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Film Formation in Rubber Gloves

Article · January 2014

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Malaysian Rubber Board
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Nurulhuda Abdullah and Amir Hashim M.Y.

Film Formation in
Rubber Gloves
Rubber medical gloves are a thin layer of rubber shaped
onto a hand-like former, by controlled dipping of the former
into a latex or rubber solution. The formation of latex film
is affected by numerous factors including the type of
latex or rubber polymer, the composition of non rubber
components as well as the particle size and distribution
of rubber particles in the latex or solution. Choosing the
appropriate types and amount of surface active materials
to control the colloidal system and polymer crosslinking
agents helps maximise physical strength, while relatively
smooth films of reasonable strength and elasticity can be
formed. Thus, the colloidal behaviour of latex before film
formation and reactivity of crosslinking agents while in
the latex and during film formation are essential towards
process improvements within the glove manufacturing
industry.
From a colloidal perspective, latex is defined as an
aqueous dispersion of rubber or polymer particles,
commonly in a spherical shape1,2 . The colloidal stability of
latex is produced by a balancing of electrostatic repulsion,
van der Waals attraction and steric attraction or repulsion,
promoting stronger particle-medium attractions as
opposed to the attraction between particles. Stability of
natural rubber latex is retained due to the effect of non
rubber constituents such as proteins and soaps that are
in the serum. While synthetic latex contains charged
functional groups which act as a stabiliser for dispersing
hydrophobic polymers in water, carboxylic, sulphonic
acid groups and tertiary amine groups are among the
common stabilisers used during manufacturing. Latex
stability is a complex characteristic comprising of several
complementary substances and possible competing
mechanisms. In manufacturing of rubber gloves, the
stability of latex is regarded as an imperative and critical
aspect affecting the properties of finished products.
Achieving a precise level of latex colloidal stability is
required, as film formation is difficult with very high
stability and low stability on the other hand, leads to
premature coagulation of the rubber particles. Therefore,
understanding the correct balance between stability
and instability of latex is a necessity in latex technology
as manufacturing of rubber gloves involves a controlled
interruption of the colloidal stability of rubber or polymer
dispersions in latex.
Factors Contributing towards Film Formation
Colloidal Stability
Glove manufacturing processes begin with latex
compounding, prepared by mixing the latex with selective
materials either in the form of a dispersion, solution or
emulsion (sulphur, zinc oxide, accelerator, activator,
surfactant, antioxidant, pigment, filler, etc.). Stability of a
latex system is attributed to the potential energy barrier
present between each latex particle and these added
materials. The latex system intrinsically possesses a
high energy state1 and introduction of chemicals into
the system may interrupt such stability, while inducing
a thermodynamic driving force from rubber particles
to aggregates (Figure 1). Materials in the compounding
formulation should have a sufficient energy barrier to
remain stable during the latex handling stage which
involves pumping, agitation as well as heating and thus,
must be stable enough to resist physical and thermal
impacts during the glove manufacturing stages, while
allowing formation of a coherent, uniform and strong gel
on the former.
Figure 1. Stability of latex colloids.
Latex Vulcanisation and Network Formation
The subsequent process following the introduction
of vulcanising ingredients into latex systems may be

16
MRB Rubber Technology Developments
Dissolution of crosslinking reagents
in latex aqueous phase
Crosslinking reaction during prevulcanisation process
may proceed in two manners:

hypothetically projected in two different manners2,3. It
has been suggested and widely accepted that the process
may take place (i) soon after direct contact between the
reactants and rubber (ii) upon dissolving of vulcanising
ingredients in the aqueous serum of latex, prior to
diffusion and vulcanisation in the rubber particles. The
accelerator and sulphur are to be dissolved in the aqueous
phase of latex before reacting to form active intermediate
species on the surface of the latex particles, which diffuse
and then crosslink the rubber molecules3. Although the
nature of this intriguing active intermediate species is in
dispute, these species are postulated to be more soluble3
than the accelerator in the latex serum.
A deduction of the subsequent process post chemical
migration into rubber phase in latex state based on two
probable means3,4 i.e. the crosslinking process occurs
simultaneously upon the arrival of active species or the
crosslinking process occurs after diffusion of active
species into the rubber phase. These two circumstances
are expected to be highly important for film formation
from vulcanised latex (Figure 2). If the reaction occurs as
soon as the chemicals absorbed onto the rubber surface,
mobility of the rubber chains are reduced, it is difficult for
particles to coalesce, thus a highly coherent film would
not be expected. In contrast, latex particles composed of
homogeneously crosslinked particles might be expected
to coalesce well and form a film possessing optimal
physical properties.
It is reported elsewhere5 that the crosslinking reaction
of sulphur is slow enough to allow for diffusion of the
Dissolution of crosslinking reagents Crosslinking reaction during prevulcanisation process
in latex aqueous phase may proceed in two manners:
a) If crosslinking reaction is faster than
chemicals diffusion
b) If chemicals diffusion is faster than
crosslinking reaction
Figure 2. Schematic mechanism of chemical transport and crosslinking manner during prevulcanisation of latex.
COPYRIGHT © MALAYSIAN RUBBER BOARD
Nurulhuda Abdullah and Amir Hashim M.Y.
vulcanising agent inside the rubber particle. This in
turn promotes the formation of a highly homogeneous6
rubber network with excellent physical properties. On
the other hand, the peroxide vulcanisation process is
rapid, hindering further diffusion of reactants into rubber
molecules. Hence, vulcanisation takes place on the
surface7, creating a core−shell like structure that prevents
additional peroxide from penetrating into the rubber
particles.
The maturation or prevulcanisation stage is the period
during which compounded latex is stored after mixing
before it is released into the production line. During
maturation, crosslinking of rubber molecules takes place
within dispersed rubber particles in the aqueous phase
of latex. It appears that during prevulcanisation,
intraparticle crosslinking takes place 6 and there is no
interaction with other particles, thus prevulcanised latex
should have a similar appearance to that of unvulcanised
latex i.e. retain its original fluidity, essentially having
a similar distribution of latex particle shapes and
sizes3. However, this latex compound has a limited life
span compared to that of an over matured latex which
may result in poor quality of films. Interestingly, the
vulcanisation process of individual rubber particles
during the prevulcanisation stage does not destroy the
stable colloidal characteristic of the latex3. Quantification
of the degree of vulcanisation during maturation of
prevulcanised latex is often determined as a function
of time, by measuring dimensions of the test piece
before and after immersion in solvent3. The degree of
crosslinking can be manipulated by controlling either the
Highly crosslinked shell Latex Particle
Crosslinking reagents
Homogeneously crosslinked
17
Volume 14(1) 2014
Nurulhuda Abdullah and Amir Hashim M.Y.
Porcelain or steel
former
Dipping process
Coagulant
Figure 3. Coagulation process.
reaction temperature, maturation hour or stirrer speed
during storage inside the compounding tank 8.
During wet gel formation, clean formers are initially
dipped into a strong electrolyte solution, usually
comprised of calcium nitrate and calcium carbonate as
coagulants. Solution that adheres to the surface of the
former is completely or partially dried to form a layer
of electrolyte coating on the surface of formers. These
electrolyte-coated formers are then dipped into previously
maturated prevulcanised latex leading to deposition
of wet gel latex on the surface of formers while the
interstices between rubber particles are still filled with
water9. Intrinsically, the process interrupts and destroys
latex colloidal stability, causing latex particles to adhere
to adjacent particles, forming a stable continuous solid
phase on the formers with dispersed water occluded
within the network10. Thickness of the latex gel formed
is found to be verily dependent on the concentration of
calcium ions used and the immersion time.
The process stageFormer surface
at which deposited prevulcanised
latex articles are further cured via heating treatment is
Latex particles
known as post vulcanisation. Mostin manufacturers focus
water (wet gel)
on crosslinking which takes place in the dry film (post
vulcanisation) by manipulating the process parameters
such as temperature and curing time to achieve required
product properties. It is undeniable that drying is a vital
18
coalescence of particles
forming coherent film
MRB Rubber Technology Developments
Former surface
Electrolyte-coated
formers
Partially dried
before entering
compounded latex
dipping tank
phase in processing of latex films, giving the film its firm
structure 9. The process of forming a film from an aqueous
dispersion of rubber or polymer particles involves the
removal of water from the latex dispersion surface and
compaction of latex particles into a close pack array.
Basic steps include (i) loss of water from the wet gel film
by means of evaporation, (ii) particle deformation and (iii)
coalescence of particles forming a coherent film (Figure 4).
Before entering the post vulcanisation state, the
latex article still contains a large amount of water after
forming a solid phase during the wet gel process. As the
water is trapped inside the network, it is not easy to be
removed. Thus, the removal of water in film formation
significantly affects the properties of end products. The
drying process depends on material and heat transfer as
well as a variety of physical and chemical parameters. In
film formation, the drying process is accompanied with
further vulcanisation and both processes are not always
synchronised11.Former surface
Insufficient vulcanising or lengthy drying
may deteriorate performance of the latex film. Control
and balance of theWater evaporationconcerning both drying
relationship
during drying
and vulcanising processes is another key factor in rubber
glove production.
The microstructure of sulphur crosslinked rubber
particles between pre- and post vulcanised latex films
(Figure 5) are clearly in a different modus. Rubber particles
Former surface
Particles deformation
 former
Dipping process
Coagulant
in films of post vulcanised latex are embedded in a mass
of other interlinked rubber particles (Figure 5b) while
the prevulcanised latex films indicate that the structure
contains more interparticle rubber network. During the
prevulcanisation state, crosslinking of rubber occurs
commonly within each rubber particle (intraparticle).
While interparticle crosslinking occurs after the gel layer
formed is cured by drying in the oven (post vulcanisation).
Therefore, complete intraparticle networking of
rubber molecules is expected to form in over matured
prevulcanised latex, inhibiting further interparticle
networking during the film drying process. Poorly
Former surface
Latex particles in
water (wet gel)
coalescence of particles
forming coherent film
Former surface
Figure 4. Schematic diagram of latex film formation.
Figure 5. TEM micrograph image of sulphur (a) prevulcanised film12 (b) post vulcanised film13.
Partially dried
before entering
compounded latex
dipping tank
Nurulhuda Abdullah and Amir Hashim M.Y.
coalesced particles within a latex film would lead to
potentially poor film formation and premature rupture.
In rubber glove manufacturing, it can be concluded that
the quality of films is dependent on an elusive balance
between these two networking behaviours of intra- and
interparticle occurring during the manufacturing process.
Strength and coherence of the final film is associated6
with higher intraparticle crosslink density and secondary
valence forces between the particles, including temporary
chain entanglements in prevulcanised latex. As the
wet gel film undergoes drying and post vulcanisation,
the overall film strength is contributed by the two
Former surface
Water evaporation
during drying
Former surface
Particles deformation
19
Volume 14(1) 2014
Nurulhuda Abdullah and Amir Hashim M.Y.
aforementioned parameters together with interparticle
networking. Concurrently, prevulcanisation offers a
means of designing the correct amount of crosslinking
required in the final vulcanised film, in order to possess
higher overall strength.
Leaching of Rubber Gloves
As observed by previous researchers, the leaching
process improves latex film properties. Leaching or
washing the rubber gloves during the manufacturing
process, eliminates the extractable protein and other
non rubber components trapped inside the film, while
enhancing physical properties of the film13,14. This
suggests that non rubber substances may be scattered in
the interfaces between particles, obstructing interrelation
of neighbouring particles in the latex film, presenting
physical barriers13. The improvement in physical strength,
particularly strength and modulus could be attributed to
removal of these barriers during leaching. Thus, leaching
enables further interparticle networking of rubber
molecules, providing unrestricted volume14.
SUMMARY
In rubber glove manufacturing, fundamental factors
ensure the consistent formation of films towards acquiring
quality rubber gloves and meeting consumer application
requirements. Controlled colloidal stability, compounding
ingredients, leaching protocols and vulcanisation
conditions significantly affect the overall properties of the
final product, either physically or chemically. Therefore,
comprehensive understanding of the entire process is
essential in order to correlate network structure with the
physical properties of rubber.
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MRB Rubber Technology Developments
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