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This paper re-examines the use of sulphuric acid as a coagulant for natural rubber
latex. It also discusses the effect ofpH of coagulation and treatment ofcoagulum on
the raw rubber properties, rheometric cure properties of ACS-1, ISO and tread
mixes, and physical properties ofvulcanisates of ISO and tread mixes. Heat ageing
and stress decay of these vulcanisates are also examined. Sulphuric acid as a coagulant does not severely alter the raw rubber properties if the pH of coagulation is kept
at pH 5. The resultant rubbers have lower Mooney viscosity, and are marginally
inferior in tensile properties on heat ageing. Rubbers coagulated with sulphuric acid
at pH below 3.5 have distinctly poorer ageing properties.
EXPERIMENTAL
and classified for two series of experiments. One series was coagulated at pH
5.0, and the other series at pH 3.5. Within
each series, four samples were coagulated
using a mixture of formic acid and sulphuric acid in the ratios 1:0, 2:1, 1:2 and
alarm manufacturers. It was also observed6 that rubber coagulated by excessive sulphuric acid tended to have retarda-
109
COMMUNICATION 672
Journal of the Rubber Research Institute of Malaysia, Volume 28, Part 3, 1980
Stress Relaxation
The rubber compounds chosen for
stress relaxation were:
Rubber
ZnO
Stearic acid
CBS
Sulphur
FlectolH
pares raw and vulcanised rubber properties of rubber samples prepared from coagulation at pH 5 andpH 3.5,and wherever
possible rubbers coagulated below pH 3.5
or at pH 2.0 have been included.
Mix A
Mix B
100
5
2
0.6
2.55
100
5
2
0.6
2.55
1.0
in the oxidative resistance against molecular oxygen. The rubber vulcanisate was
stretched at 70% strain, allowed to relax
influences the PRI values; the PRI decreases with increase of sulphuric acid in
the coagulant mixture. In tact, it was
observed that the dry rubbers prepared by
coagulation of latex at pH 3.0 and below
Effect
110
COPYRIGHT MALAYSIAN
RUBBER BOARD
Alias bin Othman and B.L. Chan: Effect of pH of Coagulation and Sulphuric Acid
100 r
80
60
'o
o
_Q.
CE
Q_
on
40
20
~B^
.5
TO
o
'
&
o
o
-o
<J
nj
a
L.
^
-o
ta
"w
3
CL
'o
ro
*
O
0L
iT)
OJ
o
o
O
O
5-0
3-5
3-0
2-0
VR
PQ
PRI (%)
N2 (%)
Ash(%)
Colour (lovibond units)
pH 5.0
73
48
86
0.41
0.25
3.0
Formic acid
pH 3.5 pH 2,0
65
43
89
0.40
0.22
4.0
63
41
77
0.48
0.23
5
Sulphuric acid
pH 5. 0 pH 3.5 pH 2.0
69
45
89
0.40
0.27
3.0
61
39
85
0.41
0.26
5.0
59
36
54
0.49
0.27
9
Formic acid
Rubber
pH 5.0
Non-viscosity
Sulphuric acid
pH 5.0
pH 3.5
pH 3.5
74
63
68
59
68
58
55
53
stabilised
Viscosity
stabilised
Sulphuric acid
With washing No washing
Formic acid
With washing No washing
Property
68
44
88
0.40
0.22
3.0
FR (mean) range
PQ (mean) range
PRI (%)
N2 (%)
Ash (%)
Colour (lovibond units)
65
42
88
0.40
0.28
4.0
69
45
87
0.40
0.24
4.0
65
41
90
0.41
0.27
4.0
Formic acid
pH 5.0
Item
Sulphuric acid
pH 5.0
pH 3.5
pH 3.5
Without
washing
, , .
Washing
Without
washing
. , .
Washing
Without
washing
Washing
Pro-oxidant
metallic ion (p.p.m.)
5.7
4.8
3.7
6.0
6.1
13.5
7.2
13.7
6.9
4.2
8.4
4.8
4.2
12.7
4.6
12.2
Total heavy8
metallic ion
content (p.p.m.)
6.7
5.7
6.3
6.9
8.0
14.5
8.5
14.6
Residual sulphate
SO4~2 (%wt)
a
0.16
Without
washing
0.26
Washing
0.20
0.37
Alias bin Othman and B.L. Chan: Effect of pH of Coagulation and Sulphuric Acid
Formic acid
Property
Sulphuric acid
pH5.0
pH3.5
pH 5.0
pH 3.5
5.2
34.1
30.8
1.42
6.0
4.6
36.0
28.3
1.37
5.8
5.6
35.4
20.8
1.35
7.8
4.7
33.0
28.4
1.44
6.2
Property
Washing
No washing
4.5
35.3
30.8
1.40
4.8
34.8
28.8
J.39
5.7
Sulphuric acid
Washing
No washing
6.1
113
5.2
34.6
29.4
1,40
7.0
5.1
33.8
28.7
1.40
6.9
Journal of the Rubber Research Institute of Malaysia, Volume 28, Part 3, 1980
TABLE 7. EFFECT OF pH ON THE TECHNOLOGICAL PROPERTIES
OF RUBBERS IN ISO MIX
Property
Formic acid
pH3.5
pH5
pH5
Sulphuric acid
pH3.5
Torque, AT (N-m)
Mooney scorch, T5 at 120 C (min)
6.3
21.0
14.7
3.51
19.6
4,5
18.3
13.8
3.55
13.2
6.8
21.5
14.7
3.47
22.2
4.3
18.7
14.4
3.38
12.6
29.2
510
14.0
1.98
60.0
79.1
28.7
510
12.8
2.02
61.0
78.4
30.0
530
12.4
2.02
62.0
79.9
29.1
550
9.1
30
8.3
29
10.2
34.2
300
57
10.2
82
+ &
8.8
30
290
53
0
11.4
1.89
62.0
76.8
220
280
43
9.1
65
+ 1.0
55
+ V4
Rubber 100, Zinc oxide 5; stearic acid 2; sulphur 2.25; Santocure NS 0.7; IRB3 35. Cured at 140 C/40 min
Alias bin Othman and B.L. Chan: Effect of pH of Coagulation and Sulphuric Acid
TABLE 8. EFFECT OF pH OF COAGULATION ON THE TECHNOLOGICAL
PROPERTIES OF RUBBER IN A TREAD MIX
Property
Formic acid
pH5.0
pH3.5
6.8
29.0
22.2
3.47
18.5
4.6
23.0
18.4
3.46
12.8
pHS.O
Sulphuric acid
pH3.5
7.0
32.0
25.4
3.16
21.0
4.5
25.7
21.2
3.29
13.0
M300 (MN/m 2 )
Hardness (IRHD)
Dunlop resilience (%)
27.1
540
2.5
11.9
65.5
62.8
26.1
520
2.4
11.8
65.5
65.2
27.1
550
2.5
11.8
63
65.3
25.1
500
2.6
12.6
66.5
65.6
15.0
57
9.2
34
300
11.3
44
M300 (MN/m 2 )
Retention (%)
14.4
53
360
67
11.5
380
73
10.8
92
97
55
9.2
78
300
60
11.3
Journal of the Rubber Research Institute of Malaysia, Volume 28, Part 3, 1980
Time (mini
600
09
07
06
0-5
Samples
A C 4 - 3 pph.m.)
- 8 C13-4 p.p.h.mD
C H7-3 (xpKm)
ACpH5.0)
- D (268 p.p.hm)
00 protected accelerated sulphur system
D CpH 3-0)
BCpH5'0)
CCpHSO)
0-4
03
Figure 2. Effect
13
CONCLUSION
is observed that this increases with increasing iron content. It is reasonable to presume from this observation that iron acts
as a pro-oxidant in vulcanised natural
rubber, accelerating basic oxidation.
116
Alias bin Othman and B.L. Chan: Effect of pH of Coagulation and Sulphuric Acid
Samples
A ( 4-3 p.p-h.m.1
B(13-4p. p hm)
CC17-3p.phm)
D (26 8 (xpJimJ
00 protected accelerated sulphur system
-0-2
400
Time (min)
600
perties
ACKNOWLEDGEMENT
Journal of the Rubber Research Institute of Malaysia, Volume 28, Part 3, 1980
9. DUN.J.R. AND SCAULAN.J. (1963) Stress
Relaxation Studies of Network Degradation. The Chemistry and Physics of
Rubber-like Substance (Bateman, L. ed),
p. 661. London: Maclaren and Son Ltd.
REFERENCES
1. RUBBER
GROWERS' ASSOCIATION
(1920) The Effect of Acids in Retarding
Rate of Cure. The Bulletin, 2, 243.
2. RUBBER
GROWERS' ASSOCIATION
(1923) Warning Against the Use of Sulphuric Acid as a Coagulant. The Bulletin,
5, 247.
Rubb.J., 111,629.
4. WILTSHIRE, J.L. (1932) Sulphuric Acid as
a Latex Coagulant. /. Rubb. Res. Inst.
Malaya, 4,94.
5. MARTIN, G. AND DAVEY, W.S. (1933)
Rubber from Latex Coagulated with Sulphuric Acid. /. Rubb. Res. Inst. Malaya,
5,282.
15. BOTT, E.G. AND GILL, L.C. (1942) Oxidation of Vulcanised Rubber by Copper and
Manganese Compounds. Trans. I.RJ., 19,
53.
118