VOLUME 19 PART 3

Significance of PRI in Raw and Vulcanised

Natural Rubber
L. BATEMAN and B. C. SEKHAR
The Plasticity Retention Index (PRI) has been developed as an objective test for the oxidis-
ability of raw natural rubber and has recently been associated with the Standard Malaysian
Rubber scheme. Extensive studies both to ascertain the preparative and treatment factors
which determine PRI and to assess its bearing on factory processing behaviour and ultimate
vulcanisate properties have been carried out and are now surveyed. It is evident that the
oxidisabttity of natural rubber as measured by PRI significantly affects its behaviour in the
factory and in service performance and that prior information on this property permits adjust-
ments in vulcanisate recipes and in processing conditions to be made so that the most advan-
tageous balance in properties is achieved.
Natural rubber possesses a chemical structure Measuring Raw Rubber Oxidisability
which makes it susceptible to oxidation. The The first problem is to devise a sufficiently
principal causes are (i) exposure to sunlight; (ii) simple and objective measure of raw rubber
high temperatures; and (iii) excessive mechan- oxidisability. Tests employed hitherto (e.g. the
ical working (PIKE AND WATSON, 1952 and Firestone Rubberscope) have provided a very
WATSON, 1953). These causes will be reip.- useful assessment over a limited range of condi-
forced if the rubber contains metallic contami- tions and when arbitrarily standardised against
nants or if naturally occurring pro-oxidants are certain technological properties, but are al-
activated (SEKHAR, 1958); they are repressed by together too subjective for general specification
the naturally occuring inhibitors (ALTMAN, purposes.
1948; CARLIER, 1961 and SUBRAMANIAM, 1965). The Plasticity Retention Index (PRI) test
Normal collection, processing, and handling developed in the N.R.P.R.A. and R.R.I.M.
of the raw rubber affects these several promot- laboratories is considered to remedy this defi-
ing or inhibiting factors, with the net result ciency. It consists of heating a rubber sample
that the marketed product may be oxidised to of fixed size and thickness at a temperature of
some extent, may be especially prone to oxi- 140°C for 30 minutes, determining the plasti-
dation, or may be highly resistant. These cha- city in numerical units on a Wallace Plasti-
racteristics will obviously bear on raw rubber meter and expressing this value as a percentage
behaviour such as ageing and mastication of the original plasticity. Precise temperature
characteristics, and will also carry through in- control and standardisation of procedure is, of
directly to vulcanisate properties which reflect course, essential for accurate results.
manifestations of this—always remembering Figure 1 shows how conventional grades of
that it is not the mere uptake of oxygen which
is important but the marked reduction in mole- rubber behave in this test—there is clearly a
cular size which follows as an inevitable con- broad correlation between a tendency to greater
sequence. Oxidised rubber is lower molecular loss in plasticity (i.e. softening) and the poorer
weight rubber and it is this fact which leads to quality of the rubber as assessed by conven-
poorer physical and technological properties, tional grading. Further, this correlation is in
unless due allowance is made or remedial mea- line with Heal's assessment of 'quality' using
sures applied. the Firestone Rubberscope (HEAL, 1963).
COMMUNICATION 393

133
 Journal of the Rubber Research Institute of Malaya, Volume 19, Part 3, 1966

much closer; the purchaser of the lower grades

J______I——————L
5 IO 15 2O 25 3O
AGEING TIME AT I4O°C (MIN.)
Figure L PRI vs oven ageing at 140° C.
The PRI values of some different types and
grades of Malaysian natural rubber are given
in Table L The figures indicate that the better
quality rubbers, as commonly accepted, have
higher PRI's with distribution values which are
buys not only inferior quality but greater vari-
ability in this property, as indeed in others as
well. Latex rubbers as conventionally processed
yield PRI values in excess of 80; remilled rub-
bers show a wide range of values with the me-
dian much below this figure. Factors which
influence these differences will be considered
in turn.
1. Effect of Exposure to Sunlight
Sunlight is a powerful degradative agent for
rubber, as is already known for tensile and
dynamic properties. The effect of sunlight ex-
posure on PRI values is shown in Table 2. The
significant fact is that whereas exposure of dry
rubber leads to a marked fall in PRI, exposure
in the wet state has a relatively inappreciable
effect.
2. Effect of Excessive Heating During Drying
Raising the drying temperature does not
necessarily reduce PRI but application of heat
to the rubber after drying reduces PRI mark-
edly, as is illustrated in Table 3.
3. Effect of Metallic Contamination
Among the metals occurring in raw latex and
solid rubber, those of significance to oxidative
degradation are copper, manganese and iron.
In some instances, however, these metals can
be present in an inert form while in others they
can actively catalyse degradation of the raw

TABLE 1. PRI LEVELS OF MALAYSIAN NATURAL RUBBER

% of 500 samples
PRI
RSS Heveacrumb Estates RemUlers
(from latex) brown crepe brown crepe

100—110 6.5 24.6

90—100 42.9 70.7 0.4 _
80— 90 50.5 4.6 11.4 —
70— 80 0.1 0.1 40.2 —
60— 70 — — 30.4 2.8
50— 60 — — 13.3 28.2
40— 50 — — 2.8 39.6
30—40 — — 1.3 28.2
20— 30 — — 0.2 1.2

134
COPYRIGHT © MALAYSIAN RUBBER BOARD
L. BATIMAN and B. C. SEKHAR: Significance of PRI in Raw and Vulcanised Natural Rubber

TABLE 2. EFFECT OF SUNLIGHT

PRI on exposure to sunlight

Sample Wet Dry
0 hrs 3 hrs 6 hrs ' 0 hrs 3 hrs 6 hrs

RSS 94 100 92 94 81 63
Cup lump 88 85 84 88 61 49
IX (remitters) 37 37 35 37 20 12
2X (remillers) 22 20 17 22 10 7

TABLE 3. EFFECT OF HEAT DURING DRYING ON PRI

After drying
During drying —————
Sample 60°C 100BC
60°C 100°C 1 day 3 days 1 day 3 days

RSS 93 79 102 89 76 —
IX Crepe 37 51 36 35 Degraded
2X Crepe 37 46 32 31 Degraded

polymer on heating. The influence of certain differently the amount and kind of non-rub-
added compounds is shown in Table 4; while bers retained in the rubber and thus the balance
copper is a potent oxidant, iron is of secondary of anti-oxidant and pro-oxidant constituents.
importance and manganese is almost without Without attempting to trace these effects in
effect in the form used. detail, the observed changes in PRI when diff-
erent processing methods are followed are set
TABLE 4. EFFECT OF METALLIC out in Table 5. The results show that while
CONTAMINATION OF LATEX RUBBER natural rubber latex in its native state is very
well protected against ageing deterioration,
Metallic salt, % PRI this favourable circumstance can be changed
by slight alterations on processing techniques.
0 94
Thus, the total solids film obtained on evapo-
0.05 Cupric sulphate oxidised ration is strongly protected (1 in Table 5), but
0.1 Manganese sulphate 94 autocoagulation leads to considerably lower
0.2 72
0.05 Ferric sulphate 83 PRI values (2 in Table 5). Excessive dilution
0.1 58 prior to coagulation induces a similar ten-
0.2 44
dency (3, 4 and 5 in Table 5).
5. Effect of Mechanical Working, Soaking, etc.
4. Effect of Purification Mechanical working (at ambient temperat-
Methods of processing latex range from auto- ures) and soaking as such have little effect on
coagulation in the field io controlled centri- oxidisability, although excessive creping causes
fugation in the factory. These processes affect a reduction in the initial plasticity (softening).

135
 Journal of the Rubber Research Institute of Malaya, Volume 19, Part 3, 1966

TABLE 5. EFFECT OF PROCESSING Effect of PRI on Technological Properties of

METHODS ON PRI Rubber Vulcanisates
Having considered how the PRI of natural
Type of preparation PRI rubber is influenced by processing treatments,
the consequential effects on the properties of
1. Total solids film 120 vulcanisates will now be briefly examined under
2. Autocoagulation 79 four headings.
3. Field latex coagula at pH 4.8 92
4. , 15%DRC pH Jt 83 1. Crosslink density. Crosslink density de-
5. t , 10%DRC pH „ 80 pends on the cure characteristics of the raw
6. Fi sldDF-C coagula , pH 5.3 96
7. ( f it t pH 5.0 100 rubber for a standard vulcanisate recipe. This
8. > i » ) pH 4.75 102 is well brought out in certain dynamic proper-
9. ji * PH 4.0 105
10. Skim coagula 37 ties. For example, if the heat build-up pattern
11. Skim coagula purified (trypsin) 56 of normal RSS, cup lump material and Miche-
lin rubber are compared using a range of acce-
lerator concentrations it can be clearly seen
In the case of soaking, significant effects on that they behave differently—the faster curing
PRI can be caused by adulterants in the water rubbers giving a lower temperature at lower
used. These deleterious agents are iron and accelerator concentrations. Table 7 and Fig-
calcium salts, and it is these which are res- ure 2 show the pattern of heat build-up in a
ponsible for the differences given by 'R.R.I. Goodrich flexometer for an extended period of
water' and 'Remillers water' in Table 6. time.

TABLE 6. EFFECT OF MECHANICAL WORKING AND SOAKING

PRI
No. of additional passes prior to crumbling
IX 2X Cup lumps Tree lace

Normal 34 21 80 24
5 passes 31 29 82 32
40 passes 33 33 70 37
Soaking 1 day (R.R.I, water) 30 29 78 23
Soaking 1 day (Remillers water) 25 17 70 15

TABLE 7. EFFECT OF ACCELERATOR CONCENTRATION ON HEAT BUILD-UP

Rubber Heat build-up

Concentration of accelerator (CBS)a 0.5 0.6 0.7 0.8

RSS 286 248 241 239

Cup lump 254 243 241 239
Michelin sheet 253 248 239 238
IX 295 271 249 246
3X 295 287 267 252

«N-cyclohexyl benzothiazole-2-sulphenamide

136
L. BATEMAN and B. C. SEKHAR: Significance of PRI in Raw and Vulcanised Natural Rubber

Mix: necessary to make comparisons at equivalent

Rubber 100 states of cure (i.e. at the same crosslink den-
HAF Black 45 sity),
Pine Tar 5 2. Molecular size. Molecular length is the
Zinc Oxide 5 fundamental characteristic of an elastic poly-
Stearic Acid 2 mer—its reduction in any way acts against the
PBNa 1 realisation of the best rubbery properties. Oxi-
CBS" 0.6 dation is always accompanied by this mole-
Sulphur 2.5 cular degradation and it occurs regardless of
whether the rubber is initially oxidised or
whether it has in some way become especially
prone to oxidation during processing in the
factory. In practice these two possibilities are
often mixed up, particularly so because factory
mixing and mastication are commonly carried
out at temperatures above 140°C where any
tendency to oxidation is strongly encouraged.
The breakdown which takes place in the
latter circumstances is markedly apparent in
Table 8. Rubbers when subjected to mixing
treatments involving mastication at 150°C un-
dergo considerable softening as expressed by
the Mooney viscosity values given in column
(a), whereas less change occurs when lower
temperatures (actually below 100°C) are em-
ployed (b). Equally important, there is an ob-
vious relationship, as would be expected, be-
tween the extent of breakdown in column (a)
relative to the initial viscosity and the PRI
value.
What this implies is that if rubbers of differ-
ent PRI are subjected to the same mixing-
mastication cycles at the higher temperatures,

PARTS CB S .£ 4000
Figure 2. Effect of accelerator on heat build-up. i/i
^3500
As degree of cure is so important, a standard .3000
curing system will appear to put the slower
curing rubber at a distinct disadvantage and o
vice versa, but this is a rate of cure effect not a 5
OS
2500
reflection on the intrinsic quality of the rubber. JA

Cure likewise affects modulus and resilience. uj

_j 2000
To assess the effects of PRI (which has no bear-
ing at all on cure behaviour), it is therefore ^ 1500
20 40 60 80 100
a
Phenyl-beta-naptbyIamine(PBN) PLASTICITY RETENTION INDEX,
ft
N-<;ydohexyl benzothiazoIe-2-suIphenamide (CBS) Figure 3. Tensile strength vs PRI.
137
 Journal of the Rubber Research Institute of Malaya, Volume 19, Part 3, 1966

strength {Figure 3), resilience (Figure 4) and

thus to heat build-up (Figure 5). Of course,
if the mixing-mastication cycles are adjusted to
77
yield the same final compound viscosity, then
this variability in vulcanisate properties can be
I 73 obviated—although in practice there are limits
to which such adjustments can be made.
3. Vulcanisate ageing. PRI is an ageing
i 69
test; therefore it gives a direct measure of the
ageing of raw rubber—the higher the PRI, the
better the ageing resistance.
This measure, or indication, carries over to
the vulcanisate but in an indirect way because
10 IS 26 34 42 50 58 66 74 82 90 98 K>6 (i) the ageing process in vulcanisates differs
PLASTICITY RETENTION INDEX, <¥b somewhat from that in raw rubber, and (ii)
Figure 4. Rebound resilience vs PRI. the chemical anti-oxidants deliberately added
during compounding exert a powerful protect-
then the lower the PRI, the lower the comp- ive action which tends to dominate the whole
ound viscosity. This last feature (reflecting ageing behaviour.
lower molecular weight) carries through to What is found is that for relatively short
technological properties, notably to tensile periods of ageing under not too severe condi-
tions, the anti-oxidant is effectively in control
and no difference between base rubbers of
320 MIX
different PRI can be traced. However, as age-
1 300 AF BLACK
HE TAB
ing becomes more prolonged or severe the anti-
28
NC D1IDE oxidant gradually becomes used up, its protec-
5 ° TElfllC ACID
tion diminishes and the character of the raw
rubber is revealed. This is so for tensile
strength (Figure 6) and for resilience (Figure 7)
I "0
E
where rubbers of lower PRI show inferiority
" Z20 in this 'ultimate' ageing. Again, this inferior-
ity can be countered by compounding with
0 20 30 40 50 60 70 80 90 KX) rather more anti-oxidant.
RUSTICITY RETENTION INDEX, 4. Non-rubber content. Skim rubber gives
Figure 5. PRI vs temperature at 3rd hour vulcanisates notoriously inferior dynamic
Goodrich fiexometer heat build-up. properties and this is generally attributed to

TABLE 8. INFLUENCE OF PRI ON COMPOUND VISCOSITY

Compound viscosity
Initial
Sample PRI Mooney (a) With (b) Without
viscosityb Vr mastication mastication
at 150°C at 150°C

RSS 74 95 47 57
Heveacrumb (from latex) 91 78 50 52
Heveacrumb (from cup lump) 77 86 43 54
Special rubber 58 106 36 53
IX Crepe 55 97 33 46

138
L. BATEMAN and B. C. SEKHAR: Significance of PRI in Raw and Vulcanised Natural Rubber

AFTER 21 DAYS 270

44OO UNAGED AGEING AT 7O°C
265
26
u_ °

RSS I % 255
o
HEVEACRUMB WL 5 250
CO

SPECIAL SAMPLE 5 245

IE
> RSS (Control)

240

235

0-2 04 0-6 08 1-0 1-2

% NITROGEN

Figure 8. Combined effect of PRI and non-

rubbers on heat build-up.
I6OO

Figure 6. Effect of oven ageing on tensile
strength. (Mix: Tread as in Table 7).
the large proportion of non-rubber substances
it contains. This is certainly true, as removal
of much of the non-rubbers results in a decid-
edly improved product. However, it has now
been found that a PRI factor is also involved,
and treatments (SEKHAR, 1965) which speci-
fically enhance resistance to oxidation and
raise the PRI give skim rubbers appreciably
40 60
AGEING PERIOD, DAYS
Figure 7. Oven ageing at 70°C gum vulcani-
sates with 1 % anti-oxidant.
better heat build-up properties than untreated
samples of similar nitrogen content (Figure 8).
Thus, both non-rubber content and PRI are
independent factors affecting dynamic charac-
teristics (in addition to vulcanisate structure as
determined by cure and to filler reinforcement).
DISCUSSION
PRI is seen to provide an informative and
numerical indication of an inherent quality of
raw rubber, its processing behaviour and the
properties of derived vulcanisates.
The importance of PRI is twofold: firstly,
it is sensitive to the treatment accorded to the
raw rubber in ways that can now be detailed
and thereby provides a quantitative yardstick
for improving or controlling the quality that it
measures; secondly, knowledge of it allows
control and rationalisation to be exercised on
processing in the manufacturing industry and
thus planned consistency realised in a sense not
possible hitherto.
In this latter respect it has to be appreciated
that the consumer's use of rubbers inevitably
involves compromise—not all the desired pro-
perties can be obtained in the fullest degree
80 100 simultaneously (some are mutually antagonis-
tic) and certainly not at the lowest cost. This
enters the picture with PRI. Treatments of
the raw rubber designed to improve certain

139
 Journal of the Rubber Research Institute of Malaya, Volume 19, Part 3, 1966
properties may involve some reduction in oxi-
dation resistance. Provided this is known in
the specific manner which PRI indicates, then
suitable compounding adjustment can be made
(within limits) and the best possible compro-
mise achieved. PRI by itself is not an index of
desirability or undesirability—it is for the
manufacturer to judge its significance in rela-
tion to the particular product being made in a
given process, but broadly uniform PRI would
almost always seem to be worthwhile. Where
the best possible oxidation resistance and thus
the retention of high molecular weight under
relatively high temperature mastication treat-
ments are sought, a high PRI is indicated;
where rapid breakdown to softer compounds
with economy in processing is called for, a low
PRI may be advantageous.
ACKNOWLEDGEMENTS
The authors are indebted to their colleagues
in the Chemical Division, R.R.I.M. and in the
N.R.P.R.A. for access to unpublished results.
Particular mention is made of the contribu-
tions of Mr J. O'Connell and Dr H.W. Green-
smith.
Rubber Research Institute of Malaya
Kuala Lumpur May 1966
140
REFERENCES
ALTMAN, R. F. A. (1948) Natural vulcanisation accele-
rators in Hevea latex. Ind. Engng, Chem. ind, (int.)
Edn. 40, 241.
ALTMAN, R, F. A. (1948) Natural antioxidants in Hevea
latex. Rubb. Chem. Technol. 21, 752.
CARLIER, G. (1961) Influence des substances non caout-
chouc natureliement presentes dans le latex d'hevea,
sur le vieillissement du caoutchouc, cru et vulca-
nise. Thesis submitted for the degree of Doctor
of Philosophy, University of Paris.
HEAL, C. J. A. (1963) Classification of natural rubber
for tyre compounds. I.R.I. Trans. 39, 5, T.262.
PIKE, M. AND WATSON, W.F. (1952) Mastication of rub-
ber. I. Mechanism of plasticizing by cold mastica-
tion. J. Polym. Sci. 9, 229.
SEKHAR, B. C. (19S8) Aeration of natural rubber latex.
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characteristics of aerated latex rubber. Rubb. Chem,
Technol. 31, 425.
SEKHAR, B. C. (1958) Aeration of natural rubber latex.
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SEKHAR, B. C. (1965) Lower grade rubber and skim
rubbers. British Patent Application No. 48702/65.
SMITH, J. F. AND SEKHAR, B. C. (1966) Lower grade
rubber and skim rubbers. British Patent Applica-
tion No. 14393/66.
SUBRAMANIAM, A. (1965) Private Communication, Rub-
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WATSON, W. F. (1953) Cold mastication of rubber-
I.R.I. Trans, 29, No. 1, 32.