Journal I Volume 5 Number 3 (1996) 1026-1265196

Effect of a Multifunctional Additive on Curing Characteristics

and Mechanical Properties of Carbon Blacks Filled
Natural Rubber Compounds

Hanafi Ismail and Zulkifli Ahmad

School of Industrial Technology, Universiti Sains Malaysia
11800 Minden, Penang, Malaysia

Aeccived : 15 May 1996; accepted 16 July 1996

ABSTRACT

The effects of a multifunctional additive on curing characteristics and mech-

anical properties of N330 and N220 carbon blacks filled natural rubber com-
pounds have been studied . The mechanical properties of vulcanizates with
carbon blacks have been enhanced by incorporating a multifunctional addi-
tive. The amounts of 2 phr and 3 phr of the additive are found to be the
optimum loading for 50 phr of N330 and N220 carbon blacks, respectively.
The optimum loading is also found to correspond approximately to the
amount needed for a monolayer coverage of the carbon black surface . As
for natural rubber and carbon black of N330 type mixes, the rate and state
of cure in natural rubber and N220 type of carbon black mixes are depen-
dent on the multifunctional additive loading as well.

Key Words : multifunctional additive, curing characteristics, mechanical properties, dispersion, carbon black

INTRODUCTION compound with 50 phr (parts per hundred rubber)

of N330 carbon black was shown to increase
In 1983, a single compounding ingredient, n-tallow- physical properties and inphase component of dyn-
1,3-propane diamine salt of carboxylic acid with the amic modulus (G') up to a loading of 2 phr, after
general structure: which there is a gradual deterioration of these
[R ' NH 2 •(CH 2) 3NH 3] 2+ 2[6-,- H33C00]- properties.
and a number of modes of action in a rubber com- Calculation shows that 2 phr of MFA cones-
pound was discovered [1] . This surfactant has been ponds approximately to the amount needed for a
termed a multifunctional additive (MFA) since it monolayer surface area of 78 m2lg as measured by
can function as a processing aid, a filler dispersant, nitrogen adsorption.
a cure accelerator and a mould release agent. In this work, carbon black N220 with a speci-
In previous reports [2, 3], the addition of fic surface area of 110 m2lg is used at loading of 50
MFA (EN 444) to natural rubber (SMR 20) phr to study the effect of different carbon blacks

207
Lfferl nF a Muliifunclional Additive an Curing Characteristiw

surface area on curing characteristics and mechan- measured by abrasion debris DIN abrader (Method
ical properties of the natural rubber compounds. A) as per BS 903 : Part A9, and by a Wallace Croy-
don IRHD Instrument according to BS 903 : Part
A26 . Dynamic properties were measured by the
EXPERIMENTAL Dartec servo hydraulic machine at room temper-
ature (25 ` C) . Transfer moulding was used to
Materials produce the double shear test pieces . with rubber
The compounding materials, their manufacturers disc dimensions of 32 mm diameter and 8 mm
and the loading were used as in ref[2] except that thickness . Cyclic tests were performed on each
N2211 grade of carbon black are employed as well specimen at double strain amplitudes (DSAS) from
as the N330. Various loadings of the MFA, expres- (100316 to 1 . The frequency was maintained at 1
sed as phr of rubber by weight were incorporated Hi throughout the range of amplitudes.
to study the concentration effects . Sulphur is added
as a cross-linking, i .e . a curing, agent . Zinc oxide
and stearic acid act together as a cure activator, RESULTS AND DISCUSSION
N-cyclohexylbenzothiazolc-2-sulphenamidc (CBS)
a Monsanto product is a curing accelerator, and Curing Characteristics
1,2-dihydro-2,2,4-trimethylquinoline (Flectol-H) is Table 1 shows that, as for SMR 201N330 mixes [2]
an antioxidant. the rate and state of cure in SMR 201N220 mixes
are also dependent on the MFA loading.
Sample Preparation Compared to the control compound (0
Mixing was carried out on a computer controlled MFA), scorch time is reduced about 67%, and l,,s
Francis Shaw Kl Intermix internal mixer . Each (cure time) is reduced by about 42% for the mix
batch was then sheeted off by one pass through a with 5 phr of MFA . The reduction of the scorch
two roll mill with the nip at approximately 3 mm, and cure times are attributed to the dissociation of
which was convenient for the subsequent prepara- MFA molecules into a primary amine and a fatty
tion of test specimens. The mixing cycle used is acid at vulcanization temperature . The MFA used
presented in our previous report [2], with the in this work has been found to dissociate at --1211
difference that the dump temperatures in mixing 'C [4] . The diamine accelerates curing and is
conditions were 110-1 16'C. responsible for the reduction of the scorch and
The compounds were vulcanized to their res- cure times as the MFA loading increases.
pective optimum cure times, t9 s as determined by a
Wallace Precision Cure Analyzer at 160 ' C, and Physical Properties
these duration values were used to vulcanize all Table 1 shows that. as expected, the physical prop-
the specimens used in this study as well. erties (i .e . hardness, tensile strength, tear strength,
and abrasion resistance) for six SMR 101N220
Mechanical Properties mixes filled different loading of MFA have a high-
The stress-strain properties and tear strength of er value if compared to SMR 201N330 at the
the vulcanizates were measured on a Hounsfield similar loading of MFA (Table 2).
500L testing machine at room temperature accord- Specific surface area of carbon black N220
ing to BS 903 : Part A2 and BS 903 : Part Al, (110 m zlg) is higher than carbon black N330 (78
respectively . The rate of separation of the grips for m 2 lg) . More MFA is needed to form a monolayer
stress-strain properties and crescent tear test coverage of a carbon black with a higher surface
(Method C) was adjusted to 500 mmlmin and trou- area . Therefore the amount of MFA needed for
ser tear test (Method A) at 100 mmlmin . Abrasion carbon black N220 is greater than for carbon black
resistance and hardness of the vulcanizates were N330 . Previous results have shown that the

lranion Polymer k+urnal 1 Volume 5 Number :f {1991 )

208
 tonal a . a a.

Table 1 . Properties of six SMA 20106(N220) mixes filled with different loadings of MFA (EN 444).
1 ,

Properties MFA (phr)

0 0 .3 1 2 3 5

Compound properties*
Max torque (Nm) 1 .90 2 .03 2 .04 2 .00 2.00 1 .91
Mln torque (Nm) 0.47 0.51 0 .50 0 .44 0 .23 0 .20
Scorch time, is (s) 45 38 32 20 18 15
tgt (a) 386 380 338 328 271 224

Vulcanizate properties
Hardness (fRHD) 71 73 75 75 76 74
Tensile strength (MPa) 25 .4 26 .4 26.9 27 .4 28 .6 26 .1
Elongation at break (%) 474 445 432 429 419 448
100 % Modulus (MPa) 3.22 3 .30 3 .65 3 .72 3.83 3 .09
300 % Modulus (MPa) 14 .50 15 .07 15 .32 15 .42 15 .70 14 .58
Tear strength (kN/m) (trouser) 52 60 67 71 78 62
Tear strength (kNlm) (crescent) 140 143 153 161 166 151
Abrasion resistance, DIN (vol,losslmm 3) 71 .5 70 .4 69 .0 67 .7 65 .8 72.1

* Wallace Precision Cure Armazer at leaf

Table 2. Properties of six SMR 20IN330 mixes filled with different loadings of MFA [2].

Properties MFA (phr)

0 0.3 1 2 3 5

Compound properties*
Max torque (Nm) 2 .41 2.51 2 .55 2.58 2.51 2.41
Min torque (Nm) 0 .64 0 .69 0.66 0.65 0.61 0 .53
Scorch time, t5 (s) 40 34 29 27 26 19
t95 (s) 375 356 330 291 287 263

Vulcanizate properties
Hardness (IRHD) 69 69 69 68 66 65
Tensile strength (MPa) 24.9 26 .1 26.2 26.6 26.5 25 .6
Elongation at break (%) 506 453 448 450 458 465
100 % Modulus (MPa) 3.3 3 .B 3 .7 3 .9 3 .7 3.8
300 % Modulus (MPa) 14 .7 16 .4 16.4 16.6 16 .3 15 .8
Tear strength (kNlm) (trouser) 46 53 63 69 47 47
Tear strength (kN/m) (crescent) 73 84 96 99 93 92
Abrasion resistance, DIN (vol.losslmm 3) 74 74 73 72 75 80

* Wallace Precision Cure Analyzer at 160 'C

Iranian Polymer Journal f Vdume 5 Number 3 (1996) 209

elkct or a Multifunctional Additive on C :urine C Jeracttristirs

Table 3 . Dynamic properties for six SMR 201N220 mixes with different loadings of MFA (EN 444) at various double strain
amplitude (DSA) and frequency of 1 Hz.

Mix A (control) Mix B (0.3 phr) Mix C (1 phr)

'DSA
1i G ` (MPa) `Tan o G ' (MPa) Tan 6 G ' (MPa t Tan 6

0.00316 7 .03 0-0699 7 .99 0 .0470 8 .61 0 .0491

0 .01 6 .19 1 .1011 7 .04 0 .0918 7 .54 0 .0933
0.0316 4 .82 0.1524 5 .32 0 .1445 5 .61 0 .1511
0 .1 3 .43 0 .1657 3 .68 0 .1647 2 .84 0 .1394
0 .316 2 .50 0 .1388 2.63 0 .1369 82 .84 0 .1394
1 .0 1 .78 0 .1180 1 .85 0 .1134 1 .95 0 .1129

Mix D (2 phr) Mix E (3 phr) Mix F (5 phr)

DSA
G ' (MPa) Tan 6 G ' (MPa) Tan 6 G ' (MPa) Tan 6

0 .00316 8.83 0 .0410 9.26 0 .0554 8 .35 0 .0640

0 .01 7.68 0 .0868 7.79 0 .0973 7 .42 0 .1040
0 .0316 5 .84 0 .1387 5.98 0.1512 5.51 0 .1555
0 .1 4 .05 0.1551 4.05 0.1647 4.02 0 .1776
0 .316 2 .86 0.1368 2.88 0.1395 2.81 0 .1568
1 .0 1 .97 0.1116 1 .98 0.1210 1 .86 0 .1341

a: Double drones amplitude

b: lnp6usc modulus

a loss anger

addition of MFA in a rubber mix improves the 29

vulcanized rubber properties e .g. tensile strength.
modulus and tear strength 12, 3] . Figures 1-3 show 28
the comparison in tensile strength, tear strength
(crescent) and abrasion resistance of N220 and
a 27

N330 tilled natural rubbers at various MFA 26

loadings . The optimum MFA loading increases
with increasing surface area . The addition of MFA 25
y
(EN 444) to an NR compound with 50 phr of N220 24
and N330 carbon black is found to increase the
vulcanizate and dynamic shear modulus, G ' , up to 23
a critical level (amount to coat the carbon black
with a monolayer q i MFA) . after which there is a 22
0 1 2 3 4 5
gradual deterioration of properties . The deteriora-
MFA Loading (phr)
tion after optimum loading is likely to be due to
the formation of a second weak MFA interlayer, Figure 1 . Relationship between tensile strength and MFA
which would reduce the carbon black-rubber inter- loading for SMR 20 compounds with two different carbon
action and results in a reduction in rubber blacks.

210 Iranian Puhunrr fauna! Volume 5 Nunther 3 (3996)

 [srnai] H . et al.

170 2 .2
+ N 330
150 r N 220
2 .0

130
1 .8
110
1 .6
90

1 .4
70

50 1 .2
0 1 2 3 4 5 0 2 3 4 5
MFA Loading (phr) MFA Loading {phr}

Figure 2. Crescent tear strength vs MFA loading with two Figure 4. Relationship between in phase shear modulus
different carbon black. and MFA loading for SMR 20 compounds with two different
carbon blacks at DSA =1 .0.
properties.
Table 3 show, the dynamic properties for six 29/N330 occurred at 2 phr while in SMR 201N220
SMR 20/N220 mixes with different loadings of EN- occurred at 3 phr.
444 at various double strain amplitude (DSA) and Figure 5 shows that the lowest value of tan r5
frequency 1 Hz. for N220 and N330 carbon blacks is obtained at 2
Figure 4 shows the plot of the inphase shear phr and 1 phr of MFA, respectively, which is less
modulus vs MFA loading at a DSA equal to 1 .0 for than the loading needed for optimum mechanical
N220 and N330 tilled natural rubbers . As for ten- properties . The increase in mechanical properties
sile strength, tear strength, and abrasion resistance. up to optimum loading is attributed to the improv-
it can be seen that the optimum peak in SMR ed carbon black dispersion, which has been observ-
52 ed by scanning electron microscopy (SEM) and
0 .14
E
E
72
0 0 .13
b
a
= 82

N
w

p 52 + N 330
N
N
n N 220
.0 0 .10

0 1 2 3 4 5 0.09
MFA Loading (phi) 0 1 2 3 4 5
1v1FA Loading (phr)
Figure 3 . Relationship between abrasion resistance and
MFA loading for SMR 20 compounds with two different Figure 5. Tan 6 vs MFA loading for SMR 20 compounds
carbon blacks . with two carbon blacks at DSA=1 .0.

Iranian f'~~h-rner Journal / Voiurru .5 Number' .s ( .7-ti/6) 211

Effect of a Multifunctional Additive on Curing Characteristics

computer aided image analysis [21. blacks is shown to increase mechanical properties
It is clear that MFA improves carbon black up to a loading (critical loading to coat the carbon
dispersion and a decrease of tan 6 would therefore black surface with a monolayer of MFA), of 2 phr
be expected . q n the other hand, the presence of and 3 phr, respectively, after which there is a
MFA et the interface is expected to weaken the gradu- al deterioration of properties . A monolayer
interfacial interaction between the carbon black cover- age of the carbon black is found to
and rubber . Calculation [51 shows that the pre- correspond to the MFA loading for optimum
sence of MFA at the interface weakens the inter- mechanical proper- ties . The deterioration after
facial interactions between the carbon black and optimum loading is due to weaken interfacial
rubber by approximately 30% . Therefore the interactions between the adjacent layers of MFA
detachment of rubber molecules from the tiller molecules.
surface is easier if MFA is present and this is an
energy dissipation process . The observed minimum
of tan 6 at 1 .0 phr and 2 .0 phr of MFA for N330 REFERENCES
and N220 is the sum of the reduction due to imp-
roved filler dispersion, and the increases due to the 1. Hepburn C ., and Mandi M . S ., Plast. Rubber Process.
increasing amount of MFA on the filler surface. Apple 6, 247, 1986.
Calculation also shows [51 that to cover the carbon 2. Ismail H. . Freakley P. K ., Sutherland I ., Bradley R . H . and

black surface with a monolayer of MFA, -2 .0 phr Sheng E., Piasf. Rubber. Composite Process. A ppt, 23, 43,
and -3 .0 phr are required for 50 phr of N330 and 1995.

N220, respectively . These values agree broadly 3. Abid in M . Z., Ismail H ., Murray G . A. W., and Freakley
with the optimum loadings observed for mechan- P . K ., Rubber W orld, 211, 1, 30, 1994.

ical properties. 4. Bradley R . H ., Sheng E ., Sutherland I., Freakley P. K.,

and Ismail H ., J. Mara. Chem ., 4, 8, 1189, 1994.

5. Ismail It ., Ph .D . Thesis, Loughborough University of

CONCLUSION Technology, Loughborough, 1994.

6. Sheng E., Bradley R . H ., Sutherland I ., Freakley P . K., and
The addition of MFA to a natural rubber com- Ismail H . Presented at International Conference on
pound with 50 phr of N330 and N220 carbon Carbon, Granada, Spain, 4—8 July 1994.

212 Iranian Pvtymer Journal / Volume i Number 3 (1996)