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RUBBER

PRE-REQUISITE

1. Show ELASTicity

2. Long chain molecule -polyMER

ELASTO-MERS
Rubbers and elastomers are synonym
 Highly amorphous
 Highly random orientation
 High elongation
GENERAL PROPERTIES OF RUBBERS

1. Flexible & stable three dimensional structure


2. Can withstand large force without deformation.
3. e.g can be stretched repeatedly to at least twice its
original length and upon immediate release of stress will
return to its original length with force
4. Do not creep under load
5. Must be amorphous
6. Tg must be below operating temperature
7. Must have low secondary forces between molecules
8. A moderate degree of cross linking must exist
9. Young modulus must be less then 1 GPa
 Tg
 There is a certain temperature (different for each polymer)
called the glass transition temperature, or Tg for short.
When the polymer is cooled below this temperature, it
becomes hard and brittle, like glass.
 Some polymers are used above their glass transition
temperatures, and some are used below. Hard plastics like
polystyrene and poly(methyl methacrylate), are used below
their glass transition temperatures; that is in their glassy
state. Their Tg's are well above room temperature, both at
around 100 oC.
 Rubber elastomers like polyisoprene and polyisobutylene,
are used above their Tg's, that is, in the rubbery state,
where they are soft and flexible.
Materials Young modulus GPa
Mild Steel 210
Copper 120
Bone 18
Plastics 2
Rubber 0.02
CLASSIFICATION

 A common classification of different types of rubber is:


 General purpose elastomers
 Special purpose elastomers
 Speciality elastomers
General Purpose Elastomers

 Natural Rubber (NR)


 Poly Isoprene Rubber (IR)
 Styrene-Butadiene Rubber (SBR)
 Butadiene Rubber (BR)
 These types have good physical properties, good process
ability and compatibility, are generally economical and are
typical polymers used in tyres and mechanical rubber
goods with demand for good abrasion resistance and
tensile properties. General purpose types constitute the
largest volume of polymer used.
Special Purpose Elastomers

 Ethylene-propylene rubber (EPM and EPDM)


 Butyl rubber (BR)
 Chloroprene rubber (CR)
 Acrylonitrile-butadiene rubber or Nitrile rubber (NBR)
 Hypalon
 Epichlorohydrin
 They have all unique properties which cannot be matched
by the general purpose types and are very important for
manufacturing of industrial and automotive rubber
products.
Speciality Elastomers
 There are a great number of polymers with very special
properties, in many cases of great importance for the
automotive-, aircraft-, space- and offshore industries. Some
of these polymers are:
 Chloro-sulfonated Polyethylene (CSM)
 Acrylic Rubber (ACM)
 Silicone Rubber (PMQ/PV/MQ/VMQ)
 Flour-Silicone Rubber (FPQ)
 Fluor Elastomers (FPM/FFKM/FEPM)
 Urethane Rubber (AU/EU)
 Epichloro hydrine Rubber (CO/ECO/GECO)
• The commercial source of natural rubber latex is
the Para rubber tree (Hevea brasiliensis).

• Other plants containing latex include:

 Gutta-percha (Palaquium gutta)


 Rubber fig (Ficus elastica)

 Panama rubber tree (Castilla elastica)

 Spurges (Euphorbia spp.)

 Common dandelion (Taraxacum officinale)

 Russian dandelion (Taraxacum kok-saghyz)


• Natural rubber is a naturally occurring polymer obtained from the
latex of rubber trees.
• Natural rubber (NR) is also known ascis-1,4-poly(isoprene).
• Natural rubber is found in the latex that comes from the rubber trees.
• It is collected in a cup mounted on each tree, by slashing the bark to
reach the latex vessels.
• The liquid is 30-40% rubber.
• The physical and chemical properties of the rubber
are influenced by the presence of the non-rubber
substances.

• NR is a natural polymeric substance having high


molecular weight, possessing visco-elastic
properties.

• Natural rubber is cis-1,4-polyisoprene, i.e. a


diene, because of this, it shows all the reactions
of an unsaturated compound.

• It gives addition compounds with hydrogen


chloride, halogens, ozone and several other
reactants that combine with olefins.
Physical properties of NR.
Chemical resistance of NR
Mechanical properties of NR
• An interesting reaction of NR is its combination
with sulphur, called ‘vulcanization’.
• This reaction converts the raw rubber into an
elastic material.
• Vulcanized rubber possesses high tensile strength,
hardness and abrasion resistance.
• Because of the unique combination of these
properties, NR finds application in the
manufacture of various types of products.
PRESERVATION OF FRESH LATEX
• Fresh Natural Rubber latex coagulates by standing on the air, and
micro-organism can attack the non-rubber components of
latex.From these reasons it must be stabilized.

• The most often used item for this stabilization is ammonia (HA latex –
maximum 0.7 % NH3). It is long term preservation

• Its combinations (LA latex – 0.2 % NH3) with secondary stabilizers,


such as dithiocarbamates, combination of tetramethylthiuram
disulfide and ZnO, lauric or boric acid. These are added to latex only in
very small amounts, normally 0.01 – 0.05 %. It is short term
preservation suitable for certain applications such as latex foam 
requires low ammonia content in order for to gel properly.
PRODUCING LIQUID CONCENTRATE

Some rubber products (e.g. foam rubber, gloves, glues) are produced directly
from latex.
The latex is modified for these reasons to have higher dry rubber content
(DRC) values (minimum 60 – 65 % of rubber).

It is performed by means of its concentrations.

There are few methods that can be used to concentrate natural rubber latex:
Concentration by creaming
Concentration by centrifugation & sedimentation
Concentration by evaporation
electro-decantation is used.

During these operations also eventual dirtiness and non-rubbery additives


are removed from rubber besides increase of the dry rubber content in latex.
PRODUCING DRY RUBBER (Coagulation)
• By adding an acid such as formic acid (HCOOH)
• Coagulation takes about 12 hours.
• The coagulum, now soft solid slabs,
• Squeezed through a series of rolls which drive out most of the water
and reduce thickness to about 3 mm (1/8 in)
• The sheets are then draped over wooden frames and dried in
smokehouses. Several days are normally required to complete the
drying process
• The resulting rubber, now in a form called ribbed smoked sheet, is
folded into large bales for shipment to the processor. It has a
characteristic dark brown color.
• In some cases, the sheets are dried in hot air rather than
smokehouses, and the term air-dried sheet is used; this is considered
to be a better grade of rubber
• A still better grade, called pale crepe rubber, involves two coagulation
steps, followed by warm air drying. Its color is light tan
COMPOUNDING

Rubber, at this stage, is


• soft,
• sticky
• thermoplastic.
• It has low tensile strength,
• prone to bacterial brake down and
• low elasticity.

Compounding is the science of selecting and


combining elastomers and additives to obtain
physical and chemical properties for a finished
product.
MAJOR OBJECTIVES OF COMPOUNDING

• Hardness
• Stress-Strain properties (Tensile strength)
• Abrasion resistance
• Set properties
• Resistance to cut growth, fatigue, flex cracking
• Resistance to degradation by
Heat, Oxygen, Ozone
Flame
Liquids
Light
• Miscellaneous property requirements
Low temperature flexibility
Electrical properties
Permeability
Contact with food stuff and drugs
Bonding to metal & textiles
Swelling
Other specific requirements
The chemicals used in latex compounding can be divided
into three general classifications:

Surface active agents (surfactants)


Liquid phase modifier
Elastomer or rubber phase modifier
CLASSIFICATION OF COMPOUNDING INGREDIENTS
1. Elastomers
2. Vulcanizing Agents (curing or crosslinking agents)
3. Accelerators
4. Activators and Retarders
5. Antidegradants (Anti-oxidants, Antiozonants, Protective
waxes )
6. Processing aids (Peptisers, Lubricants, Release Agents)
7. Fillers (carbon black, non-black materials)
8. Plasticizers, Softeners and Tackifiers
9. Colour pigments
10. Special Purpose Materials (Blowing Agents, Deodorants,
etc.)
VULCANIZATION (CURING, CROSSLINKING)
 Vulcanization is the creation of cross-links between rubber
macromolecules at which three dimensional network of rubber matrix
is formed.
 Physical bonds like hydrogen bond, polar or dispersed powers between
individual macromolecules are also the part of vulcanizate network.
 For the formation of chemical cross-links between rubber
macromolecules different chemical – vulcanization agents (sulfur,
peroxides, metal oxides, resins, quinones and others) are most often
used, which are in vulcanization process able to react with suitable
functional rubber groups and to create cross-links between them.
 Vulcanization with sulfur results in cross-linking of the hydrocarbon
chains by disulfide bonds. When the polymer is stretched, the chains
no longer can slide past each other, and tearing does not occur.
 Curing can be caused also by the different types radiation. These
radiations generate rubber macromolecules reactive forms most often
radicals. They are then cross-linked with each other. Also microwave
energy or ultrasound can cause curing creation.
VULCANIZATION PROCESS

The vulcanization or curing process occurs in three stages and each stage
is of importance and affects the service life of the finished product:
(1) Induction or flow time (Scorch resistance)
(2) Crosslinking or rate of cure
(3) Optimum state of cure or overcure

Scorch resistance is the time elapsed before vulcanization starts. It is


necessary to have suitable scorch resistance so that there is enough time
for mixing, storing and moulding of the rubber mixture into the desired
shape and size.

The cross-links are even not created or only a little. Its length depends on
the type of vulcanization system and vulcanization temperature. In the
case of sulfur vulcanization it is affected by present accelerators,
eventually vulcanization retarders or pre-cure inhibitors.
2. Crosslinking or rate of cure. The second stage is
the main vulcanization stage which is fast curing of
rubber macromolecules and the formation of ones'
own vulcanizate. That is why the vulcanization rate
can be considered as the rate of this stage.. Once
vulcanization begins, it should be completed as fast
as possible in order to have practical batch cycle.
Optimal vulcanization time is the difference between
maximum and minimum torsion moment
3. The third stage of the curing or vulcanization process is a point
at which all technological properties of the rubber compound
are forming and is necessary to cure the rubber compound to
its “optimum state of cure” (maximum stress value), but not
past that point—“overcure.” It must stop at the right time .

Technically, the most important state of cure is the so-called


“optimum state of cure.” This is when the predominant properties
of cured rubber are formed and thus its elastic behavior after
deformation in compression or tension. It is possible to stretch a
rubber compound cured to this “optimum state of cure” ten times
its original length, and after removing the tension, it will return to
its original shape and length. In addition, these cured rubber
compounds are characterized by great toughness under static or
dynamic stresses resulting in abrasion resistance higher than that
of steel.
 A cure that is longer than optimum is an “overcure.”
 In Natural Rubber (NR) compounds, reversion occurs with
overcure and the modulus and tensile strength decrease.
 In many Synthetic Rubber (SR) types, the rubber
compound continues to harden, the modulus rises, and
tensile and elongation fall.
 If overcuring (continued heating) of the rubber occurs, a
stiffening (marching modulus), or softening (reversion), of
the compound can be the result. These effects will reduce
physical and adhesion properties of the rubber compound.
These three stages are most often evaluated on the basis
of vulcanization curves measured on different types of
rheometers.
The number of created cross-links between rubber
macromolecules (characterized by crosslink density) and
their chemical structure depend mainly on the content
and activity of vulcanization agent, temperature and
vulcanization time.

ν is crosslink density, ρ is rubber density, Mc is molecular


weight of rubber segments between two cross-links
 Production of rubber is followed by processing into final
products consists of :

Compounding
Mixing
Shaping
Vulcanizing.

 Processing techniques for natural and synthetic rubbers


are virtually the same, differences being in the
chemicals used to effect vulcanization.
 Rubber is always compounded with additives to satisfy
the given application in terms of properties, cost, and
COMPOUNDING
processability

 Compounding adds chemicals for vulcanization.

 Mainly used reinforcing filler used in NR is carbon


black.

 Other additives include antioxidants , antiozonants


colouring pigments, plasticizers and softening oils,
blowing agents in the production of foamed rubber; and
mold-release compounds
 The additives must be thoroughly mixed with the base
rubber to achieve uniform dispersion of the ingredients.
MIXING
 A two-stage mixing process is usually employed.

 In the first stage, carbon black and other non vulcanizing


additives are combined with the raw rubber.

 After thorough mixing has been accomplished, and time for


cooling has been allowed, the second stage is carried out in
which the vulcanizing agents are added.

 Equipment for mixing includes the Two-roll mill and internal


mixers such as the Banbury mixer
SHAPING
 Shaping processes for rubber products can be divided into
four basic categories:
Extrusion
Calendering
Coating
Molding and Casting

VULCANIZATION

o Vulcanization is a chemical process for converting


natural rubber or related polymers into more durable
materials via the addition of sulphur or other equivalent
curatives or accelerators.
 NR Composites and Nanocomposites based on
Conventional Fillers

 NR Composites and Nanocomposites Reinforced with Carbon


Black
 NR Composites and Nanocomposites Reinforced with Silica
 NR Composites and Nanocomposites Based on Carbon
Nanotubes
 NR Composites and Nanocomposites Based on Graphene

 NR Composites and Nanocomposites Based on Natural


Fillers

 Fibre-Reinforced NR Composites and Nanocomposites


(glass, rayon, aramid, asbestos and cellulose as fibres)
 Starch-Reinforced NR Composites and Nanocomposites
 NR Composites and Nanocomposites Reinforced with
Natural Mineral Fillers
 NR Composites and Nanocomposites Based on Metal
or Metallic Compound Fillers

 Metal nanoparticles and metallic compound powders are


most widely used in polymers to strengthen the polymers,
and improve their thermal stability and gas barrier
properties.
 NR is often reinforced with various kinds of metal

nanoparticles and metallic compound powder.

 NR Composites and Nanocomposites Based on Hybrid


Fillers

 NR composites filled with hybrid fillers possess outstanding


mechanical properties that are not caused by only one filler.
 Glass Fibre/NR Composite

 Glass fibres are the most common of all reinforcing


 synthetic fibres for polymeric matrix composites
(PMCs).

 The major advantages of glass fibres are high tensile


strength, low cost, high chemical resistance and
excellent insulating properties.

 The disadvantages are relatively low tensile modulus


and high density, high hardness,sensitivity to abrasion
during handling which tends to decrease its tensile
strength, relatively low fatigue resistance.

 Fibre-reinforced NR composites are manufactured


by various processes, the most common being
 The mechanical properties of glass fibre/NR
ECHANICAL ROPERTIES OF
composites strongly depend on properties of glass
M fibres. P
GLASS FIBRE/NR COMPOSITES

 It is seen from the table that E-glass fibre has better


tensile properties than A-glass fibre.
 It is expected that E-glass/NR composites will show
better tensile properties than A-glass/NR composites.
 It is often observed that increase in fibre content leads
to an increase in the strength and modulus of a fibre
reinforced polymer matrix composite
 Mechanical properties also depend on fibre
orientation.

 It varies for unidirectional and non-unidirectional


arrangements and for long and short fibres also.

 Strength of glass fibre/NR composites can be


improved by modification of NR and glass fibre.

 Modified NR can also give higher strength and


better adhesion properties.

 Modification of glass fibre helps to improve the


fibre/matrix adhesion.
 The main use of natural rubber is in automobiles.

 Sixty per cent of all rubber consumed is for automobile


tyres and tubes.

 In heavy duty tyres, the major portion of the rubber


used is NR.

 Uses of NR in hoses, footwear, battery boxes, foam


mattresses, balloons, toys etc., are well known.

 NR now finds extensive use in soil stabilization, in


vibration absorption and in road making.
 Non-tyre rubber items include industrial products
(for example, transmission and elevator belts,
hoses and tubes, industrial lining, and bridge
bearings)

 Consumer products (like golf or football balls and


other recreational and sports goods, erasers,
footwear and other apparel)

 Articles for use in the medical and health sector


(notably, catheters and surgical gloves)

 Latex articles (typically, gloves, threads,


adhesives, and moulded foams) could be included
in different categories in terms of end-use.
 http://www.allsealsinc.com/Natural_Rubber-popup.html

 http://www.tutorvista.com/content/chemistry/chemistry-
ii/carbon-compounds/natural-rubber.php

 http://rubberboard.org.in/ManageCultivation.asp?Id=196

 Natural Rubber Materials: Volume 2: Composites


and Nanocomposites edited by Sabu Thomas, Chin
Han Chan, Laly A Pothen, Jithin Joy, Hanna Maria

 Fundamentals of Modern Manufacturing: Materials,


Processes, and system
Mikell P. Groover