Dibqufs!.!1!

INTRODUCTION
Natural rubber latex (NRL) is a natural commodity that has
tremendous economic and strategic importance. NRL is used for the production
of dipped goods, extruded threads, adhesives, carpet backing and moulded
foams. This is primarily because of the unique characteristics of NRL such as
high strength, excellent elasticity and flexibility, good formability and antivirus
protection. The additional factors which gave considerable interest in NRL
products are their low cost and biodegradability.1-5

NRL is obtained from Hevea brasiliensis tree and contains 30-40%

rubber dispersed as rubber latex particles in water.6-12 The rubber particles have
an average diameter of 1 µm and surrounded by a layer of the non-rubber
components such as proteins, lipids, carbohydrates, sugars and metal ions.13-28
Structural studies of NR showed that the rubber molecule is composed of one ω-
terminal, two trans-1, 4- isoprene units, a long chain of cis-1, 4- isoprene
repeating units ending in an α-terminal.29-34 Some of the proteins or
phospholipids are thought to co-exist at the terminal ends of the rubber
molecules and present as a charged layer covering the rubber latex particle,
thereby stabilizing the latex particles against aggregation.35-37

Figure 1.1: Surface nanostructure of NRL particle obtained using AFM imaging

1 
 Proteins

ω - Terminal Hydrogen bond

Figure 1.2: Structure of proteins present in NRL

H3C H
n

Figure 1.3: Chemical structure of NRL (cis-1, 4-polyisoprene)

The unique mechanical properties of NR results from both its highly

stereoregular microstructure and the rotational freedom of the α-methylenic C-C
bonds and from the entanglements resulting from the high molecular weight
which contributes to its high elasticity.38

NRL proteins are organic substances that contain carbon, hydrogen,

nitrogen, oxygen, and sulphur. They are naturally occurring polymers that may
contain hundreds of individual amino acid residues linked together by peptide
bonds. The smaller degraded NR proteins of 10 amino acids or less are typically
called peptides. The proteins of NRL constitute about 2% by weight of the field
latex.12 These proteins may be expected to be attached on the surface of the
rubber particles by excluded volume effect of the lipids. Lipids associated with
NR are comprised mainly of neutral lipids and phospholipids. The principle
phospholipids of the rubber particles are α-lecithin.6

2 
 Figure 1.4: NRL obtained from Hevea brasiliensis tree by tapping

NRL is obtained from rubber tree by the process of tapping. Ammonia

is usually added to the latex as a preservative to increase the alkalinity (pH) and
retard microbial growth. The additional benefit from adding ammonia is the
increase in stability of the NRL due to the increase in negative surface charge of
the rubber particles. NRL undergoes several changes during ammonia addition
and storage. Typically some of the proteins are partially degraded by the
alkaline conditions imparted by the ammonia. The changes in the composition of
proteins in NRL affect the physical properties of the latex. Some of the proteins
lose their secondary structure and are partially hydrolyzed to small peptides.
The resulting field NRL is further processed to a concentrate by creaming or
centrifugation. These processes concentrate the latex to about 60% rubber
content. Significant quantities of non-rubber material such as proteins are
removed during this processing step. This concentrated form of ammoniated
latex is used for the production of dipped rubber products such as medical
gloves.12

Natural rubber is sticky and nonelastic by nature. The vulcanization is

a process that transforms the predominantly thermoplastic or raw rubber into an
elastic or hard ebonite-like state. This process is also known as “crosslinking”

3 
or “curing” and involves the association of macromolecules through their
reactive sites. The crosslinking imparts various properties to rubber. It improves
its tensile strength, becomes more resistant to chemical attack and is no longer
thermoplastic. It also makes the surface of the material smoother, prevents it
from sticking to metal or plastic, chemical catalysts and renders it impervious to
moderate heat and cold. In addition, it is a good insulator against electricity and
heat. These attractive physical and chemical properties of vulcanized rubber
have revolutionized its applications. This heavily crosslinked polymer has strong
covalent bonds, with strong forces between the chains, and is therefore an
insoluble and infusible thermosetting polymer. The most important vulcanizing
agent for rubber is sulphur because of its low cost, ease of availability and
minimal interference with other compounding ingredients. Various
concentrations of sulphur are used to manufacture different kind of rubber
compounds. During vulcanization, sulphide bridges are formed between
adjacent rubber chains.39

Vulcanisation
S

Figure 1.5: Vulcanisation (Formation of sulphide bridges between adjacent

rubber chains.)

Thus in order to enhance the physical properties of the rubber

products, NRL must be prevulcanised before use.40

1.1 Prevulcanisation

Prevulcanisation is an important term used in latex technology, which

is the process of crosslinking the rubber particles in latex stage without affecting
the colloidal stability of the latex. Thus prevulcanised latex, in effect, is a latex
of vulcanized rubber. The appearance of prevulcanised latex is very similar to
unvulcanized latex and the original fluidity of latex is retained during

4 
prevulcanisation. During prevulcanisation, crosslinking of the rubber molecules
takes place inside discrete rubber particles dispersed in the aqueous phase of the
latex without affecting their state of dispersion appreciably. The particles in the
prevulcanised latex exhibit similar Brownian movement as in unvulcanised latex
and after prevulcanisation particles have same shape, size and size distribution
as those in the initial unvulcanised latex.41-44

Using prevulcanised latex effective control of the physical properties

can be exercised before the articles are manufactured from it. Prevulcanised
latex is used nowadays for the development of products, since initial
crosslinking of the rubber particle is possible during prevulcanisation, and
complete vulcanization is achieved by simply drying the product.45,46 This
enables the manufacturer to decrease the time required for an optimum cure in
the circulating hot air oven. An additional benefit is that less time at elevated
temperatures means less opportunity for oxidative degradation. Prevulcanised
latex is widely used for the manufacture of various dipped goods such as gloves,
toy balloons, condoms, catheters, adhesives, latex foam, latex thread, textile
combining, latex composites and blends.47-50

There are different techniques used for the prevulcanisation of NRL.

They are reaction of rubber particles with sulphur or peroxide and irradiation of
latex with UV and γ-rays. The rate of prevulcanisation reaction varies with
different vulcanizing systems and the extent of prevulcanisation has a profound
effect on the final vulcanisate properties.

1.2 Radiation Prevulcanisation

Radiation vulcanization of NRL involves radiation induced

crosslinking of macroscopic particles of NR dispersed in the aqueous medium.

5 
1.2.1 γ-radiation/Electron Beam Prevulcanisation

Prevulcanised NRL prepared by using gamma radiation or high energy

electron beams in place of sulphur in conventional process is known as
Radiation Vulcanized Natural Rubber Latex (RVNRL).51-71 The main
components of NRL are NR and water. Upon irradiation, both NR and water
molecules absorb radiation energy independently. The radiolysis products of
water are diffused into NR particles and react with NR molecules. The OH
radicals, H radicals and hydrated electrons formed are involved in the radiation
induced crosslinking of NRL.39

. .
Radiolysis of NR RH R + H

. .
Radiolysis of water H2O OH + H

. .
Hydrogen abstraction RH + OH R + H2O

Figure 1.6: Radiation prevulcanisation of NRL

Radiation vulcanization needs more than 200 kGy radiation dose to

achieve maximum tensile strength. The use of very high dose of radiation for
vulcanization of NRL deteriorates properties of the rubber due to the main chain
degradation. In practice, radiation vulcanization (RV) accelerators or sensitizers
are used to reduce the radiation dose at which maximum tensile strength could
be obtained (Dv). Polyfunctional monomers which contain more than two
polymerizable C=C double bonds in a molecule, monofunctional acrylic
monomers and halogenated hydrocarbons were used as vulcanization
accelerators.53-57

6 
 The commonly used sensitizers are n-butyl acrylate (n-BA), neopentyl
glycol diacrylate, dimethacrylate, 2-ethyl hexyl acrylate (2-EHA), phenoxy ethyl
acrylate (PEA), trimethylol propane trimethacrylate (TMPTMA), trimethylol
propane triacrylate (TMPTA), chloroform (CHCl3) and carbon tetrachloride
(CCl4).54-57 Using these vulcanization accelerators radiation dose could be
reduced from 300 kGy to 15 kGy. Among the monofunctional monomers, n-BA
is the most effective vulcanization accelerator because it not only imparts much
better physical properties at lower Dv but also unreacted n-BA is not retained in
the final product.53,58 PEA is more effective accelerator for RVNRL since it
imparts approximately equivalent physical properties compared to that of n-BA.
However, when compared to n-BA, the sensitizing effect of PEA is
comparatively lower, and therefore, similar physical properties could be
obtained at a slightly higher dose. Even though TMPTMA is a polyfunctional
monomer, it is less capable of imparting better physical properties at similar
dose.57

The physical and mechanical properties of irradiated NRL depend on

many factors such as irradiation dose, sensitizer content, dry rubber content and
storage time.53-59

Radiation vulcanization improves the properties of rubber and has a

number of advantages over the conventional method of vulcanization. In γ-ray
vulcanization, the crosslinking occurs by elimination of hydrogen and direct
carbon-carbon bonds are formed, which are more stable than sulphur bonds.
RVNRL was claimed to be more user friendly than NRL prevulcanized by
sulphur curing system. This process uses no curatives like sulphur, ZnO and
dithiocarbamates. The absence of Type IV allergy inducing chemicals in
RVNRL make it a suitable material for manufacturing of many kinds of latex
products, especially those come into direct contact with users. The products
prepared using RVNRL possess low cytotoxicity and are more transparent and
soft.60

7 
 The radiation vulcanization process is a much simpler energy saving
process compared to the conventional thermal process which has two
vulcanization steps before and after dipping. But the tensile strength and 100%
tensile modulus values of rubber films made from this type of latex is not as
high as found in many traditionally prevulcanised latex films which incorporate
a post vulcanization step. Also, there are a lot of health hazards associated with
this process and the expense of the equipment needed is very high.

During irradiation of NRL for vulcanization, the latex proteins

undergo disintegration which leaves a high soluble protein content in the latex
products. The soluble protein content in the cream phase decreased where as that
in the serum phase increased with radiation dose. Thus the amount of EPs in
RVNRL is greater than in conventional sulphur vulcanisate.

NRL can be radiation vulcanized quite effectively and easily in presence

of styrene butadiene rubber latex (SBRL).60 One important application stipulated
for RVNRL is for the manufacture of dipped products like surgical gloves,
examination gloves, condoms, catheters, and so on.70 Various steps involved in
the development of RVNRL products are shown in Figure 1.7.

Antioxida n t

N R la te x

M ixin g Irrad iation Pre vu lca n ise d N R la te x

n -BA

D ip pin g

L ate x p ro du cts

Figure 1.7: Various steps involved in the development of RVNRL products

8 
1.2.2 UV-radiation Prevulcanisation

Ultraviolet (UV) light is widely applied for modifying the properties of

polymer bulk materials and polymer surfaces.72-76 The prevulcanisation of NRL
based upon an UV induced pre-curing of the latex emulsion has been described
recently by S.Schlogl et al.77-80 This new technology makes the manufacture of
examination and surgical gloves feasible without using any sensitizing or
allergenic processing agents.

In the photochemical process, a selected photoinitiator and a

polyfunctional thiol are added to the NRL. On UV irradiation the bond cleavage
of the photoinitiators occurs, generating free radicals and crosslinking of the
latex particles is then achieved by a thiol-ene addition reaction. The thiol-ene
reaction involve the reaction of unsaturated C=C bonds with thiol derivatives
such as alkyl thiols, thiol glycolate esters, or thiol propionate esters.81,82 Thiols
based on propionate esters and glycolate esters comprise a higher reactivity
compared with alkyl thiols due to a weakening of the thiol moiety by hydrogen
bonding of the thiol hydrogen groups with the ester carbonyl. Due to their
commercial availability and widespread use, trimethylol propane tris (3-
mercaptopropionate) (TriThiol) and pentaerythritol tetra (3-mercaptopropionate)
(Tetra Thiol) were used as crosslinking agents in the photochemical
prevulcanisation.

The initiation mechanism involves the excitation and cleavage of a

photoinitiator. In the prevulcanisation process, Type I photo fragmenting
photoinitiators, which undergo homolytic bond cleavage under UV irradiation to
yield free radicals, has been used. Regarding the efficiency of the photoinitiator
system, not only the reactivity of the compound but also the fit of the light
source to the absorption spectrum of the photoinitiator, the transmission
properties of the reaction mixture and photophysical (e.g. quantum yield) have
to be considered. For photochemical crosslinking to proceed efficiently, the
absorption bands of the photoinitiator must overlap with the emission spectrum
of the light source. Regarding the prevulcanisation of the latex, an undoped

9 
medium pressure mercury lamp was used. Besides the photoinitiator
concentration, the incident light intensity controls the rate of initiation in
photochemical crosslink reactions.

The prevulcanisation process was carried out by emulsifying the

processing chemicals such as photoinitiator and thiol crosslinker in deionized
water. The emulsion of the chemicals was then added to high ammonia NRL
comprising a dry rubber content of 40 wt%. The UV induced reaction involves a
radical addition of thiols to nonactivated C=C bonds. Using thiol derivatives
bearing more than two thiol moieties crosslinking of diene rubbers can be
achieved efficiently. The photoreactions have been investigated using real time
FTIR and Raman spectroscopy.

To provide a continuous irradiation of the liquid latex the

prevulcanisation is carried out in a falling film photo reactor. Falling film
reactors are well known and are used in various industrial technologies
including water waste treatment and preparative organic chemistry.83 Due to the
low light transmissivity of NRL, the concept of the falling film process allows a
homogeneous irradiation of the reaction mixtures in thin films with thicknesses
in the range of millimeters. Compared with thin film reactors there is no contact
between the reaction medium and the UV lamp. This new technology operates at
room temperature and crosslinking is accomplished within minutes, allows
enormous cost saving options compared with conventional sulphur vulcanization
processes which are carried out at elevated temperatures for hours in batch
processes.79

10 
Figure 1.8: Schematic representation of a falling film photo reactor used for the
production of UV prevulcanised surgical gloves

UV prevulcanised NRL was used for the production of latex gloves by

a conventional dipping process.78,79The dipped latex articles display excellent
mechanical properties as well as good stability against ageing and gamma
sterilization. Skin sensitization, irritation and cytotoxic tests prove the good skin
compatibility of UV crosslinked NRL gloves. Various steps involved in the
manufacture of UV prevulcanised surgical gloves are illustrated in Figure 1.9.

11 
 Falling Film Photoreactor

Coagulant Bath Oven UV pre-cured Latex

Cleaning Bath Chain Machine Beading Unit

Stripping Powdering Oven Leaching Bath

Gamma UV pre-cured
Quality Control Packaging Unit
Sterilization Surgical Gloves

Figure 1.9: Processing steps involved in the manufacture of UV prevulcanised

surgical gloves

1.3 Peroxide Prevulcanisation

Prevulcanised latices prepared by using organic peroxide and/or

hydroperoxide involving free radical crosslinking is referred to as Peroxide
Vulcanized Natural Rubber Latex (PVNRL).84-88 The process involves the
heating of NRL in the presence of organic peroxide. After cooling, films are
casted and dried, yielding vulcanized rubber films with a tensile strength as high
as 251 kg/cm2.

The organic peroxides undergo homolytic cleavage at elevated

temperature. The resulting free radicals induce abstraction of hydrogen atoms
from the polymer backbone. These in turn create free radicals on the polymer
backbone, which allow the chains to form carbon-carbon crosslinks with one
another. These carbon-carbon bonds are stronger and more stable than those

12 
formed by sulphur crosslinking. Also, the bond is very predictable one, unlike
the many different types carbon-sulphur bonds.89-94 It is also possible to add
coagents during compounding to add a slightly different characteristic to some
of the carbon-carbon bonds. The additions of certain coagents help to improve
certain specific physical properties, such as tear strength.

The mechanism of peroxide prevulcanisation of NRL is given in Figure 1.10.

H3C

RO + CH2 C CH CH2

H3C

ROH + CH2 C CH CH

H3C

2 CH2 C CH CH

H3C

CH2 C CH HC

CH2 C CH CH

H3C

Figure 1.10: Mechanism of peroxide prevulcanisation of NRL

Organic peroxides break apart (homolytically cleave) in a very

predictable manner. At any given temperature, organic peroxides have a half

13 
life. This is the time it takes for one half of the currently present peroxide to
homolytically cleaves. In order to make sure that only trace amounts of organic
peroxides remain after curing, it is important to keep the latex film at its
predetermined curing temperature for the proper number of half-lives. For
instance, after six half lifes, approximately 1.6% of the peroxide is left intact,
and after eight half-lives only about 0.4% of the peroxide is left intact. A
presumed safe target is eight or more half-lives. There are a very large number
of organic peroxides, combinations of organic peroxides and coagents to choose
from. Some peroxides decompose at very low temperatures, such as dibenzyl
peroxide, while others decompose at very high temperatures, such as 2, 5-
Dimethyl-2, 5-di (t-butyl-peroxy) hexane. It is important to use an organic
peroxide which does not homolytically cleave at too low of a temperature, since
it would then not be possible to dry the water out from the latex prior to
vulcanization subjecting the film to severe degradation. It is preferable to choose
a peroxide that can homolytically cleave rapidly at a temperature lower than the
degradation temperature of the base polymer. By choosing the right peroxide
and temperature combination, cure times of about two minutes to about nine
minutes are conveniently used, while allowing adequate time for latex particles
to fuse, and sufficient safety in the water drying process.

In peroxide prevulcanisation, along with hydrogen peroxide (H2O2) an

activator is used which does not encourage the decomposition of the H2O2 to
produce molecular oxygen under the condition of treatment. The activator is
suitably added to the unsaturated polymer as an aqueous solution or dispersion.
The amount of such an activator employed may be as little as one millimole per
mole of H2O2. Usually inorganic and organic compounds which yield peracids
or persalts by reaction with H2O2 in aqueous medium were commonly used as
activator. Examples for inorganic activators are sodium and potassium salts such
as the molybdates, tungstates, stannates, borates, pervandates, aluminates,
bicarbonates, lithium chloride and boric acid. Examples of organic activators
include formic acid, formaldehyde and fluoroacetic acid. Such an activator may
be conveniently formed in situ but may alternatively performed if desired. For

14 
example performic acid may be formed by the reaction of formaldehyde with
H2O2 preferably in the mole ratio 1:2. The peracid so formed is present as one
component of an equilibrium system comprising water, H2O2, organic acid and
organic peracid. In some instances no activator needed to be added since the
unvulcanized polymer latex may contain such an activator owing to its method
of preparation.

This process requires large and expensive heated pressure vessels. To

avoid the use of pressure vessels, some PVNRLs are made with the use of
catalysts at low temperatures. Such methods generally produce lower tensile
strength films and leave chemical residuals in the film. The physical properties
and ageing resistance of the peroxide vulcanisate are poor.

1.4 Sulphur Prevulcanisation

The possibility of vulcanizing the dispersed phase of NRL without any

concomitant colloidal destabilization was first investigated by Schidrowitz in the
early years of this century.95-97 His interest was in making a cellular rubber
directly from NRL. Although he succeeded in prevulcanising NRL, he did not
achieve his principal objective because prevulcanised NRL is not a suitable
material for the production of latex foam rubber due to the inherently poor gel
strength. The method of prevulcanising NRL disclosed in his first patent was to
heat the latex with sodium polysulphide, S and ZnO at 145ºC for 30-45
minutes.96,97 At the conclusion of the process it was necessary to reduce the
steam pressure very slowly to prevent the latex from boiling over. Relatively
high vulcanization temperatures were necessary because very active organic
accelerators of sulphur vulcanization were not available at first. Subsequently,
water soluble accelerators of high activity became available. By their use, it was
possible to reduce the intensity of vulcanization conditions.

15 
1.4.1 Preparation of Sulphur Prevulcanised NRL (SVNRL)

It is done by allowing the latex particle to react with sulphur and one or
more organic vulcanization accelerators and also with an inorganic
vulcanization activator.

Sulphur prevulcanisation process involves the following steps

(1) De-ammoniation by aeration

The purpose of reducing the ammonia content and replacing it with a

fixed amount of alkali is to minimize the risk of ZnO thickening when the latex
is subsequently heated for vulcanization.

(2) Latex is colloidaly stabilized by the addition of small amounts of a caustic

alkali and a hydrocolloid stabilizer like sodium carboxy methyl cellulose.

(3) Compounding of the latex with appropriate amounts of sulphur,

accelerator and ZnO. It is desirable to warm the compounded latex for 30
minutes at 300C prior to the addition of the vulcanizing ingredients. This
will help to reduce the variability of the latex to the vulcanization reaction
by accelerating certain chemical changes which occur slowly at normal
ambient temperatures.

(4) Heating the latex slowly to a temperature in the range 55-80ºC and then
maintaining the temperature at this level until the desired degree of
vulcanization has been achieved.

Care must be taken to (a) maintain constant stirring keeping the

vulcanizing ingredients in suspension (b) minimize the skin formation
(c) control temperature.

(5) Cooling

When the desired degree of vulcanization has been attained, the latex is
cooled, run off into containers, strained and then bulked.

16 
(6) Removal of residual vulcanizing ingredients

Vulcanizing ingredients sediment during this time and so can be

eliminated at this stage.

(7) Maturation

Prevulcanised latex is allowed to mature for sufficient time before product

manufacture. During maturation, crosslinking of the rubber molecules
takes place inside discrete rubber particles dispersed in the aqueous phase
of the latex.43 Maturation will impart good technical properties and will
remove the air bubbles introduced into the latex compound while
compounding.

The variables which affect sulphur vulcanization are

1. The level of sulphur

Vulcanization systems used (efficient and conventional vulcanization

system) have a profound effect on the extent of crosslink formation during
prevulcanisation. The conventional vulcanization (CV) system is
characterized by a low accelerator and high sulphur combination, while
efficient vulcanization (EV) system has a high accelerator and low
sulphur combination.41

2. Particle size of sulphur dispersion.

3. The nature and levels of the accelerators.

4. Whether the vulcanization accelerators are to be water soluble or water

insoluble or a combination.

5. The particle size of dispersions of any water insoluble accelerator which

are used.

6. Whether or not to use an inorganic activator and if so the type and

amount.

17 
7. The temperature-time profile which is imposed for the reaction.

8. The extent to which the reaction is allowed to continue.

Polysulphidic content is high as the extent of prevulcanisation of the latex

compounds increases. It was reported that the extent of prevulcanisation
affects the aged and unaged physical properties of latex threads.48 The
extent of prevulcanization has been analyzed by crosslink density
measurements.41

1.4.2 Mechanism of Sulphur Prevulcanisation of NRL

The chemical mechanism of the vulcanization is not well understood

and is still contoverisal.43 Early studies suggested, and others just assumed that
vulcanization takes place upon direct contact between the latex particles and the
vulcanizing reagents, since the latter (sulphur, ZnO and ZDC) are insoluble in
water. Yet others preferred the premise that the reactants must first dissolve in
the aqueous phase before diffusing into the latex particles.98-100

The presence of water in the latex is essential for the occurrence of the
sulphur prevulcanisation of NRL at unexpectedly low temperatures. The
enhanced solubility of sulphur and accelerator in the latex aqueous phase
facilitate sulphur prevulcanisation. The first important step of the reaction is the
formation of a sulphur-accelerator species in the aqueous phase of the latex.
This species or some derivative of it then transfers to the rubber phase and
crosslink the rubber molecules therein. Many hypotheses have been proposed on
the transport of the vulcanizing reagents through the aqueous phase. If this
species is surface active, the most obvious mode of transfer is adsorption from
the aqueous phase on to the surface of the rubber particle. Van Gils, Porter,
Rawi and Rahim showed that both the accelerator and sulphur dissolve in the
aqueous phase of ammonia preserved NRL before migrating to the rubber
phase.98-100 The Zn atoms of the accelerator form complex with hydroxide ions
from the water to provide the sulphur-accelerator species with water solubility
for transfer to the rubber phase.
18 
 The sequence of events following the arrival of the vulcanizing
reagents at the surface of the latex particles is of paramount importance in
influencing the morphology of the latex particles.43 The microscopy techniques,
such as AFM and transmission electron microscopy (TEM), have been used in
the elucidation of chemical mechanism of latex prevulcanisation.43,45,46 The
surface morphology of prevulcanised NRL films monitored using AFM provides
new insight into the prevulcanisation mechanism. Based on AFM studies,
C.C.Ho and M.C.Khew proposed the following mechanism for the
prevulcanisation of NRL.43 Basically the prevulcanisation mechanism is
controlled by the relative rates of the diffusion of vulcanizing reagents and the
crosslinking reaction within the latex particles. The rate of crosslinking reaction
is much faster than the diffusion rate of the reagents in the rubber phase during
prevulcanisation. Hence crosslinking takes place on the surface of the latex
particles before the reactants can diffuse into the core. This leads to an
unvulcanised core surrounded by a highly crosslinked shell of rubber molecules,
resulting in inhomogeneous latex particles. This crosslinked shell acts as the
recipient surface for the arrival of more crosslinking reagents and becomes a
hindrance to further diffusion of these materials into the core. The difference in
diffusion rates of the two phases during the gradual coalescence of the film
results in the collapse of the denser shell of the particle. The hardened shell of
the partially vulcanized particles also retards the diffusion of the rubber
molecules and thus hinders further gradual coalescence of the latex particles in
the film. Hence the film surface remains rough and uneven for the highly
crosslinked latex films. A homogeneously vulcanized particle is not achieved by
prevulcanisation. Thus complete vulcanization could not be achieved even after
postvulcanisation.43

19 
Figure 1.11: Proposed mechanism of latex prevulcanisation and film formation

The phase transfer/bulk polymerization/TEM technique has been

successfully applied to elucidate the internal morphology of prevulcanised NR
and skim latex particles.45,46,101-105 The technique involves the titration of
negatively charged latex particle with an aqueous solution of cationic surfactant
such as benzyldimethyl hexadecylammonium chloride (BHAC) in the presence
of a non-water miscible monomer e.g., styrene, until reaching the end point. Due
to the neutralization, the latex particles completely transfer from the aqueous
phase into the organic phase. The monomer containing swollen rubber particles
was then polymerized. After sectioning the specimen and staining with OsO4,
the rubber particles embedded in polystyrene (PS) was studied under TEM. By
using this process, the freeze-drying of latex normally required for specimen
preparation is omitted and, hence, the disturbance of rubber particle structure is
minimized. The internal morphology of prevulcanised NRL particles under
TEM showed that the sulphur and γ- radiation systems caused homogeneous
crosslink inside each particle while a non-uniform network, a dense network
near the surface of the particle was noticed in the sample employing peroxide.

20 
Figure 1.12: TEM micrographs of crosslinked NR embedded in a PS matrix:
(a, b) sulphur prevulcanised and (c, d) peroxide prevulcanised
latex particles

1.4.3 Methods for Assessing the Degree of Vulcanization of Prevulcanised

NRL
(1) The chloroform-coagulation test

A sample of prevulcanised latex is coagulated by mixing with an

equal volume of chloroform and the degree of vulcanization is evaluated from
the appearance of the coagulum. 106

21 
(2) The equilibrium swelling test

In this method, the degree of vulcanization is judged from the

extent of equilibrium swelling of films dried down from the latex, the swelling
being carried out under controlled conditions using a suitable solvent.107-110

(3) The relaxed –modulus

In this method, the degree of vulcanization is judged from the

relaxed modulus at 100% extension of films dried down from the latex.111-114

(4) The prevulcanisate relaxed-modulus (PRM) test.

This method assesses the degree of latex prevulcanisation by

way of measurement of the elastic modulus of a film dried down from the latex.

Only the chloroform coagulation test is peculiar to prevulcanised

NRL which is applied to the latex itself, and not to films dried down from the
latex. The other three tests are applied to films from the latex and are in
principle applicable to any elastomeric films including post vulcanized films
derived from rubber latices.

1.4.4 Structure of Films Derived from SVNRL

Particles in prevulcanised latex would dry down to coherent, well

integrated films because the crosslinks between the rubber macromolecules
would restrict the ability of the molecular segments in one particle to
interdiffuse with those of contiguous particles. Three theories have been
proposed to explain the strength and coherence of films derived from
prevulcanised NRL.44 They are

(1) The primary valence bond theory

(2) The bond adhesive theory

(3) The secondary valence bond theory

22 
(1) The Primary Valence Bond Theory

Here strength is attributed to the formation of interparticle

covalent chemical bonds between the rubber macromolecules in contiguous
particles, such bonds being formed as the film dries. These bonds immobilize
the rubber macromolecules within the individual particles. Two types of
network can be distinguished in deposits from sulphur prevulcanised latices.
One type is formed during the prevulcanisation reaction and the other type is
formed as the film dries. There is a ready mechanism by which such interparticle
bonds can form. Rearrangements of polysulphidic links among themselves at
elevated temperature together with formation of further sulphur crosslinks, if
residual vulcanizing ingredients are present, which lead to the formation of
interparticle crosslinks. But the formation of interparticle crosslinks during
drying is not essential for the formation of strong coherent deposits from
prevulcanised latices. Due to this reason, the primary valence bond theory has
been rejected.

(2) The Bond Adhesive Theory

Here the strength and coherence of deposits from SVNRL, is

due to a close packed assemblage of small particles of vulcanized rubber bonded
together with non-rubber substances situated in the interfaces between the
particles. If all the non-rubber substances are removed from the film and the
theory is correct, then it would be expected that the film would disintegrate. But
results of Humphreys, Wake and Ghazaly revealed that the strength and
coherence of the films is not primarily depending upon the presence of
appropriate non-rubber substances in the latex.

(3) The Secondary Valence Bond theory

Strength is attributed to secondary valence bonds formed

between segments of the rubber macromolecules in the surface of contiguous
particles. These interactions are developed as the latex dries and the surface of

23 
contiguous particles come into increasingly close contact and as the region of
overlap between the surfaces of the two particles increases in volume. Although
individual bonds are very weak, the total force required to separate particles is
sufficient to account for the strength and coherence of the deposit. Thus in order
to separate two contiguous particles, it is necessary to break the entire secondary
valence bonds which have been formed in the region of overlap between the
surfaces of the two particles. The tensile strength of prevulcanised latex films
and behaviour of prevulcanised latex films towards rubber solvents can be
satisfactorily explained using this theory. Lebedev et al. provide evidence for the
correctness of this theory.

1.4.5 Factors Affecting Sulphur Prevulcanisation of NRL

(1) Temperature

Gorton studied the effect of temperature upon the rate of sulphur

prevulcanisation of NRL using ZDC as accelerator and a small amount of ZnO
as activator.111,112 Over the temperature range 40-70ºC, the rate of crosslinking
increased with increasing prevulcanisation temperature as is evidenced by the
modulus of the vulcanisate. Tensile strength and elongation at break were better
when prevulcanisation was conducted at lower temperatures and at each
temperature with a shorter heating time.

(2) Level of vulcanizing ingredients

Gorton studied the effect of levels of sulphur and accelerator

upon the sulphur prevulcanisation of ammonia preserved NRL using a small
amount of ZnO keeping the accelerator/sulphur ratio constant.111 Although the
level of sulphur and accelerator was increased by a factor of 10, the effects upon
film properties after any given time of prevulcanisation were found to be
relatively slight. This is because the amount of vulcanizing ingredients which
become available for reaction with rubber under these conditions were probably

24 
determined by factors other than merely the amount of ingredients present in the
system.

(3) Presence/absence of a sparingly soluble inorganic zinc compound

It is desirable to minimize the level of sparingly soluble Zn

compounds in the compounding ingredients for the following reasons. (1) in
order to minimize the colloidal destabilization arising from the formation of Zn-
ammine ions in the aqueous phase of the latex. The higher the temperature more,
serious is the problem likely to be. (2) to achieve maximum optical clarity in the
eventual rubber film. Merril studied the effect of ZnO upon sulphur
prevulcanisation reaction. In the absence of ZnO, the level of free accelerator
decrease sharply as prevulcanisation proceeds and eventually falls to zero. The
rate of decrease of the level of free accelerator is greatly reduced if a small
amount of ZnO is present because ZnO regenerates the accelerator.

(4) Nature of dithiocarbamate accelerator

Gorton studied the effect of nature of dithiocarbamate

accelerator upon sulphur prevulcanisation using ZDC, zinc di-n-butyl
dithiocarbamate and their corresponding sodium salts as accelerator and ZnO as
activator.111,112 Zinc di-n-butyl dithiocarbamate is more active in promoting
crosslinking at lower prevulcanisation temperature and also give highest tensile
strength than ZDC.

(5) Degree of dispersion of insoluble vulcanizing ingredients

Results of Gorton and Pendle showed that the particle size of the
sulphur and accelerator have no significant effect upon the tensile properties of
the films obtained from the latex.112 It indicates that the amount of vulcanizing
ingredients which become available for reaction with rubber under these
conditions is not significantly affected by the area of interface between the
sulphur or accelerator particles and the aqueous phase.

25 
(6) Effect of addition of surfactant

It was reported that addition of small amounts of carboxylate,

sulphonate and sulphate surfactants enhanced the mechanical and chemical
stabilities of NRL by rearranging the indigenous soaps, derived from protein-
lipid, and making them more effective as stabilizers. This ability depended
largely upon the chain length of their alkyl group and the optimum enhancement
was observed when the alkyl chain of the surfactants consisted of approximately
45
11 carbon atoms. The sulphur prevulcanisation of NR particles was enhanced
by the presence of sodium dodecyl sulphate (SDS) which causes an increase in
the amount of negative charge on the surface particles.

1.4.6 Mechanical Properties of SVNRL

(1)Tensile strength

Blackley and Merril reported that the tensile strength of films

from prevulcanised NRL compounds depends on the ability of the particles to
coalesce and integrate when the film dries and on the concentration of the
crosslinks in the rubber.44 The tensile strength of vulcanized film depends upon
the conditions under which the film was dried but is always considerably greater
than that of unvulcanised films. The effect of crosslink concentration upon the
tensile strength of pre and post vulcanized NRL films has been investigated by
Porter.99 The ratio of interparticle to intraparticle crosslinks was found to be
higher in a sulphur post-vulcanized film as compared with a sulphur
prevulcanized film. 113,114 When the film is prepared from a highly crosslinked
latex, coalescence of the rubber particle becomes more and more difficult
resulting in lower tensile strength.

Justin Che et al. studied the structural development and morphology in

unvulcanized and vulcanized (both pre- and postvulcanized) NRL both in a
relaxed state and under deformation by multiple-quantum (MQ) NMR and in
situ wide-angle X-ray diffraction (WAXD), respectively. Vulcanization was
carried out using both sulfur and peroxide, showing important differences on the
26 
spatial distribution of cross-links according to the source of vulcanizing agents.
Sulfur prevulcanization promotes the formation of highly homogeneous
networks in the dispersed rubber particles, whereas peroxide vulcanization
makes broader spatial crosslink distributions. The latter is compatible with the
formation of core–shell network structures. Molecular orientation and strain-
induced crystallization were analyzed by both stress–strain relations and
WAXD. An increase in the vulcanizing agent concentration led to an increase in
modulus and crystalline fractions. For sulfur vulcanization, the additional heat
treatment (postvulcanization) increased the interactions between rubber particles
and unreacted vulcanizing agents. For peroxide vulcanization, the additional
heat treatment led to chain scission reactions and degradation of network
points.114

Figure 1.13: Comparison of pre and post vulcanisation

(2)Behaviour towards rubber solvents

When immersed in rubber solvents such as toluene or

chloroform, it is found that films from SVNRL swell very considerably to give
gels which are mechanically rather weak. Humphrey and Wake observed that if
significant post vulcanization is avoided, films from SVNRL tend to disintegrate
into a mass of very small separate particles of vulcanized rubber swollen with
solvent. Prevulcanised film can readily rupture if a drop of solvent is placed
upon it whilst it is held in an extended condition. It is for this reason that latex

27 
dipped gloves are more readily damaged by oil and grease than are those which
have been vulcanized after the glove film has been formed. However this
disadvantage of prevulcanised films relative to post vulcanized films can be
mitigated to some extent by subjecting the prevulcanised film to post
vulcanization.

1.4.7 Comparison of Sulphur Prevulcanisation of NRL and Sulphur

Vulcanization of Dry NR

Sulphur prevulcanisation of NRL occurs at much lower temperatures

and is more facile than sulphur vulcanization of dry NR using an identical
vulcanizing system. 40,42 The results obtained by Loh illustrate that sulphur
prevulcanisation occurs much more rapidly than does vulcanization of solid NR
at the same temperature using the same vulcanizing ingredients. Analogous
results are obtained for artificial latex of synthetic cis-1, 4-polyisoprene and the
corresponding dry solid polymer. The unexpected facility of sulphur
prevulcanisation of synthetic polyisoprene latex compared to ammonia
preserved NRL is due to the absence of non-rubber substances in them. The
speed of the prevulcanisation reaction seems to be associated primarily with the
presence of water.41

Prevulcanisation of NRL has two particular advantages over vulcanized dry

rubber.

(i) Prevulcanised latex tends to be very much stronger and elastic as the
elastomer chains have not been degraded by the mechanical work needed to
incorporate curatives into the dry material.

(ii) Since even post vulcanization takes place at a relatively low

temperature (generally below 1200C) possible to incorporate colouring
chemicals which could not survive the high temperature used for cost effective
conventional vulcanization (typically 100-2000C).

28 
1.4.8 SVNRL-Industrial Grades

Three grades of high ammonia and one grade of low ammonia

prevulcanised latex are available. The high ammonia grades are distinguished as
low modulus (LR), medium modulus (MR) and high modulus (HR) according to
the modulus of films which dry from the latex. The low ammonia grade used for
heat sensitized dipping of films having medium modulus and high optical
clarity. Other grades of SVNRLs available are (1) grades having reduced
concentration of non-rubber substances by double centrifugation of latex. (2)
grades having low levels of extractable N-nitrosoamines and N-nitrosatables in
films dried from the latex. (3) grades which are currently available from
Revertex under the trade name ‘Revoltex’. There is no need for further
vulcanization of films from these latices with additional vulcanizing ingredients.

P r e v u lc a n i s a t i o n o f N R l a t e x

R a d ia tio n

S u lp h u r P e r o x id e
γ − r a y / e l e c tr o n b e a m U V - ra ys

H ig h a m o n ia te d H i g h a m o n i a te d H ig h a m o n i a t e d H ig h a m o n ia te d
N R la te x N R la te x N R la t e x N R la te x

A d d i t i o n a n d m i x in g o f
R e d u c tio n o f N H 3
a t-b u ty l h y d ro p e ro xid e
A d d it i o n a n d m i x i n g o f A d d it i o n a n d m i x in g o f
a n - b u ty l a c ry la te e m u l s i f i e d p h o t o i n i t ia t o r
s e n s itiz e r a n d th i o l c r o s s li n k e r

P r e v u lc a n i s a t i o n
A d d i t i o n a n d m i x in g o f γ − r a y i r r a d ia t i o n U V - ir ra d ia tio n
s t a b il i s e r s , S, ZD C, a t 5 0 -7 0 0C
ZM BT, ZnO and
a n t io x id e n t d i s p e r s i o n s

C o m p o u n d m a tu ra tio n a n d
A d d itio n o f a n tio x id a n t
p r e v u lc a n i s a t i o n a t 3 5 - 8 0 0 C

P r o d u c t f a b r ic a t i o n , d r y i n g P r o d u c t fa b r ic a tio n

a n d p o s t v u l c a n i s a ti o n a n d d ry in g

Figure 1.14: Various methods for prevulcanisation of NRL

29 
1.5 Film Formation Process

Polymer latex films are formed by spreading water based latex

dispersion onto a substrate and allowing the water to evaporate until the particles
come into contact and fuse together.14 The fundamental process involves the
transformation of the particles in a stable latex dispersion into a continuous
film.115-118 Early work on the mechanism of latex film formation was carried out
by Dillon et al., Brown, Voyutskii, Bradford and Vanderhoff, and Mason.119-121
Over the years, various improvements to these early models have appeared, and
the general picture that emerged recognizes, conceptually for an idealized
model, the film formation process as being divided into three distinct stages. The
first stage involves the linear cumulative water loss with time of the
concentrated latex dispersion, with increasing restricted Brownian motion of the
particles until they come into contact. The packing of the latex particles with
interstices water depends on the polydispersity of the particle size and the ionic
strength of the original latex dispersion. Further, slower evaporation of water
leads to deformation and coalescence of the soft deformable particles in the
second stage. Deformation is driven primarily by capillary and osmotic forces
and resisted by electrostatic/steric repulsion and viscous and elastic deformation
of the polymeric particles. At the end of this stage, the film is dry but particle
contours are still discernible, the particles having deformed into a polyhedral
structure. At the final stage, interdiffusion of polymer chains across the particle-
particle interface occurs (termed further gradual coalescence or autoadhesion), if
the film is at a temperature above the glass transition temperature (Tg) of the
latex particles, resulting in a mechanically continuous homogeneous film. Any
residual water left in the film would escape by diffusion through capillary
channels between the deformed particles or through the polymer itself.

30 
Figure 1.15: A pictorial representation of the stages of latex film formation
from soft polymer particles (a) the latex dispersion (b) the solvent evaporates
leaving the particles in close contact (c) deformation and packing of the particles
(d) further coalescence produces a mechanically rigid film.

The nascent film is normally weak. Its mechanical properties, such as

tensile strength, improve gradually, often requiring days or weeks to reach their
final properties. It is commonly believed that the enhancement of tensile
strength is a consequence of polymer diffusion across the particle-particle
interface in the film. Important factors responsible for interdiffusion capability
of polymers in lattices are the molecular weight of the polymer, film formation
31 
temperature, the spatial distribution of chain ends near the interface, and the
steric and electrostatic stabilization of the latex.122-127

Many studies of the latex filming process, utilizing a variety of

techniques, have been published. TEM of latex films has been the traditional
method for examining the film morphology. Roulstone et al. and Wang et al.
used freeze-fracture transmission electron microscopy (FFTEM) to investigate
the deformation, coalescence and fusion process in poly (butyl methacrylate)
(PBMA) particles in the latex film with a particle diameter of 114-400 nm. The
molecular interdiffusion phenomena in the third step have also been extensively
studied by techniques such as non-radiative energy transfer (NRET) method and
small-angle neutron scattering (SANS). 116

Latex film formation studies of synthetic latexes by AFM have been

actively pursued recently.128-152 The time and temperature dependence of particle
deformation/flattening at the surface of PBMA latex has been measured by Goh
et al. and Lin et al. respectively. Besides the influence of time and temperature
on the film formation process in the second and third steps, attention was also
paid to the effect of particle size on the sintering temperature of latex filming.
However, the Tg of almost all the polymers investigated are close to or above
room temperature, such as PBMA and polystyrene. Lin et al. monitored the
flattening rates of PBMA film from the corrugation heights of the latex particles
as a function of time at different annealing temperatures. They found that the
kinetics of film formation obey the time/temperature superposition principles
and demonstrated a direct relationship between film formation kinetics and
rheological properties.

In contrast, there is very little work done on the film formation of NRL,
even though NRL is used extensively in the manufacture of gloves,
prophylactics, and other dipped-goods that also involve film formation of the
latex particles. In fact, the necessary condition of such applications is the
formation of a continuous film with the appropriate mechanical strength. Apart
from the much larger particle size and wider size distribution, one obvious

32 
difference between synthetic and NRL is that NRL also contains a host of non-
rubber materials in small amounts. These non-rubbers are either soluble in the
aqueous phase or adsorbed on the latex particle surface. The latex particles in
commercial latex concentrate are stabilized by an adsorbed layer of mainly long-
chain fatty acid soaps, polypeptides, and proteins. NRL forms a continuous,
almost transparent film when allowed to dry as a thin spread on a substrate.
Once initial contact between the latex particles is achieved by gelation following
the uniform destabilization of the latex particles, dehydration of the aqueous
phase retained in the interstices of the 3-D gel network of latex aggregates
follows.

aqueous phase

Figure 1.16: Latex particles in colloidal suspension (Particles dispersed in

aqueous phase are separate, uncrosslinked, and homogeneous throughout.)

Figure 1.17: Particles with prevulcanisation (Dispersed particles, still separate

but lightly crosslinked.)

33 
Figure 1.18:Particles with procure (Particles with crosslinked surface and very
slightly crosslinked interior.)

[Upon drying, precured particles agglomerate and form only a weak film
because the thick particle skin interferes with homogeneous vulcanization.]

[Prevulcanised particles agglomerate and form a good film with homogeneous

crosslinking.]

Figure1.19: Film formation contrasts

The extent of prevulcanisation has a profound effect on the formation of

the latex film. A coherent film would not be achieved if the particles were
highly crosslinked near their surface owing to the restricted mobility of the
rubber chains at the particle surface. On the other hand, homogeneously cross-
linked particles fuse well and form a film with optimum physical properties.45

34 
1.6 Uses of Prevulcanised NRL

Prevulcanised NRL is a very convenient raw material mainly for the

manufacture of thin film-products.45 Partially prevulcanised NRL has been
found to be capable of yielding thin films which have very satisfactory
mechanical properties, especially if those films have been further vulcanized.
The principal mechanical properties of interest of thin rubber films are tensile
strength, puncture strength and extension at break.

Prevulcanised latex widely used for the production of various dipped

goods the bulk of which is in the form of examination and surgical gloves.43 In
the context of dipping, the use of partially prevulcanised NRL offers a
considerable economic advantage relative to post vulcanisable NRL in that its
use enables a large quantity of rubber to be partially vulcanized as bulk latex
instead of having to be entirely vulcanized when spread out as a thin film over
the surface of innumerable formers. Prevulcanised latex when used for making
gloves need not undergo a thorough vulcanization process since this has already
taken place during the mixing and heating up of the chemical mixtures with
latex.

Technically the dipping process using NRL involves the following basic
steps. (i) latex compounding by mixing the latex with dispersions of vulcanizing
reagents (sulphur, ZnO, and organic accelerator such as ZDC and additives such
as surfactant, antioxidant, pigment, filler and so forth); (iii) agitating the mixture
during a period of maturation at 20-700C; (iii) forming the articles by dipping so
as to deposit a thin layer of the compounded latex on a former. A former is a
solid surface on to which a thin layer of latex can be coated by dipping it in the
latex and then withdrawing it. The thin latex film formed after drying can be
stripped off. The former, made of ceramic, takes the shape of a hand in the case
of glove manufacturing; (iv) leaching followed by heating to dry and vulcanise
the wet gel and (v) stripping the film from the former.43

35 
 The principal latex dipping processes are simple or straight dipping,
coagulant dipping, heat sensitized dipping, and electrodeposition. In straight
dipping, the clean and dry former is immersed into the latex, slowly withdrawn,
inverted, rotated, and dried. In coagulant dipping, the former is dipped into a
coagulant solution (e.g., calcium nitrate, calcium chloride), withdrawn, and
allowed to dry partially. It is then lowered into the latex compound and, after a
suitable dwell time, slowly withdrawn, inverted, rotated, and dried. Straight
dipping gives a very thin deposit of latex film, whereas coagulant dipping gives
a higher thickness of latex film deposited on the former. The thickness of the
latex film deposited on the former depends on several factors, namely, the
properties of the latex compound, the type and temperature of former, the
concentration and nature of the coagulant, the rate of withdrawal, and the dwell
time of the former.47

Figure 1.20: Production of latex gloves and toy balloons by dipping process

Prevulcanised latex is ideal for small scale manufacturers of balloons

and gloves where it does not require compounding the latex to produce superior
products.42 This will bring down the cost of production of small scale units. It
has long shelf storage life, online process life, consistency and stability.

36 
 From the point of view of a manufacturer, the use of prevulcanised latex
simplifies a great deal the whole manufacturing process. Depending on what
products are being made, the prevulcanised latex could be used as it is (as in the
case of toy balloons after the addition of pigments) or after some dilution with
water to achieve a final latex solid content of as low as 30% (as in the case of
examination gloves). What one needs to do next is to mix for about 30 minutes
and allow enough time, usually 16-24 hours for deaeration before the latex is
ready for dipping, casting, extrusion, spraying, painting, coating etc.

Another important advantage is the low residual chemicals, particularly

the accelerators. This results in a cleaner latex compound with low toxicity level
which of utmost importance for the manufacturing of medical devices such as
gloves, baby teats, condoms, catheters and medical tubings. Testing of these
articles has been carried out by medical device manufactures tacking their
destination and service conditions. This includes chemical analysis of extracts,
skin irritation, skin sensitization, muscle implantation pyrogeneity, cell
cytotoxicity etc.

Latex medical articles made from prevulcanised latex are in most cases
biologically less active than those made from typical post vulcanisable latex
compounds. Biological activity is usually caused by ingredients that have not
fully reacted in the process of vulcanization. These could migrate into human
bodily fluid such as fluid from mucous membranes, blood, saliva and other
physiological fluids.

Prevulcanisation can be used to control the degree of crosslinking.43

Using prevulcanised latex, a higher degree of cross-linking can be achieved
compared with that of a purely post vulcanized latex film. No maturation period
is required as in the case of post vulcanisable latex compound where a
maturation stage is almost always a prerequisite for making reasonably good
quality latex products. Maturation is a stage when sufficient time must be
allowed for both the naturally occurring and added surfactant and fatty acid
soaps to reach equilibrium. Maturation allowed time for the maximum

37 
dissolution of sulphur-accelerator species to migrate into the rubber particles.
Also, a controlled degree of vulcanization must take place during this stage
before the latex compound is ready to be used. To use the latex compound too
early or too late would result in under curing and over curing respectively.

Generally speaking, unlike prevulcanised latex, post vulcanizable latex

compound would have a marching curve immediately after compounding in
terms of degree of vulcanization. Hence, in the case of post-vulcanisable latex
compound, it is more difficult to prevent situations of over-curing when
cracking and tearing of, for instance, gloves and condoms are frequently
encountered. This is attributed to the fact that the tensile strength reaches a peak
before reclining as the crosslink density increases. In short, post- vulcanisable
latex compound has short shelf life of usually from 2 days to 2-3 weeks
depending on the curative formulation. On the other hand prevulcanised latex
generally has a very much longer shelf-life of 6 to 9 months. Therefore less
stringent process controls are required for prevulcanised latex.

The viscosity of post-vulcanisable latex compound increases with time,

unlike prevulcanised latex. This is basically a result of zinc-ammine thickening.
This involves the dissolution of ZnO by ammonia in the presence of ammonium
salts releasing zinc-ammine complex ions which in turn would react with
stabilizers on the latex particles namely the fatty acid soaps and proteins forming
insoluble zinc soaps and proteinates. The end result is the loss of stability
accompanied with increasing viscosity. Although the vulcanization stage is not
required for prevulcanised latex, in practice, an oven is still required to
accelerate the drying.

Sulphur prevulcanisation can also be extended to epoxidised natural

rubber latex (ENRL). ENRL is a chemically modified form of NRL. ENR was
produced by attaching the epoxy group to NR molecule. The epoxidation has
been mainly carried out in latex stage using freshly prepared peracetic acid,
performic acid or the mixture of H2O2 and organic acid, i.e. formic acid or acetic
acid.153, 154

38 
 Epoxidation O

H2O2/ HC(O)H

n Latex medium n-m m

Natural Rubber Epoxidised Natural Rubber

Figure 1.21: Synthesis of epoxidised natural rubber

ENR has been shown to exhibit beneficial properties, particularly its oil
and chemical resistance, air permeability and adhesive properties. It would be
useful if these desirable properties of ENR could be exploited in latex dipped
product applications. However, uncompounded ENRL has been shown to be
incapable of being satisfactorily processed by coagulant dipping due to its
inability to gel on the former and because of the formation of a very thin latex
deposit. The main reason for this observation is the stabilization of ENRL by
high level of non-ionic surfactant. Whilst the non-ionic surfactant is necessary to
keep the latex stable during epoxidation reaction with acetic acid and H2O2, it
however, keeps the latex chemically too stable against the calcium salt coagulant
such as Ca(NO3)2.

Figure 1.22: Schematic representation of γ-radiation prevulcanisation of ENRL

particle

Skim latex, a byproduct of field NRL concentrated by centrifugation can

be prevulcanised using sulphur and peroxide systems. 102,104,155 By applying
centrifugation process, most of the non-rubbers solids, about two thirds of the

39 
water-soluble non-rubbers and small NR particles or skim rubber are removed.
While the surface-active species or indigenous surfactants remain in the serum
and/or on the rubber particles in the concentrate fraction. However, the skim
rubber has always been discarded and has not received much attention due to the
high ratio of aqueous phase in the latex. Previous study reported that the skim
latex contained about 7% TSC and 5% DRC. Although skim rubber was studied
for its use as an urea encapsulant in the controlled release application, a better
understanding of the properties of skim particle is still needed in order to
facilitate its recovery and to explore other potential use.155

Owing to its small particle size, skim rubber would be a good choice for
use as agglomerating latex in the heterocoagulation process which involves
agglomeration of small particles onto a large core particle. This technique
generally offers the possibility of a better control for certain composite latex
particle morphology, especially the core–shell type. An interpolymer complex
principle was also successfully applied to prepare the heterocoagulated
NR/polychloroprene (CR) with core–shell structure. Due to the low glass
transition temperature (Tg), the NR/CR core–shell particle was obtained without
annealing the aggregate at high temperature. Better oil resistance of film casted
from heterocoagulated latex than that of NR film also confirmed the role of high
polar CR, the agglomerating latex or shell layer. The study of replacing CR by
skim NRL, naturally abundant and low cost products, in the heterocoagulation
technique was, therefore, of great interest. To improve oil resistant property,
prevulcanisation was the minimum requirement for skim rubber modification.104

Sulphur prevulcanised skim latex has higher degree of crosslinking

compared to that of peroxide prevulcanised skim latex. The presence of
hydrolysis product of skim latex, protein, could facilitate the rate of diffusion of
vulcanising reagents into the rubber phase and act as sulphur-cured activator.
Previous works reported that small amounts of proteinaceous substances in
NRL, being surface active, resulted in an increase in curative concentrations in
rubber particles. Since the rate of diffusion of alkoxy radicals derived from

40 
t-BuHP/fructose system into the rubber phase was lower than that of the
vulcanisation, the radicals generated in the aqueous phase reacted first with the
rubber molecules on the surface of PVNRL particles followed by abstraction of
hydrogen atoms to produce rubber radicals which readily combined to form
crosslinks. The high dissolution of alkoxy radicals in the initial stage resulted,
therefore, in the high crosslink density and, hence, low swelling ratio of the
PVNRL film. However, with longer prevulcanisation time, the constant swelling
ratio of PVNRL film was obtained and its value was higher than that of SVNRL
film. This might result from the effect of non-rubber substances which acted as
an inhibitor in the free radical polymerisation reaction. The role of protein–lipid
surrounding rubber particles on relatively low conversion in NR was reported
when the in situ polymerisation of styrene in NR and DPNR latex particles was
studied. It was believed that the indigeneous proteins in NR acted as free radical
scavengers which retard polymerisation and termine the grafting reaction
altogether. The small size of skim particle or large particle surface area should
also be responsible for the high degree of crosslinking. A mesh structure of all
sulphur-crosslinked skim particles containing PS, prepared by using the phase
transfer/bulk polymerisation process, irrespective of size, was uniform. In the
peroxide-cured latex, the network structure was noticed mostly in the form of
film.104

The prevulcanised skim latex having high degree of crosslinking and

homogeneous crosslink structure was used for the preparation of composite latex
particle of NR/ prevulcanised skim rubber by heterocoagulation technique. Data
from zeta potential measurement and the better resistance to toluene of films
casted from the heterocoagulated lattices when compared with that of the NR
film indicated the existence of SVNR on the outer layer of the composite
particles. The use of crosslinked skim as agglomerating latex in the
encapsulation of disinfectant agent for the preparation of NR medical glove is
also the ongoing research.104

41 
 Prevulcanised latex can be used for the preparation of various nano
composites and blends.41,49,50 Polymer nano composites represent a new
alternative to conventionally (macroscopically) filled polymers. Nano
composites are materials that have a nanometer scale dispersion of reinforcing
agents (at least one dimension). Because of their nanometer size filler
dispersion nano composites exhibit markedly improved properties when
compared to the pure polymers or their traditional composites. These include
increased modulus and strength, outstanding barrier properties, improved
solvent and heat resistance and decreased flammability. Clay and clay minerals
such as sodium montmorillonite, saponite, hectorite, bentonite etc have been
widely used as natural fillers in making the nano composites. The main reasons
for adding clay fillers to rubber are to enhance the mechanical properties and to
make the final products less expensive. 156-166
Commercial clay has been used as filler for rubber. The reinforcing
capacity of clay is poor because of its large particle size and low surface
activity. On the other hand, minerals have a variety of shapes suitable for
reinforcement, such as fibrils and platelets. Layered clays are comprised of
silicate layers having a planar structure of 1 nm thickness and up to 500 nm
length. The layers cannot be separated from each other through general rubber
processing. Since inorganic ions absorbed by clay can be exchanged by organic
ions, research succeeded in intercalating many kinds of polymers and to prepare
clay/polymer nano composites. Rubber–clay nanocomposites were prepared
from latex by a coagulation method and an improvement in mechanical
properties was reported.156-160

The conventional compounding technique was used to prepare

nanocomposites from latex. Some layered silicates are suitable additives for
latex, provided that they can form dispersions adequate for latex compounding.
NRL was compounded with dispersions of layered silicates and other
vulcanizing ingredients in order to produce vulcanized NR–clay nano
composites. In aqueous dispersions, the clay ‘swells’ and makes its good
dispersion in the rubber possible. Recently, Varghese et al. studied the properties

42 
of natural rubber and synthetic rubber lattices reinforced with layered
silicates.163,165 Presence of precipitated silica, china clay and whiting decreased
tensile strength and elongation at break but increased the modulus of the
prevulcanised latex film.

Poor tear resistance is a common problem encountered in medical

gloves and condoms. Fillers such as carbon black, ultra-fine calcium carbonate,
silica and starch are normally added to the NRL products for reinforcement.
These fillers however, are not good enough. Besides strength, the NRL products
should also be biodegradable. To produce totally biodegradable, NRL products
will require the complete change of the raw material (latex). However to
produce partial biodegradable NRL products is easier and can be achieved by
adding biodegradable material as one of the components in the NRL
formulation. A suitable biodegradable material is natural fibers because natural
fibers are abundant, cheap and due to their intrinsic properties could also
reinforce the NRL products.2

Natural fibers such as flax, hemp, banana and oil palm are known to
reinforce polymers. The reinforcement of rubber with natural fibres is possible
by combining the elastic behavior of the rubber matrix with the strength and
stiffness of the natural fibres. The degree of reinforcement of rubber by natural
fibers depends on the fiber concentration, fiber dispersion within the rubber
matrix. Poor fiber dispersion is the biggest problem encountered when mixing
rubber with natural fibers and this always results in the reduction of the overall
strength of the composites. Poor dispersion of the natural fibers with rubber
could be improved by modification of fiber surface by the use of bonding agent
and chemical modification of the fiber surfaces. Recently A.S.Siri Nuraya et al.
reported the use of banana stem powder as reinforcing filler for NRL. The
prevulcanised NRL films containing banana stem powder have properties
comparable to those films containing the same amount of calcium carbonate and
colloidal silica.2

43 
 Several investigations have been made in the past few years in the field
of blending of polymers. Blending is used extensively to improve the processing
characteristics as well as the properties of the end products. Excellent reports
regarding latex blends exist in the literature. Okikura conducted a series of
studies on the recent trends in the practical blending of various kinds of latices.
Shundo, Imoto, and Minoura found out a relation between the properties of
unvulcanized and vulcanized blends of NR and SBR prepared by means of
solution blending, latex blending, roll blending, and Banbury mixer blending. In
most cases, latex blending results in a good degree of dispersion, which cannot
be achieved by other blending techniques. Additionally, NR/SBR blends showed
a direct relation to their blend ratio, regardless of blending method used. The
blends of SBR and NR latices have many potential advantages. For example,
blends of 38% solid NRL and 22% solid SBR latex in the 70/30 ratio have good
processability. These blends combine better crack resistance, wet grip, and
weather resistance of SBR and the superior strength properties and low
temperature characteristics of NR.41

The effects of various factors like vulcanizing systems, prevulcanization

time, accelerator system, and shear rate on the rheological behavior of NR/SBR
latex blends have been analyzed. The rate of prevulcanization reaction in
homopolymer latices and their blends has been investigated by the variation of
viscosity in each time. NR and NR-rich blends show the highest increase in
viscosity with prevulcanization time compared with SBR and SBR-rich blends.
This is due to the lower unsaturation and low solid content of SBR latex. In most
cases pseudoplastic behavior is observed except in the case of SBR and SBR-
rich blends. The dilatant behavior of SBR and SBR-rich blends is attributed to
the high temperature sensitivity of SBR latex. 41

Prevulcanised NRL can also be used for the modification of asphalt

emulsion applicable for high way construction application. Asphalt emulsion is
manufactured by emulsification of asphalt, and it is an energy saving,
ecologically safe material because it does not need any heating processes which

44 
can emit gas and fire hazard in its use. Using prevulcanised NRL as an
admixture of asphalt emulsion, thermal stability and useful mechanical
properties of the asphalt emulsion were improved. The mechanical and physical
properties including softening point and penetration of asphalt emulsion were
also very well modified by the vulcanized rubber phase. The increase in
vulcanizing agent could also increase softening point. At low polymer contents,
the samples reveal the existence of dispersed polymer particles in a continuous
bitumen phase, whereas at high polymer contents a continuous polymer phase
was observed.167

Recently it has been reported that prevulcanisation of NRL does not

hinder the formation of conjugated sequences, which is a precondition for
developing intrinsic electrical conductivity in polymers. So prevulcanised NRL
can be dopped by iodine to become electrically conducting and the dopping
process is not affecting the flexibility or processability of the films. The
incorporation of a steric stabilizer such as starch enhances the solution dopping
of the prevulcanised NRL resulting in flexible semiconducting thin films with an
optimum enhancement in the electrical conductivity behavior and a decrease in
optical band gap. Doped vulcanized NRL promises to be a cost effective and
highly efficient material for use in solar cells and light emitting diode
materials.168-171

Polymethyl methacrylate (PMMA) particles were deposited onto the

sulphur prevulcanised NRL film by using the layer-by-layer technique in order
to increase the roughness and hence, decrease the friction on the rubber surface.
Prior adsorption of PMMA particles, the sulphur prevulcanised NR sheet was
pretreated with argon plasma followed by UV induced graft co-polymerisation
of polyacrylamide to generate charge on the NR film. This modified sulphur
prevulcanised NRL can be used for the development of gloves designed for the
hypersensitive person because here the direct contact between the rubber and
skin is decreased. 172-174

45 
 Recently it was reported that maleated suphur prevulcanised NRL (M-
SVNRL) can be prepared by grafting maleic anhydride on to SVNRL particles
by using benzoyl peroxide as an initiator. The tensile strength, modulus,
hardness and elongation at break of SVNRL film dramatically increased after
grafting with maleic anhydride. Due to the reduction of double bond, the thermal
stability of M-SVNRL film was better than that of SVNRL. The environmental
friendly M-SVNRL would be further applied as a compatibilizer between NR
and biopolymer.175,176

However, there are some disadvantages for prevulcanised latex.

These are the inherently darker colour and the higher tackiness. Another
disadvantage of prevulcanized NRL is that the wet gel strength of the dipped
films may be lower than that of nonprevulcanized latex films, thus requiring
some changes in the manufacturing process.

1.7 Latex Allergy

Allergy to latex was first recognized in the late 1970s and since
then it becomes a major health concern as more individuals continue to be
impacted. Allergic reactions can affect the skin, eyes, mouth, nose, throat, lungs
and heart. Symptoms range from skin rashes, redness, itching to dizziness and
abdominal pain. Up to 6% of the general populations are allergic to NRL.177-225

Latex allergies are of two types. They are

(1) Type IV allergy

Type IV (delayed type) hyper sensitivity is usually caused by

chemicals such as accelerator, antioxidants, emulsifiers etc. added to the latex.215
Type 1V reactions are generally not life threatening and tend to be localized
near the area of contact. The cytotoxicity and tissue irritancies of NRL materials
were correlated to the residual amount of zinc dithiocarbamate accelerators.
MBT-type accelerators are known as contact allergens. DTB-type accelerators
have been reported to show strong cytotoxicity.199

46 
(2) Type I allergy

It is caused by proteins present in the latex and these type

reactions tend to be general and can be life threatening.106,203

The proteins help to maintain the latex colloidal stability during

collection and transport prior to manufacture. But the presence of proteins in NR
has been assumed to exert influence on some undesirable properties such as poor
creep and stress relaxation, increasing storage hardening and moisture
adsorption. Recently, the extractable proteins in the latex products are found to
be responsible for the allergic reactions and it is recommended these proteins
should be removed. Consequently, when measures are taken to remove or
degrade these proteins, other problems can be introduced, such as destabilization
of the latex and changes in its coagulation properties. The proteins can be
removed either in latex stage or by treatment of the finished product.

1.8 Protein Removal in Latex Stage

Deproteinised natural rubber (DPNR) latex is a purified form of NRL

with very low nitrogen and ash content. Either mechanical or chemical means
are common for reducing protein content of latex. The mechanical process
involves multiple centrifugation or membrane filtration of diluted latex. The
chemical treatment involves a combination of digestion with a proteolytic
enzyme or displacement of adsorbed proteins using a surfactant and the
subsequent purification of the treated latex by centrifugation or creaming.

47 
1.8.1 Mechanical Processes Used for Deproteinisation

• Centrifugation
Most of the protein (75%) in field NRL is freely dissolved in the serum
fraction while a minor fraction (25%) is bound to the surface of the rubber
particles. NRL is typically concentrated to reduce the water content. When latex
is centrifuged, the field latex is concentrated from about 33% rubber solids to
60% solids. About one-half of the soluble proteins are removed from the NRL
by this process. Since most of the reduction is from the natural rubber serum
fraction, the actual percentage of protein bound to rubber particles is increased
from 25% to about 50% of the total.12

If the NRL is processed further by another round of centrifugation, the

latex protein content can be reduced even further. This is usually achieved by
diluting the centrifuged NRL concentrate with water back to about 30% solids,
and then recentrifuging it back to 60% solids. This additional processing can
further reduce the serum proteins by another 50% or more. Therefore, double
centrifuging of latex can reduce the overall protein content by 63% or greater.
Although this approach is a simple way of reducing the protein content of NRL,
it may not be the most cost effective. Each time the latex is concentrated by
centrifugation, about 10% of the rubber is lost to skim latex, and fresh field latex
cannot be processed since the centrifuges are being used. In addition, the double
centrifuged latex may have to be supplemented with chemical stabilizers to
maintain the NRL stability and to prevent any unacceptable coagulation from
occurring. The EP content attributable to serum proteins in finished unleached
gloves made from double- centrifuged NRL can be reduced by 60% or more
when compared with gloves made from single-centrifuged latex. However, the
EP attributable to bound proteins is not affected by this process and therefore the
reduction in total antigenic protein content in finished gloves may be somewhat
less than 60%. Another 50% reduction in serum-EP might be possible by using
triple-centrifuged NRL (recentrifugation of double-centrifuged NRL).

48 
 • Creaming
Creamed NRL is produced by modifying the buoyant density of the
latex and thereby accelerating the natural creaming of NRL. Creaming is a
process of concentrating NRL so that the rubber particles in the latex rise slowly
to the top to form a creamed rubber layer on the liquid. This process is similar to
the creaming of milk. Creaming is usually carried out in large vessels with the
addition of creaming agents that increase the buoyant density of latex, such as
alginate and methylcellulose type polymers. As the rubber gradually rises to the
top of the liquid and is concentrated, the aqueous serum phase is removed from
the bottom of the vessel, leaving the creamed latex concentrate in the tank.

This process of creaming NRL is sometimes more effective but slower

than centrifugation. NRL concentrations up to 68% are typical of creamed latex;
thus more of the serum phase is removed than in centrifuged latex. Following
the creaming of rubber, much of the soluble protein is removed when the
aqueous phase is drained from the bottom of the latex tank. The creaming of
NRL may be more effective in reducing smaller latex proteins than the
centrifugation process. This may be due, in part, to the addition to NRL of
colloidal creaming agents that may release some of the proteins that are bound
to rubber in the serum phase, thus further reducing the overall total protein
levels in the concentrate.12

1.8.2 Chemical Processes Used for Deproteinisation

The proteins are efficiently removed from NR in latex stage by using

proteolytic enzyme, surfactant and denaturing agents like urea, guanidine
hydrochloride etc. 10-13, 204-214

The use of proteolytic enzymes to digest NRL proteins has been known
for many years and found broad application in rubber industry.12 Proteases are a
form of hydrolytic enzyme that cleaves peptide bonds and are available
commercially in large supply. Typically these commercial enzymes are
produced from the fermentation of select nonpathogenic strains of bacteria.

49 
Proteolytic enzymes are used in many applications such as in the manufacture of
leather, in food processing including meat tenderizing, and in the manufacture of
cheese, beer, and baked goods. The use of proteases in washing detergents for
home use is fairly common. However, it is only recently that the use of these
enzymes has been shown to reduce allergenic proteins in medical gloves. These
enzymes break up the proteins into smaller pieces, which facilitate their
removal. Concentrated enzyme powders or solutions should be handled carefully
to avoid inhalation of aerosols, as they are potential allergens. Care must be
taken to remove residual proteolytic enzymes, which may also give rise to an
allergic response.106 Moreover, a long incubation time is needed for enzymatic
deproteinisation.

Stabilized liquid Papain obtained from papaya plant (Carica papaya)

can be used for deproteinisation of NRL in a single centrifuging process. This
low protein latex is used for the production of surgical gloves with low levels of
EP content.211

The use of nonionic surfactant is a comparatively better method for

deproteinisation and it will not affect the mechanical properties to a greater
extent. Polyethylene glycol (PEG) is an important non-ionic surfactant used for
the purpose. EP content of NRL was found to decrease with PEG treatment and
reduction increased with increase in the molecular weight of PEG. With PEG
treatment there is 35% reduction in the EP content without any compromise on
the mechanical properties of the latex; however, thermal stability of low-protein
latex was found to be reduced. 106

Tanaka and coworkers have effectively eliminated proteins from NRL

employing a proteolytic enzyme/ surfactant combination. The former breaks
down the proteins linkages selectively and the latter washes out resulting
oligopeptides. Results of nitrogen contents and FTIR of DPNR in the form of
dried film indicated the presence of remaining proteins bound to the DPNR
particles.103

50 
 The enzyme treatment is very effective in reducing antigenic proteins in
NRL. While this technology adds marginally to the production cost of standard
grades of NRL, it is still quite cost-effective when compared with postwashing
NRL products or the use of synthetic latex. Moreover, enzyme-treated NRL
maintains the excellent physical properties and performance of NRL.

The enzyme deproteinization was found to be less efficient when the

rubber particles had been previously irradiated. This might be due to the change
of proteins structure when subjected to γ-ray which resulted in the decrease of
enzyme activity.The evidences obtained from the morphology study of DPNR
latex particles using TEM support this. Here also phase transfer/bulk
polymerization/TEM technique was used for morphology study. The enzyme
alcalase/SDS system was used for deproteinisation. Two types of crosslinked
DPNR latex particles, i.e., γ-radiation vulcanized-deproteinized NR (RV-
DPNR), obtained from enzymatic deproteinization of the γ-radiation vulcanized
natural rubber (RVNR) latex, and deproteinized-γ-radiation vulcanized NR (DP-
RVNR), prepared by irradiation of the DPNR latex with γ-ray, are titrated with
an aqueous solution of cationic surfactant (BHAC) in the presence of styrene. At
the critical transfer concentration (CTC), a hydrophobic layer around the latex
particles forms and the rubber particles transfer into the styrene monomer. The
styrene containing transferred rubber particles is then polymerized in bulk and
the rubber particles embedding in polystyrene (PS) matrix can be sectioned for
the TEM study. By using this method, the air, freeze or chemical drying step of
rubber latex normally required before the embedding step for specimen
preparation is omitted and, hence, the disturbance of actual DPNR particle
structure is minimized.103

The CTC values of the deproteinized latices, i.e., RV-DPNR and DP-
RVNR were approximately twice the value of RVNR latex. This could be due to
an increase in the amount of negative charges on the surface of the DPNR
particles resulted from the added anionic surfactant (SDS) during the
deproteinization process. Consequently, the high quantity of the added cationic

51 
surfactant (BHAC) for neutralization of the rubber particles was required.
Although, the CTC values of both deproteinized latices were similar, it was
observed that the CTC of RV-DPNR latex was slightly higher than that of DP-
RVNR. Therefore, it was reasonable to assume that the phase transfer technique
could be employed to indicate the presence of negative charges, partly derived
from residual proteins, on the surface of DPNR latices. Deproteinization of the
latex before irradiation (DP-RVNR) removed a large proportion of the proteins
and therefore the membrane might be partly destroyed during deproteinization.
The degree of crosslinking of γ-radiation vulcanized NRL was found to decrease
when the proteins had been previously removed by using proteolytic enzyme.103

The nitrogen content of both deproteinized NR lattices (RV-DPNR and

DP-RVNR) was lower than that of concentrated NRL because some of proteins
in the former latices were eliminated by using the enzyme alcalase/SDS system.
This deproteinization technique was very effective in removal of more than half
of the original proteins. It was reported that the nitrogen content of rubber was
reduced from 0.3% to 0.01% by using this technique. The proteins bound to NR
particles were not completely removed. It is of interest to note that the nitrogen
content of the NRL which was vulcanized before deproteinization; RV-DPNR,
were greater than those of DP-RVNR.103

DPNR latex contains very low nonrubbers, especially protein (<0.02

wt% nitrogen content). The faster rate of flattening of DPNR films observed in
AFM study is attributed to the very low non-rubber content of these films, which
poses minimal hindrance to deformation of the articles. The loss of naturally
occurring antioxidants during deproteinization reduces the oxidative resistance
of the DPNR latex films. 14

The treatment of latex with urea and a polar organic solvent in the
presence of surfactant also used to produce protein free NRL. Acetone and
anionic surfactant were found to be effective. The combination of urea and
acetone in the presence of an anionic surfactant such as SDS is found to be
effective for the removal of proteins. Urea is well-known to change only

52 
conformation of the proteins but not cleave any chemical linkages, the removal
of almost all proteins from NRL with urea may suggest that most proteins
present in NR are attached just on the surface of the particles with physical
interaction.219,220 Acetone was the most effective solvent for the removal of the
proteins compared with ethanol and 2-propanol i.e., the total nitrogen content
decreased dramatically from 0.053-0.026 w/w% when 2.5 w/w% of acetone is
added into the latex. This may be explained to be due to the effect of acetone on
the precipitation of the proteins in the aqueous media.13

Figure 1.23: A schematic representation of the proposed mechanism by (a)

enzymatic treatment and (b) surfactant washing or physical treatment.

Recently, it was reported that the addition of calcium chloride solution

and sodium dodecyl sulphate into concentrated NRL effectively removes the
proteins from the NRL. The CaCl2 was obtained indirectly from egg shells. The
pyrolysis of egg shells from chickens, ducks and birds at 9000C for 2 hours
transforms the crystal structure of CaCO3 into CaO with a high purity, creates a

53 
small and uniform particle size, a suitable specific surface area and an average
pore diameter that is suitable for reacting with hydrochloric acid to obtain
CaCl2.206

1.9 Protein Removal by Product Treatment

Certain allergic reactions are caused by proteins leached from the

surface of latex products. Recently there have been reports that NRL gloves and
other surgical aids can cause hyper sensitivity reactions. Gloves made from NRL
contain mainly proteins tightly bound to the rubber particles, having molecular
weight of 14 and 24 kDa and the serum derived proteins of molecular weights
14, 24, 29, 36, 45 and 100 kDa. Even after various processing operations during
the manufacture, these proteins are found to remain with the glove. The proteins
strongly adhering to the rubber particles may not get removed easily. The serum
proteins give rise to the bulk of EP.201

1.9.1 Leaching of Gloves

Leaching is the process of removal of hydrophilic materials from the

latex dipped products by washing them in water.14 The removal of excess water
soluble non-rubbers such as proteins, Ca(NO3)2 and other added compounding
ingredients results in the improvement of physical properties such as tensile
strength, film clarity, prevention of surface blooms and reduction in water
absorption and electrical conductivity of latex dipped products. The
effectiveness of the leaching process is critical in the determination of the
overall quality of gloves produced. 12, 200,201

There are two types of leaching processes: wet gel leaching and dry film
leaching. The wet gel leaching involves the washing of the wet gel i.e., gelled
deposit on former, prior to drying and vulcanization. It is usually carried out
online. Dry film leaching consists of washing the dried vulcanized latex product
after removal from the former and is an off line process. When complete
removal of hydrophilic material is required dry film leaching for an extended
period of 16-48 hours depending on the type of product is made. A substantial

54 
amount of water soluble protein is generated upon drying and vulcanization of
dipped products and those proteins are drawn towards the surface away from the
former during this stage giving rise to asymmetry of EP distribution. Any form
of leaching or washing including the slurry dip after drying is therefore expected
for further removal of the EP.

The most efficient way of reducing water-soluble components in NRL

gloves is to perform both wet-gel and dry-film leaching. In either leaching
process, it is essential to maintain the cleanliness of the leach water. This is
usually accomplished by adding and removing some of the leach water
continuously (water turnover of at least 1–2 gal per minute). In addition to water
turnover, effective leaching is improved when the ratio of leach water volume to
total weight of rubber gloves increases. Poor water turnover and/or low volume
of unclean leach water can increase the amount of EP in gloves produced. Hot
12
and cold water leaching is now used extensively within the dipping industry.

The efficiency of leaching may be determined by several parameters.

These include the leaching time, the leach water temperature, and the rate of
leach water turnover.12 Although water leaching is an effective means of
reducing the EP content of gloves, the results can vary widely depending on how
the latex was compounded. The influence of glove thickness and the processing
conditions have been studied by researchers. Their findings indicate the
following:

• There is a need for the protein to migrate to the glove surface to facilitate
extraction.

• The thinner the glove, the more effective is protein removal.

• Gloves produced from latex with lower rubber content (40%) had a higher
level of EPs than gloves generated from latex with higher rubber content (60%).

For NRL gloves, wet gel leaching, i.e. leaching before curing the rubber,
was found to be less effective than dry film leaching. This was thought to be due

55 
to the protein having insufficient time to migrate to the film surface during the
manufacturing process. Wet gel leaching is important for removing salts,
peptides, soaps, and surfactants from the rubber so that a continuous rubber film
with good barrier properties is formed, but it is not effective in leaching out
larger proteins that are sequestered within the hydrated coagulated film. The
effect of brief wet gel leaching on EPs is strongly influenced by the thickness of
the latex film; the effect could be either positive or negative depending on the
film thickness.200

Irrespective of film thickness or latex DRC dry film leaching was

found to be far more effective than wet gel leaching for the removal of soluble
proteins. Only proteins that had migrated to the surface of the film could be
extracted with water rapidly. Migration of soluble proteins to the surface had not
yet taken place to an appreciable extent when the latex film was in the wet-gel
state. When the wet-gel leached film was completely dried by prolonged heating
after the leaching step, more proteins migrated and appeared at the surface from
where they are easily extractable. To remove soluble proteins efficiently,
therefore the wet–gel leach should be supplemented with a dry film leach since
most of the proteins removed are already at the film surface. 200

The migration of soluble proteins to the surface of the latex film as it

dries has important implications in the manufacture of dipped latex products. As
most of the soluble proteins are concentrated on the surface of the film away
from the shaping former, a large proportion of the EPs can be extracted from the
product even by washing only one surface of the film on-line (while the film is
still on the shaping former). Although the EPs from the surface in contact with
the shaping former are left untreated by this approach, the amount of proteins
extractable from this surface is very low relatively. Other treatments to reduce
EPs (chlorination, dipping with a non-latex coating etc.) can similarly be carried
out on-line with one film surface receiving the treatment. The results from an
on-line treatment of the latex film might not be as effective in reducing EPs
when compared with a thorough off-line operation, but the advantage of the

56 
latter should be gauged by the benefit gained in the context of the allergy
response. Once surface proteins have been removed by dry-film leaching,
further drying of the washed film before storage or packing does not cause more
proteins to migrate to the surface. Indeed, this drying step appears to lock in
whatever residual soluble proteins that still remained. 200

The ammonia solution, sodium lauryl sulphate (SLS) solution and

water-methanol mixture are reported to be effective in removing proteins from
rubber products.201 KOH solution and acid can also be used for the leaching of
NRL films. The crosslink density and EP content of the films reduced with
increasing pH of the KOH solution.221,222

The better EP removal during the treatment of glove samples with

ammonia solution could be attributed to the hydrolysis of proteins into
fragments which are removed during leaching. SLS is used for the solubilisation
of major proteins in various membranes. Proteins can be denatured to individual
polypeptides by treatment with this detergent by breaking down the S-S bond to
S-H bonds. SLS gets attached to the polypeptides and makes them more soluble.
The better leaching effect of SLS solution may be due to the interaction of the
SLS micelles with the rubber particle proteins in the latex glove to form a
soluble protein-lipid-detergent complex. Thus the rubber particle proteins will
also be leached out during the treatment. Methanol being an organic solvent also
has some solubilizing effect on the proteins, though not as effective as SLS or
ammonia.201

The use of ultrasonics in the leaching system can accelerate the removal
of latex protein over leaching on its own. The effect seems to be more
pronounced in pre-vulcanised films than in post-vulcanised films and there is
apparently no detrimental effect on tensile properties.

57 
1.9.2 Post Washing and Chlorination of Gloves

The washing and surface treatment of NRL gloves with chlorine ions is
an effective means of reducing the EP content on the glove surface. Chlorination
leads to significant changes on the surface structure. Chlorination performed in a
low-pH aqueous leach causes the breaking of bonds in the rubber polymer and a
hardening of the film surface. As a result of this surface modification, the rubber
film becomes more slippery and the coefficient of friction is much reduced.
Although this process is commonly used to improve the donnability of gloves, it
can result in decreased grip on the outside of the glove for the wearer. Moreover,
the chlorination process can be difficult to control, and result in small fissures in
the rubber film that can compromise shelf-life and barrier integrity of the glove.
In comparison, extensive postwashing in water alone can be almost as effective
as chlorination, but without the adverse side effects of chlorine on film physical
properties.12

Various reactions are possible during chlorination. In aqueous solution,

chlorine released from sodium hypochlorite by conc.HCl reacts with NR via
ionic mechanism to form carbonium ion which crosslinks with each other and
undergoes cyclisation. Thus NR surface can act as a barrier for migration of
proteins. Denaturation of proteins may also be possible by chlorination which
makes them insoluble. The after treatments, neutralization with ammonia
solution and subsequent washing, will also enhance the removal of EP.201 There
could be crack formation on the surface of the gloves at higher doages or longer
durations of chlorination. This is reflected in the physical properties. Tensile
strength and ageing resistance are reduced in the case of highly chlorinated
samples.12

The use of fumed silica, as little as 1-2 pphr may significantly reduce EP
from latex gloves without adversely affecting the dipping process.61 Steam
autoclaving can also be used for protein reduction of latex gloves but it will
affect physical properties unless precautionary measures are taken at the
compounding stage.106

58 
1.10 Importance of Low Temperature Vulcanization

Vulcanisation temperature is very important in determining the

quality of the rubber products. Optimum properties are obtained when curing is
done at the lowest possible temperature. Low temperature vulcanisation results
in products of good quality and appearance. The modulus developed decreases
as the vulcanization temperature is increased. High temperature vulcanization
has the following disadvantages (1) high energy consumption (2) leads to the
degradation of rubber (3) less safety (4) high insulation costs (5) less flexibility
in designing the compound for each component at high temperature (6)
inconvenience in the curing room (7) chances of over vulcanization.226-235

Room temperature prevulcanisation of NRL has the following

advantages.

(1) It does not affect the colloidal stability of the latex. (2) Vulcanisation is the
most energy requiring step in latex technology. If it can be done at room
temperature, we can save a large amount of energy. Energy saving decreases
pollution and fuel consumption, thus enhancing the environment and of course
saving money. (3) It need less sophisticated equipments and thus simplify the
process. (4) We can use less thermal stable reinforcements and additives. (5) We
can eliminate the chance of premature vulcanization and scorching.

1.11 Objective of the Present Work

The primary objective of the present work is to develop a novel

accelerator system for the prevulcanisation of NRL at temperature lower than
that employed conventionally. At present, sulphur prevulcanisation of NRL is
done industrially by heating the compounded latex at 600C for 2-3 hours. This
will affect the colloidal stability of the latex and also the physical properties of
the films dried down from the latex. Lowering the prevulcanisation temperature
has a great influence on improving the quality of the dipped rubber products,
since rubber undergoes lesser degradation at lower temperature.

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 The nature of accelerator used for crosslinking is an important factor
affecting the temperature of sulphur prevulcanisation. Xanthates and
dithiocarbamates are two important ultra fast accelerators used in rubber
industry. In latex technology, the use of mixed accelerator systems for
prevulcanisation has received much attention since such systems usually exhibit
synergism. In this study, different xanthates in combination with zinc diethyl
dithiocarbamate (ZDC) were used for the low temperature prevulcanisation of
NRL. Xanthates in the form of sodium, potassium, and zinc salts were used for
the purpose. Prevulcanisation of NRL can be effectively carried out at room
temperature and at 400C using xanthate/ZDC accelerator combination without
affecting the colloidal stability of the latex. Due to the world wide spread of
epidemic diseases such as AIDS, hepatitis B and influenza (H1N1), it becomes
increasingly urgent to develop high performance NRL gloves. The present
accelerator system can be used for the production of examination gloves and toy
balloons with improved properties at low temperature.2

The study can be outlined under the following heads

(1) Preparation of following xanthates

(i) Zinc butyl xanthate, Zn(bxt)2
(ii) Zinc isopropyl xanthate, Zn(ipxt)2
(iii) Sodium butyl xanthate, Nabxt
(iv) Potassium butyl xanthate, Kbxt
(v) Potassium isoamyl xanthate, Kiaxt
(2) Characterisation of xanthate using different techniques
(i) FTIR spectroscopy
1
(ii) H-NMR spectroscopy
(iii) TG/DTA

(3) Detailed study of zinc butyl xanthate

™ Optimization of preparation method
™ Cytotoxicity study

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(4) Low temperature prevulcanisation of NRL using Zn(bxt)2/ZDC
accelerator system
¾ Optimization of accelerator concentration
¾ Optimization of prevulcanisation time
¾ Effect of storage on colloidal properties of prevulcanised latex
¾ Thermal ageing study
¾ Comparison with conventional high temperature
prevulcanisation system
(5) Low temperature prevulcanisation of NRL using Nabxt/ZDC and
Kbxt/ZDC accelerator system
• Optimization of prevulcanisation time
• Comparison of the accelerating properties of Nabxt and Kbxt
• Thermal ageing study
• Surface morphology study using AFM
(6) Low temperature prevulcanisation of NRL using Kiaxt/ZDC
accelerator system
™ Optimization of prevulcanisation time
™ Thermal ageing study
(7) Studies on the effective removal of extractable proteins from
prevulcanised NRL film by leaching procedure
¾ Use of different media for effective protein removal
¾ Effect of protein removal on mechanical properties
¾ Comparison with postvulcanised NRL film
(8) Production of examination gloves and toy balloons at low temperature
™ Optimization of cure time
™ Evaluation of mechanical properties

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