Rubbers 1

 Rubber is an elastic substance obtained from the exudations of

certain tropical plants (natural rubber) or derived from petroleum
and natural gas (synthetic rubber).
 Because of its elasticity, resilience, and toughness, rubber is the basic
constituent of the tires used in automotive vehicles, aircraft, and
bicycles.
 More than half of all rubber produced goes into automobile tires; the
rest goes into mechanical parts such as mountings, gaskets, belts,
and hoses, as well as consumer products such as shoes, clothing,
furniture, and toys.

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 Types of rubbers:
 There are many different kinds of rubber, but they all fall into two
broad types: (1) natural rubber (latex—grown from plants) and (2)
synthetic rubber (made artificially in a chemical plant or
laboratory).
 Commercially, the most important synthetic rubbers are styrene
butadiene (SBR), butadiene rubber (BR), chloroprene rubber
(CR)…etc
 Although natural rubber and synthetic rubbers are similar in some
ways, they're made by entirely different processes and chemically
quite different.
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1. Natural rubber:
 Natural rubber is made from a runny, milky white liquid called latex that oozes from
certain plants when cutting into them.
 Although there are something like 200 plants in the world that produce latex, over
99 percent of the world's natural rubber is made from the latex that comes from a
tree species called Hevea brasiliensis, widely known as the rubber tree.
 This latex is about one third water and one third rubber particles held in a form
known as a colloidal suspension.
 Natural rubber is a polymer of isoprene (also known as 2-methylbuta-1,3-diene)
with the chemical formula (C5H8)n.
 To put it more simply, it's made of many thousands of basic C5H8 units (the
monomer of isoprene) loosely joined to make long, tangled chains. These chains of
molecules can be pulled apart and untangled fairly easily, but they spring straight
back together if you release them—and that's what makes rubber elastic. 5
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2. Synthetic rubbers:
 Synthetic rubbers are made in chemical plants using petrochemicals as their
starting point.
 One of the first (and still one of the best known) is neoprene (the brand name for
polychloroprene), made by reacting together acetylene and hydrochloric acid.
 Emulsion styrene-butadiene rubber (E-SBR), another synthetic rubber, is widely
used for making vehicle tires.
 Note:
 For the rest of this chapter, we'll concentrate mostly on natural rubber.
 See MMTH p. 185 about NR and Synthetic rubber mechanical properties.

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 Natural rubber processing:
 Fresh field latex and the field coagula are not suitable for storage and
are open to bacterial attack and degradation. Therefore, these two
forms of the crop need processing into a form which is suitable for
long-term storage and marketing.
 These primary processing operations are carried out in the
plantation itself.
 The various marketable forms of raw natural rubber include (1)
preserved field latex and concentrated latex, (2) ribbed smoked
sheet (RSS) and air dried sheet (ADS), (3) block rubber or TSR, (4)
PLC and estate brown crepe (EBC) and (5) other low grade crepes
made from field coagulum. 9
1. Preservation and concentration of latex:
 A number of rubber products such as gloves, rubber bands, balloons,
foam mattresses, elastic threads, adhesives, etc., are made directly
from latex.
 About 10% of the global production of NR is processed as preserved
and concentrated latex.
 Preservation of latex is aimed at preventing bacterial activity and
enhancing its stability. This is achieved using preservatives such as
ammonia. For effective preservation of latex, ammonia is used at a
concentration of 0.7 to 1.0% by weight.
 Natural rubber latex concentrate is marketed to strict technical
specifications. The current ASTM D 1076 - 02 specifications for latex
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concentrates are reproduced in Table 1.
See ASTM D 1076 – 02

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Concentrated Latex
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2. Ribbed smoked sheet (RSS):
 This is the oldest method of processing of NR latex and is still widely
adopted by rubber growers owing to its simplicity, low cost and
viability even when the quantity of latex is small.
 Drying of sheets is ideally carried out in smoke houses or hot air
chambers and the dried sheets thus obtained are termed ribbed
smoked sheet or air dried sheet, respectively.
 There are six grades of sheet rubber which are designated as RSS 1X
and RSS 1 to RSS 5.
 These are graded according to the Green Book. RSS 1X is the best
and RSS 5 the worst.
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 Video: https://www.youtube.com/watch?v=-
eeQ826RJ08
Video:
https://www.youtube.com/watch?v=GDdUi24g20o

Ribbed Smoked Sheets (RSS)

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3. Technically specified or block rubber (TSR):
 Originally, most of the solid rubber used was in the form of ribbed smoked sheets
or RSS rubber. By the early 1970s, however, TSR or rubber was introduced into the
market.
 TSR which is also known as block rubber is graded according to precise technical
parameters such as dirt content, ash content, nitrogen content, volatile matter and
properties of the rubber such as its Wallace Plasticity (PO) and its Plasticity
Retention Index (PRI).
 The TSR grades most widely used by the tyre and rubber industry are the TSR-20
and TSR-10 grades from Indonesia, Thailand and Malaysia which are known as
SIR20, STR20 and SMR20 respectively.
 Block rubber can be produced both from field latex as well as from latex
coagulum or what is commonly known as cup lump. Tree lace and unsmoked
sheets can also be used in producing block rubber.
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Technically specified or block rubber (TSR)

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4. Pale latex crepe (PLC) and sole crepe:
 NR latex contains certain yellow carotenoid pigments. PLC is a light coloured
premium grade of NR from which the yellow pigments have been removed or
bleached. After removal by bleaching, the latex is then coagulated and dried, after
which we get the pale crepe in block or sheet form.
 These pale crepes are the superior grades among the other crepe rubber because
of its high purity and light color. Therefore they are used for pharmaceutical and
adhesive applications. Most importantly, it is preferred in products for which a light
colour is important.
 Pale crepe is also graded visually according to the Green Book. The main criterion
is colour. The grades are PLC 1X, PLC 1, PLC 2 and PLC 3. PLC 1X is the best and
PLC 3 is the worst. Thick and thin versions of these grades are available.
 Sole crepes are used by the footwear industry and are made by laminating plies of
pale crepe to the required thickness and consolidating them by hand rolling and
finally through even speed rollers.
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Pale latex crepe (PLC)

Sole crepes 19
5. Field coagulum crepe:
 Among the various field coagulum materials, cup lump (latex gets dried up in the
cup) and tree lace (latex get dried up on the tapping channel on the tree) are
collected every tapping day and are processed fresh or after storage, into estate
brown crepe.
 Earth scrap, tree scrap and scrap stored for long periods are lower quality
materials and hence the crepe processed from these will be of inferior quality.
 Different grades of field coagulum crepe are used in appropriate proportions in
blends with other forms of natural rubber to make products such as tyres,
footwear, retreads or mechanical goods.
 Grading of field coagulum crepe also is done visually as per the norms prescribed
in the Green Book. Here also the main criterion is colour. Different grades are
available in each type.
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Rubber Cup Lump collecting Rubber Cup Lump
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1. What is the different between natural rubber (NR) and
synthetic rubber?
2. What is the tree name that most widely exploited
commercial source of NR?
3. What is the form of NR harvesting from the rubber tree?
4. What are the various marketable forms of raw natural
rubber (NR)?

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 Properties of natural rubber:
 Natural rubber (NR) consists of thousands of isoprene units linked
together to form a polymer.
 It is a high molecular weight polymer having the chemical structure,
cis-1,4 polyisoprene.
 The physical and chemical properties of the rubber are influenced
by the presence of the non-rubber substances and the degree of
crosslinking.

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 Polyisoprene:
 Polyisoprene, polymer of isoprene (C5H8) is primary chemical constituent of
natural rubber.
 Depending on its molecular structure, polyisoprene can be a resilient, elastic
polymer (elastomer), as in the case of natural rubber and isoprene rubber, or a
tough, leathery resin, as in the case of natural and synthetic balata or gutta-percha.
 The chemical structure of isoprene can be represented as CH2=C(CH3)—CH=CH2.
 Polyisoprene—built up from the linking of multiple isoprene molecules—can
assume any one of four spatial configurations, or isomers, each of which imparts a
unique set of properties to the polymers.

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 As the repeating units of polyisoprene, the four isomers have the following
structures:

 Of these four isomers, the most important are the cis-1,4 polymer and the trans-1,4
polymer.

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 Cis-1,4 Polyisoprene:
 Natural rubber (NR) consists almost exclusively of the cis-1,4
polymer, which is produced in the milky latex of certain plants—most
notably the rubber tree.
 The uniqueness of natural rubber lies in its physical properties of
extensibility and toughness, summarized by its ability to be stretched
repeatedly to seven or eight times its original length.
 The 'cis-' indicates that substituent groups are on the same side of the
C=C double bond, as shown on the following page.
 The high cis- content (~99%) of natural rubber latex is what gives its
elastic properties.
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 Trans-1,4 Polyisoprene:
 Trans-1,4 polyisoprene is the dominant isomer in gutta-percha and balata, two
materials that, like natural rubber, are derived from the milky exudate of certain
trees.
 Unlike the cis-1,4 polymer, however, the trans-1,4 polymer is highly crystalline, so
balata and gutta-percha are tough, hard, and leathery materials.
 Trans-1,4-polyisoprene (gutta-percha) resembles plastic and is used e.g. in golf
balls, deep sea cables, electrical wires orthopedic applications, belting and
adhesives.
 Gutta-percha can also be obtained from the pruning of special trees which are
native to Malaysia.

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 Important characteristics of natural rubber (NR):
 Raw rubber: it doesn’t have many considerable mechanical
characteristics for engineering application.
 Vulcanised rubber: The physical properties of vulcanised natural
rubber are dependent on several factors such as degree and type of
crosslinking, type and amount of fillers, degree of filler dispersion
and presence of plasticisers.
 Some of the important properties and characteristics of vulcanised
NR are discussed in the following sections.

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1. Strength:
 As in the case of other engineering materials, strength properties are of great
importance in most of the practical applications of rubber. Many of these
properties can be defined and measured.
 The most widely measured among these are tensile strength, tear strength and
resistance to fatigue.
 Perhaps the most striking characteristic of NR, compared with most synthetic
elastomers is its high tensile strength even without the help of any reinforcing
agent.
 The tensile strength of NR vulcanisates frequently exceeds 30 MPa. Strength of NR
is also characterised in terms of tear resistance. It is also observed that tear
resistance is greatly increased by reinforcing fillers.

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2. Resistance to abrasion:
 The mechanisms by which abrasion occurs when a rubber is in moving contact with any
surface are somewhat complex, involving principally, cutting of the rubber and fatigue.
 It is generally accepted that some of the synthetic rubbers such as SBR and BR are
superior to NR in abrasion resistance. However, it may be pointed out that the relative
wear rating of compounds depends on the nature of the track as well as load.
 On smooth surfaces SBR is superior to NR, but on increasing roughness the difference
between the two is reduced and reversal of ranking can be observed.
 Tyre surface temperature is another important factor influencing the relative wear
rating of NR and SBR. At low tyre surface temperature, as encountered during winter, NR
is superior. At high surface temperature the reverse is true, the reversal occurring at
about 35 °C.

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3. Resistance to ageing:
 Being an unsaturated polymer, NR is highly susceptible to degradation by oxygen,
ozone, radiation, heat and chemicals.
 The naturally occurring antioxidants present in the rubber protect it from degradation
during coagulation and subsequent processing and drying of the coagulum and also
during storage.
 These antioxidants are partially lost and/or used up during further processing and
hence additional anti-degradants are needed to ensure adequate service life of end
products.
 The changes occurring during degradation of rubber include chain scission,
crosslinking and introduction of new chemical groups.
 Natural rubber degrades mostly by chain scission, resulting in a weak softened stock,
often showing surface tackiness. Oxygen is considered to be the most powerful
degradant for NR.

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 Vulcanisation:
 Most useful rubber articles, such as tires and mechanical goods, cannot be made without
vulcanization. Unvulcanized rubber is generally not very strong, does not maintain its shape after
a large deformation, and can be very sticky. In short, unvulcanized rubber can have about the
same consistency as chewing gum.
 This is generally achieved by reaction with sulphur and accelerators at an elevated
temperature. Also, in addition to sulfur, many other substances have been introduced as
components of curing (vulcanization) systems.
 Vulcanization increases elasticity while it decreases plasticity. It is generally accomplished by the
formation of a crosslinked molecular network (Fig. 1.). Vulcanization, thus, is a process of
chemically producing network junctures by the insertion of crosslinks between polymer chains.
 A crosslink may be a group of sulfur atoms in a short chain, a single sulfur atom, a carbon to
carbon bond, a polyvalent organic radical, an ionic cluster, or a polyvalent metal ion.
 The process is usually carried out by heating the rubber, mixed with vulcanizing agents, in
a mold under pressure. vulcanization occur only after the rubber article is in its final form (Fig.
3.).
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 Vulcanization by sulfur without accelerator:
 Initially, vulcanization was accomplished by using elemental sulfur at
a concentration of 8 parts per 100 parts of rubber (phr). It required 5
hours at 140°C.
 The addition of zinc oxide reduced the time to 3 hours. The use of
accelerators in concentrations as low as 0.5phr has since reduced the
time to as short as 1 to 3 minutes.
 As a result, elastomer vulcanization by sulfur without accelerator is
no longer of much commercial significance.
phr - Parts per hundred rubber
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 Accelerated-sulfur vulcanization:
 Accelerated-sulfur vulcanization is the most widely used method. For many
applications, it is the only rapid crosslinking technique that can, in a
practical manner, give the delayed action required for processing, shaping,
and forming before the formation of the intractable vulcanized network.
 It is used to vulcanize natural rubber (NR), synthetic isoprene rubber (IR),
styrenebutadiene rubber (SBR), nitrile rubber (NBR), butyl rubber (IIR),
chlorobutyl rubber (CIIR), bromobutyl rubber (BIIR), and
ethylenepropylene- diene-monomer rubber (EPDM).
 Typically a recipe for the vulcanization system for one of the above
elastomers contains 2–10phr of zinc oxide, 1–4phr of fatty acid (e. g.,
stearic), 0.5–4 phr of sulfur, and 0.5–2phr of accelerator. Zinc oxide and the
fatty acid are vulcanization system activators.
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Non-sulphur vulcanisation:
 These systems are of far less industrial significance such as:
 Vulcanization by phenolic curatives, benzoquinone derivatives, or
bismaleimides
 Vulcanization by the action of metal oxides
 Vulcanization by the action of organic peroxides
 Dynamic vulcanization

 https://www.youtube.com/watch?v=sFjGQxUTVJE
 https://www.youtube.com/watch?v=3SDRyB4RUxA
 https://www.youtube.com/watch?v=TPtc_bAhGeg
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 Applications:
 Natural rubber is a general purpose elastomer. Its high resilience,
low heat build-up and excellent dynamic properties coupled with
outstanding processability, make it an ideal rubber for automotive
tyres.
 Therefore, it is no surprise that around 55% of all the NR is used in
tyres. The major non-tyre applications include beltings, hoses, cycle
tyres, footwear, engineering products, latex products such as dipped
goods, rubber backed carpets and adhesives.

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 Tyres:
 Use of NR is preferred in tyres
because of its high strength
combined with high elasticity.
 On icy roads skid resistance of NR is
better than that of synthetic rubbers.
 The low skid resistance in
combination with high wear
resistance of NR at low temperature,
makes OENR particularly suitable for
winter tyres.

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 Engineering applications:
 Most engineering applications of NR involve its use as a spring. In
comparison with metal springs, NR springs require no maintenance,
have high energy storage capacity and non-linear load deflection
characteristics, can accommodate a certain amount of misalignment
and are easier to install.
 The typical engineering applications of NR include antivibration
mountings, flexible couplings, bridge bearings, bearings for
buildings for protection from earthquakes, dock fenders and rail
pads.

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 Conveyor beltings:
 Top grade conveyor beltings can be made from NR except
for those used in underground mines (problems of
inflammability).
 In service, NR offers reasonably good resistance to wear
and chipping by such abrasive materials as stone, coal and
ores. For moderate heat resistance NR is blended with SBR.

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 Linings:
 Linings based on NR are ideal for protection against corrosion and
abrasion of chemical plant.
 NR is resistant to most inorganic acids, salts and alkalies except the
concentrated materials and is widely used for linings of tanks,
especially those containing caustic solutions.
 Soft linings from NR are highly resistant to abrasion, even better than
mild steel in that respect and hence are ideal for equipment used for
handling slurries and sand blasting.

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 Conclusion:
 Thus NR is an ideal elastomer suitable for most general purpose and
engineering applications. However, the most important aspect of NR
is that it is environmentally friendly.
 It is a product of nature and the energy requirement for its production
is only a small fraction of that required for synthetic rubbers.
 While production of synthetic rubber causes large-scale pollution
including release of large quantities of carbon into the atmosphere,
production of NR starts with fixing up of the carbon from the
atmosphere.
 Therefore, use of NR has a definite positive impact on the
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environment.
1. What is the chemical structure of NR?
2. Raise 3 important characteristics of rubber?
3. What is vulcanisation of rubber?
4. What is the role of accelerator in sulfur vulcanisation?
5. What are the components produced from natural rubber (NR)?

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1. What is natural rubber (NR)?
2. Why do we need vulcanisation of rubber?
3. What are the main characteristics of vulcanised rubber?
4. What is the accelerated-sulfur vulcanization?
5. Take 5 pictures of components made of rubber in the plant?

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Q&A
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