Effect of Storage on the Colloidal Properties of Room-temperature Prevulcanised Natural Rubber Latex

Effect of Storage on the Colloidal

Properties of Room-temperature
Prevulcanised Natural Rubber Latex
S. Palaty1*, P.V. Devi1, and J. Honey2
1Department of Chemistry, Bharata Mata College, Thrikkakara, Cochin 682 022, India
2Facultyof Applied Sciences, Indian Institute of Space Science and Technology,
Thiruvananthapuram 695022, India

Received: 2 August 2010, Accepted: 20 December 2010

SUMMARY
This paper reports on the study of the prevulcanisation of natural rubber latex
(NRL) at room temperature. NRL was prevulcanised at room temperature
using a zinc butyl xanthate [Zn(bxt)2]–zinc diethyl dithiocarbamate [ZDC]
accelerator system. High-temperature (55–60°C) prevulcanisation of NRL was
also done using the conventional accelerator system. Effect of storage on the
colloidal properties of room-temperature prevulcanised latex was studied up
to 30 days, and these properties were compared with those of conventional
high-temperature prevulcanised latex. The colloidal properties were found to be
superior for the room-temperature prevulcanised latex. The mechanical stability
time (MST) of room-temperature prevulcanised latex increases on storage.
The room temperature prevulcanised latex is found to be stable for 30 days of
storage.

Keywords: prevulcanisation; colloidal properties; mechanical stability time; volatile

fatty acid number; potassium hydroxide number

INTRODUCTION
Prevulcanisation is the period for which the compounded latex is stored after
mixing prior to use in the production line. During prevulcanisation, crosslinking
of the rubber molecules occurs inside discrete rubber particles dispersed in

Corresponding author.
©Smithers Rapra Technology, 2011

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S. Palaty, P.V. Devi, and J. Honey

the aqueous phase of the latex. Prevulcanisation offers a means to control

the extent of crosslinking needed in the final vulcanised film. Prevulcanised
latex does not need further compounding by the product manufacturer and
requires less energy for drying. The production of various dipped goods, the
bulk of which is in the form of examination gloves, uses prevulcanised latex [1].
Natural rubber latex (NRL) particles were covered with some proteins and
phospholipids, which gave colloidal stability to the NRL [2]. The study of colloidal
stability of prevulcanised latex is very important in the latex dipped goods
manufacturing industry. The colloidal stability of prevulcanised latex depends
on many factors such as the nature of the latex, the amount of potassium
hydroxide (KOH) and carboxylate soap, the dosage of vulcanising ingredients,
and the prevulcanisation conditions such as time and temperature [3]. There
are two opposing factors that affect the colloidal stability of prevulcanised
latex. One is the presence of residual vulcanising ingredients such as zinc
oxide (ZnO), which reduces the colloidal stability by ZnO thickening. The other
is the addition of alkalis and carboxylate soaps, which increases the stability
by increasing the negative charge on the surface of rubber particles and by
increasing surface adsorption. The properties of sulphur prevulcanised latex
may undergo changes during storage because of the presence of surface-
active agents and residual vulcanising ingredients. During storage, the chemical
composition of the latex changes significantly owing to the action of bacteria,
enzymes and preservatives. These changes are reflected in the properties of
the latex, particularly its mechanical stability time (MST), volatile fatty acid
(VFA) number, and potassium hydroxide (KOH) number, and hence they have
received most attention [4].
The temperature of vulcanisation is very important in determining the quality
of the rubber products. Optimum properties are obtained when curing is done
at the lowest possible temperature [5]. At present, prevulcanisation of natural
rubber latex is done by heating it for 2–3 hours at 55–60°C, which affects its
colloidal stability. Thus, the main drawback of high-temperature prevulcanised
NRL is its low colloidal stability. Other disadvantages of this high-temperature
vulcanisation include high energy consumption, degradation of rubber
molecular chains, poorer safety, high insulation costs, less flexibility in designing
the compound for each component at high temperature, inconvenience in
the curing room, and the risk of overvulcanisation. However, low-temperature
vulcanisation results in products of good quality and fine appearance. The
effect of vulcanisation time and storage on the stability and physical properties
of high-temperature prevulcanised NRL was reported earlier [3].
This paper reports on the study of the colloidal stability of room temperature
prevulcanised latex stored for a period of 30 days. These properties were
compared with those of high-temperature prevulcanised latex. The room-

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 Effect of Storage on the Colloidal Properties of Room-temperature Prevulcanised Natural Rubber Latex

temperature prevulcanisation of NR latex was done using a zinc butyl xanthate

[Zn(bxt)2]–zinc diethyl dithiocarbamate [ZDC] accelerator system [6-8].
The important colloidal properties of the prevulcanised latex studied are the
total solids content (TSC), the dry rubber content (DRC), the ammonia content,
the VFA number, the KOH number, the MST, and the coagulum content. The
TSC of latex is the percentage by mass of the whole latex that is non-volatile
under specified conditions of drying in an open atmosphere at an elevated
temperature. The DRC is the percentage by mass of the latex that is coagulated
under specified conditions of colloidal destabilisation. The ammonia content
represents the free alkali content of the latex. The VFA number indicates the
number of grams of KOH required for neutralising the volatile fatty acid in a
latex sample containing 100 g of TSC. The KOH number represents the number
of grams of KOH equivalent to the anions present as ammonium salts in a
quantity of latex that contains 100 g of TSC. The mechanical stability of the
latex is its ability to withstand colloidal destabilisation effects of mechanical
influences such as shearing and agitation. The coagulum is the material that is
retained by a mesh of arbitrary size under specified conditions of filtration [9].

EXPERIMENTAL

Equipment Used
The equipment used in this study included a Brookfield LVT viscometer
(Brookfield Engineering Laboratories, Inc., Strongton, MA), mechanical
stability apparatus (M/s Klaxon Signals, Oldham, UK), an MKVI digital pH
meter (Systronics Naroda, Ahemedabad), a centrifuge (Elektorcraft [India] Pvt.
Ltd, Mumbai, India), a hot air oven (Rotek RHO-98-HFSS; B&C Industries,
Kerala, India), Markham-type still apparatus, a water bath, and a ball mill with
a speed of 50 rpm.

Materials Used
High-ammonia (HA) centrifuged NRL conforming to the BIS 5430-1981 was
purchased from Njavallil Rubber Latex Pvt. Ltd, Cochin, India, and was used
for prevulcanisation. The compounding ingredients, such as zinc diethyl
dithiocarbamate (ZDC), zinc oxide (ZnO), sulphur (S), and dispersal F (M/s
Standard Chemicals Co. Pvt. Ltd, Chennai, India) were commercial grade.
Acetic acid, hydrochloric acid, barium hydroxide [Ba(OH)2], ammonium
hydroxide, KOH, and formaldehyde (supplied by E. Merck Ltd, Mumbai,

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S. Palaty, P.V. Devi, and J. Honey

India) were analytical grade and were used as supplied. For the preparation
of Zn(bxt)2, commercial-grade n-butyl alcohol, KOH, zinc chloride (ZnCl2),
and carbon disulphide (CS2) were used.

Experimental Procedure
The colloidal properties of the high-ammonia centrifuged latex were determined
according to IS 9316-1987 and are reported in Table 1. Zn(bxt)2 was prepared
in the laboratory as reported earlier [7, 8, 10]. Zinc butyl xanthate was prepared
by reacting equimolar amounts of n-butyl alcohol, potassium hydroxide, carbon
disulphide, and zinc chloride. 50% dispersions of the vulcanising agents were
prepared using the required amount of vulcanising agents and distilled water
by grinding in a ball mill under standard conditions. Dispersol F was used as
the dispersing agent during ball milling to prevent the dispersed particles from
reaggregation; chemically, it is sodium naphthalene formaldehyde sulphonate.
NRL was deammoniated to 0.2% before compounding to avoid ZnO thickening.
NRL was compounded as per the formulations given in Table 2.

Table 1. Properties of the high-ammonia (HA) centrifuged NR latex

used for prevulcanisation
Properties Value BIS 5430-1981 Test methods
requirements
Dry rubber content (mass %) 59 60a IS 3708(part 1) 1985
Total solids content (mass %) 60 61.5a IS 3708(part 1) 1966
Non rubber solids (mass %) 1 2b IS 9316(part 4)1988
Ammonia content (mass %) 0.86 0.6a IS 3708(part 4)1985
Volatile fatty acid number 0.02 0.15b IS 3708(part 7) 1986
Potassium hydroxide number 0.33 1b IS 3708(part 5)1985
Mechanical stability time (s) 990 475a IS 3708(part 6)1985
Coagulum content (mass %) 0.01 0.05b IS 3708 (part 3)1987
a Minimum
b maximum

Prevulcanisation of compound A was performed by heating the latex mix at

55–60°C for 3 h. Compound B was kept at room temperature, with occasional
stirring. The time required for its prevulcanisation at room temperature was
optimised as 5 days [7]. The colloidal properties of the prevulcanised latex
were determined after 5, 10, and 30 days of storage and compared with those
of high-temperature prevulcanised latex; the results are given in Figures 1 to

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 Effect of Storage on the Colloidal Properties of Room-temperature Prevulcanised Natural Rubber Latex

Table 2. Formulation of latex mixes

Ingredients Parts by weight (g)
A B
NR latex 167 167
10% KOH 1.5 1.5
10% potassium oleate 0.75 0.75
10%Vulcastabe VL 1.0 1.0
50% S 2.5 2.5
50% ZDC 1.5 1.5
50% ZnO 1.0 1.0
50% Zn(bxt)2 — 1.5

10. The important colloidal properties studied here are the TSC, the DRC, the
non-rubber solids, the ammonia content, the VFA number, the KOH number,
the MST, the Brookfield viscosity (cP), the coagulum content, and the pH.
The test methods used are given in Table 1.
The TSC and DRC values were determined using the conventional method
of heating in a hot air oven. If m0 is the initial latex sample mass and m is
the mass of the residue after evaporation (at 100°C for 2 h), then TSC = (m/
m0) 100. Also, if m0 is the initial latex sample mass and m is the mass of dry

Figure 1. Effect of storage on the TSC of compound B and its comparison with
compound A

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S. Palaty, P.V. Devi, and J. Honey

Figure 2. Effect of storage on the DRC of compound B and its comparison with
compound A

Figure 3. Effect of storage on the non-rubber solids of compound B and its

comparison with compound A

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 Effect of Storage on the Colloidal Properties of Room-temperature Prevulcanised Natural Rubber Latex

Figure 4. Effect of storage on the ammonia content of compound B and its

comparison with compound A

Figure 5. Effect of storage on the VFA number of compound B and its comparison
with compound A

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S. Palaty, P.V. Devi, and J. Honey

Figure 6. Effect of storage on the KOH number of compound B and its comparison
with compound A

Figure 7. Effect of storage on the Brookfield viscosity of compound B and its

comparison with compound A

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 Effect of Storage on the Colloidal Properties of Room-temperature Prevulcanised Natural Rubber Latex

Figure 8. Effect of storage on the MST of compound B and its comparison with
compound A

Figure 9. Effect of storage on the coagulum content of compound B and its

comparison with compound A

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S. Palaty, P.V. Devi, and J. Honey

Figure 10. Effect of storage on the pH of compound B and its comparison with
compound A

coagulum separated from it using acetic acid, then DRC = (m/m0) x 100. The
difference between the percentage of TSC and DRC gives a measure of the
percentage of non-rubber solids. The ammonia content was determined by
titrating a certain amount of diluted latex with standard hydrochloric acid.
The VFA number of prevulcanised latex was periodically determined using a
Markham-type still apparatus. The VFA number was measured by the quantity
of Ba(OH)2 that is required to neutralise the distilled-off short-chain fatty acids.
The calculation of the VFA number is as follows:

A × N × 561
VFA number =
w × TS

where A is the quantity of Ba(OH)2 solution (in mL) required for titration of
the sample, N is the normality of the Ba(OH)2 solution, w is the mass of latex
corresponding to 10 mL of acidified serum, and TS is the percentage of total
solids in the latex. The potassium hydroxide number was determined by
reducing the ammonia content of the test latex sample to a specified level
by reacting with formaldehyde, diluting with water to a definite TSC, and then
titrating with standard carbonate-free aqueous KOH solution.

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 Effect of Storage on the Colloidal Properties of Room-temperature Prevulcanised Natural Rubber Latex

The MST was determined using a mechanical stability apparatus. In this test,
a specified amount of prevulcanised latex of specified TSC is subjected to
mechanical agitation under specified conditions, and the time required to
produce the first obvious sign of flocculation is recorded as the MST (in s).
To determine the coagulum content, a known quantity of latex is diluted with
a known volume of 5% potassium oleate solution and filtered through an 85
mesh sieve, and the coagulum retained on the sieve is dried and weighed.
If m0 and m are the masses of latex test sample and the dried coagulum
respectively, then:

m
Coagulum content =   × 100
 m0 

Viscosity measurements of the prevulcanised latex were carried out with

a Brookfield LVT viscometer. The experiments were performed by varying
the size and speed of the spindle in order to achieve a shear stress close to
100%. The pH of the latex was determined using a pH meter according to
ISO standard 976-1986.

RESULTS AND DISCUSSION

Table 1 shows the colloidal properties of the high-ammonia centrifuged
latex. The maximum and minimum limits are given. The test methods are
also indicated.
From Figures 1 to 3 it is clear that the TSC, DRC, and non-rubber solids of
room-temperature prevulcanised latex remain almost constant during the
entire period of storage of 30 days and are comparable with the corresponding
characteristics of high-temperature prevulcanised latex. The ammonia
content of the room-temperature prevulcanised latex decreases slightly on
storage (Figure 4). The VFA number of the room-temperature prevulcanised
latex increases on storage (Figure 5). However, it does not exceed the
acceptable VFA number limit for the concentrated latex industry, i.e. 0.15.
During storage, bacterial degradation of the latex constituents causes the
formation of short-chain fatty acids (mostly of formic, acetic, and propionic
acids), with a resultant decrease in the pH value of the latex (Figure 10) and
a corresponding increase in the VFA number11. Thus, the VFA number is used
as an important measure of the level of deterioration and stability of the latex,
and it is a good indicator of the state of preservation of the latex. The KOH
number of the room-temperature prevulcanised latex increases slightly on
storage (Figure 6). This indicates an increase in the concentration of acids,

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S. Palaty, P.V. Devi, and J. Honey

which are present as ammonium salts [12]. However, even after 1 month,
the value is very much lower than the acceptable limit of 1. The increase in
Brookfield viscosity during storage (Figure 7) is due to ZnO thickening of the
latex and also to the slow liberation of Zn ions from the accelerator [1]. The
zinc ions tend to destabilise the latex by neutralising some of the fatty acid
anions and proteinate anions on the rubber particle surface. The coagulum
content of the room-temperature prevulcanised latex remains almost constant
during storage (Figure 9) and is comparable with that of high-temperature
prevulcanised latex.
The MST of the room-temperature prevulcanised latex increases on storage
(Figure 8). On storage, the ammonia present in the latex, the alkali, and the
potassium soap added during compounding slowly hydrolyse the proteins
and phospholipids to fatty acid anions and other products. The liberated
fatty acid anions are adsorbed at the particle interfaces and thus enhance
the stability of the latex owing to a higher surface charge and therefore a
higher repulsive energy between particles [4]. This accounts for the increase
in MST of the prevulcanised latex. High-temperature prevulcanised latex has
a low value of MST compared with room-temperature prevulcanised latex.
Thus, one of the advantages of room-temperature prevulcanised latex is its
high colloidal stability, which will be of significant technological importance
to the rubber dipped goods manufacturing industry, providing a means for
effecting better product quality control and improvement. Another important
advantage is its non-consumption of energy during prevulcanisation, which
will make the process highly economic.

CONCLUSIONS
The colloidal properties of room-temperature prevulcanised latex, prepared
using a Zn(bxt)2–ZDC accelerator system, are found to be superior to those of
conventional high-temperature prevulcanised NR latex. The mechanical stability
time of room-temperature prevulcanised latex increases on storage and has
a high value compared with that of high-temperature prevulcanised NR latex.
Even after 1 month of storage, the values of the VFA number and KOH number
of room-temperature prevulcanised latex are much lower than the acceptable
limits of these values for the concentrated latex industry. Properties such as
the TSC, DRC, non-rubber solids, and coagulum content of room-temperature
prevulcanised latex have values comparable with those of high-temperature
prevulcanised NR latex. Thus, room-temperature prevulcanisation of NR latex
using a Zn(bxt)2–ZDC accelerator system leads to a high energy saving and
makes the process more economic. The colloidal stability of the latex can be
improved owing to the non-application of temperature.

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 Effect of Storage on the Colloidal Properties of Room-temperature Prevulcanised Natural Rubber Latex

ACKNOWLEDGEMENT
The authors would like to acknowledge KSCSTE and the University Grants
Commission for financial support.

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