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RECYCLING OF RUBBER

1. RUBBER

1.1 Introduction

Rubber is a tough elastic polymeric substance made from the latex of a


tropical plant or synthetically is called rubber. Rubber is produced from natural or
synthetic sources. Natural rubber is obtained from the milky white fluid called latex,
found in many plants; synthetic rubbers are produced from unsaturated hydrocarbons.
Long before Columbus arrived in the Americas, the native South Americans were
using rubber to produce a number of water-resistant products. The Spaniards tried in
vain to copy these products (shoes, coats and capes), and it was not until the 18th
century that European scientists and manufacturers began to use rubber successfully
on a commercial basis. The British inventor and chemist Charles Macintosh, in 1823,
established a plant in Glasgow for the manufacture of waterproof cloth and the
rainproof garments with which his name has become synonymous. A major
breakthrough came in the mid 19th century with the development of the process of
vulcanisation. This process gives increased strength, elasticity, and resistance to
changes in temperature. It also renders rubber impermeable to gases and resistant to
heat, electricity, chemical action and abrasion. Vulcanised rubber also exhibits
frictional properties highly desired for pneumatic tyre application. Crude latex rubber
has few uses. The major uses for vulcanised rubber are for vehicle tyres and conveyor
belts, shock absorbers and anti-vibration mountings, pipes and hoses. It also serves
some other specialist applications such as in pump housings and pipes for handling of
abrasive sludges, power transmission belting, diving gear, water lubricated bearings,
etc. In this brief, we will be looking primarily at the reclamation and reuse of scrap
tyres. This is simply due to the fact that this is the major source of waste rubber in
developing countries.

1.2 History of Rubber

Rubber was known to the indigenous peoples of the Americas long before the
arrival of European explorers. In 1525, Padre d'Anghieria reported that he had seen
Mexican tribal people playing with elastic balls. The first scientific study of rubber
was undertaken by Charles de la Condamine, when he encountered it during his trip to
Peru in 1735. A French engineer that Condamine met in Guiana, Fresnau studied

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rubber on its home ground, reaching the conclusion that this was nothing more than a
"type of condensed resinous oil".

 The first use for rubber was an eraser. It was Magellan, a descendent of the
famous Portuguese navigator, who suggested this use. In England, Priestley
popularized it to the extent that it became known as India Rubber. The word
for rubber in Portuguese - borracha - originated from one of the first
applications for this product, when it was used to make jars replacing the
leather borrachas that the Portuguese used to ship wine.

 Returning to the works of Condamine, Macquer suggested that rubber could


be used to produce flexible tubes. Since then, countless craftsmen have
become involved with rubber; goldsmith Bernard, herbalist Winch, Grossart,
Landolles and others. In 1820, British industrialist Nadier produced rubber
threads and attempted to use them in clothing accessories. This was the time
when America was seized by rubber fever, and the waterproof footwear used
by the indigenous peoples became a success. Waterproof fabrics and snow-
boots were produced in New England.

 In 1832, the Rosburg factory was set up. Unfortunately, cold weather affected
goods made from non-vulcanized natural rubber, leaving them brittle and with
a tendency to gum together if left in the sun, all discouraging consumers. After
a long period attempting to develop a process to upgrade rubber qualities (such
as including nitric acid) that almost ruined him, in 1840 Goodyear discovered
vulcanization, quite by accident.

 An interesting fact: in 1815, a humble sawyer - Hancock - became one of the


leading manufacturers in the UK. He had invented a rubber mattress and
through an association with Macintosh he produced the famous waterproof
coat known as the "macintosh". Furthermore, he discovered how to cut, roll
and press rubber on an industrial scale. He also noted the importance of heat
during the pressing process, and built a machine for this purpose.

 Macintosh discovered the use of benzene as a solvent, while Hancock


discovered that prior chipping and heating were required in order to ensure

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that the rubber dissolved completely. Hancock also discovered how to


manufacture elastic balls. Finally, in 1842, Hancock came into possession of
vulcanized rubber produced by Goodyear, seeking and finding the secret of
vulcanization that brought him a vast fortune.

 In 1845, R.W. Thomson invented the pneumatic tire, the inner tube and even
the textured tread. In 1850 rubber toys were being made, as well as solid and
hollow balls for golf and tennis. The invention of the velocipede by Michaux
in 1869 led to the invention of solid rubber, followed by hollow rubber and
finally the re-invention of the tire, because Thomson's invention had been
forgotten. The physical properties of rubber were studied on the textured tread.
In 1850 rubber toys were being made, as well as solid and hollow balls for
golf and tennis. The invention of the velocipede by Michaux in 1869 led to the
invention of solid rubber, followed by hollow rubber and finally the re-
invention of the tire, because Thomson's invention had been forgotten. The
physical properties of rubber were studied by Payen, as well as Graham,
Wiesner and Gérard.
 Finally, Bouchardt discovered how to polymerize isoprene between 1879 and
1882, obtaining products with properties similar to rubber. The first bicycle
tire dates back to 1830, and in 1895 Michelin had the daring idea of adapting
the tire to the automobile. Since then, rubber has held an outstanding position
on the global market.

1.3 Types of Rubber

In rubber there are two types of Raw materials they are

1) Natural Rubber

2) Synthetic Rubber

1.3.1 Natural rubber

Natural rubber is extracted from rubber producing plants, most notably the tree
Hevea brasiliensis, which originates from South America. Nowadays, more than 90%
of all natural rubber comes from these trees in the rubber plantations of Indonesia, the
Malay Peninsula and Sri Lanka. The common name for this type of rubber is Para

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rubber. The rubber is extracted from the trees in the form of latex. The tree is
‘tapped’; that is, a diagonal incision is made in the bark of the tree and as the latex
exudes from the cut it is collected in a small cup. The average annual yield is
approximately 2 ½ kg per tree or 450kg per hectare, although special high-yield trees
can yield as much as 3000kg per hectare each year. The gathered latex is strained,
diluted with water, and treated with acid to cause the suspended rubber particles
within the latex to coagulate. After being pressed between rollers to form thin sheets,
the rubber is air (or smoke) dried and is then ready for shipment.

1.3.2 Synthetic Rubber

There are several synthetic rubbers in production. These are produced in a


similar way to plastics, by a chemical process known as polymerisation. They include
neoprene, Buna rubbers, and butyl rubber. Synthetic rubbers have usually been
developed with specific properties for specialist applications. The synthetic rubbers
commonly used for tyre manufacture are styrene-butadiene rubber and butadiene
rubber (both members of the Buna family). Butyl rubber, since it is gas-impermeable,
is commonly used for inner tube. Table 1.1 below shows typical applications of
various types of rubber.

Table 1.1 Applications of different classes of rubber in the manufacture of


vehicle tyres.

Types of Rubber Application


Natural rubber Commercial vehicles such as lorries, buses
and trailers.
Styrene-butadiene rubber (SBR) Small lorries, private cars, motorbikes
and Butadiene rubber (BR) and bicycles
Butyl rubber (IIR) Inner tubes.

The raw materials that make up tyres are natural and synthetic rubbers, carbon,
nylon or polyester cord, sulphur, resins and oil. During the tyre making process, these
are virtually vulcanised into one compound that is not easily broken down.

Polymers may be divided into two main groups: thermoplastics and


thermosetting materials. Thermoplastics soften when heated, and so may be molded
and then cooled to obtain the desired shape. In principle, this process may be repeated

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either by direct reheating or preferably after grinding into granules, of scrap products.
Thermosetting materials like rubbers on processing and molding are crosslinked, and
therefore cannot be softened or remolding by heating again. Chemical additives
(mostly in minor quantities) are generally incorporated into both thermoplastics and
thermosets as stabilizers, flame-retardants, colorants, plasticizers etc. to optimize
product properties and performance. Thus thermoplastics are more readily recyclable
than thermoset polymers and rubbers. Thus recycling of thermoplastics simply
involves a reversible physical change by heating the resin above its processing
temperature for shaping it and then cooling it to room temperature to obtain the
desired recycled product. But in case of thermosetting materials like rubbers recycling
is not easy. The three dimensional network of the thermoset polymer system must be
broken down either through the cleavage of crosslinks, or through the carbon–carbon
linkage of the chain backbone. This is a much more severe process and the
fragmented products obtained by such cleavage are entirely different from the starting
thermoset or even its precursor thermoplastics material. Thus recycling of
thermoplastics is less troublesome and so the technology for its refabrication is both
well established and economical. Thus a recycled thermoplastic material competes
directly with the virgin polymer. Its commercial viability depends upon the
performance/ cost benefit of the finished product. In contrast, the technology for
recycle of thermoset polymers including rubbers is complex, costly and less viable
commercially. In case of recycling of thermoplastics, reclaim thermoplastics are used
along with virgin resins and fresh additives in the formulation to obtain desired
properties in the product. As with the properties of recycled plastics which undergo
significant reduction of physical property in its recycle, still it retains an acceptable
fraction of virgin resin properties. Similar picture is also found in reclaim rubber.
Although reprocessing of thermoset is difficult still the use of reclaimed/ reground
thermoset resins in new polymer formulations is found with some influence on flow
and deformation characteristics during processing. Perhaps these are used as fillers.
Whereas crosslinked elastomers (thermosets) are easily reclaimed to a thermoplastic
mass suitable for subsequent crosslinked product although remaining present in a
virgin matrix polymer. Although chemical conversion of waste thermoplastic
materials can regenerate their respective monomer providing value added products but

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till date there is no such endeavor to regain monomeric constituent from


corresponding elastomeric waste.

1.4 Production of Rubber Products

The modern process of rubber manufacture involves a sophisticated series of


processes such as mastication, mixing, shaping, moulding and vulcanisation. Various
additives are included during the mixing process to give desired characteristics to the
finished product. They include:

Polymers Vulcanisation accelerators


Activators Vulcanisation agents
Fillers (carbon black) Fire retardants
Anti-degradants Colorants or pigments
Plasticisers Softeners

Fillers are used to stiffen or strengthen rubber. Carbon black is an anti-


abrasive and is commonly used in tyre production. Pigments include zinc oxide,
lithopone, and a number of organic dyes. Softeners, which are necessary when the
mix is too stiff for proper incorporation of the various ingredients, usually consist of
petroleum products, such as oils or waxes; pine tar; or fatty acids. The moulding of
the compound is carried out once the desired mix has been achieved and vulcanisation
is often carried out on the moulded product.

1.5 Vulcanisation
To understand the process of vulcanisation it is worth discussing, briefly, the
molecular structure of rubber. Crude latex is made up of a large number of very long,
flexible, molecular chains. If these chains are linked together to prevent the molecules
moving apart, then the rubber takes on its characteristic elastic quality. This linking
process is carried out by heating the latex with sulphur (other vulcanising agents such
as selenium and tellurium are occasionally used but sulphur is the most common).
There are two common vulcanising processes.

• Pressure vulcanisation. This process involves heating the rubber with sulphur
under pressure at a temperature of 150oC. Many articles are vulcanised in moulds
that are compressed by a hydraulic press

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• Free vulcanisation. used where pressure vulcanisation is not possible, such as with
continuous, extruded products, it is carried out by applying steam or hot air.
Certain types of garden hose, for example, are coated with lead, and are
vulcanised by passing high-pressure steam through the opening in the hose.

1.6 Uses of Rubber

 Rubber is useful in manufacture of articles such as balloons, balls, cushions, and


air hoses.
 The flexibility of rubber is often used in tyres and rollers wide a varities of
devices.
 It is used in rainwear diving gears and chemical medicine tubes and lining of
storage tanks.
 It is used for power transmission belting and for water lubricated bearings in deep
well pumps.
 These are used as insulation and for protective gloves, shoes and blankets.
 It is used for articles such as telephone housings, parts per radio sets, metres and
other electrical instruments.
 The coefficient of friction of rubber which is high on dry surface and low on wet.

1.7 Major Environmental Problems


We know that almost most of the business organizations will raise
environmental issues to a certain extent whether big or small. It is as important as
making profit for the business organization to adopt necessary measures to alleviate
the environmental issues caused as a result of their activities. Despite the numerous
benefits that are rendered to the modernization of this world by natural rubber, the
consequence of natural rubber processing has yet provide a serious problem due to its
highly polluted effluents. The rapid growth of this industry generates large quantities
of effluents coming from its processing operations which is really a big problem
because of its wastewater contains high biological oxygen demand and ammonia.
Without proper treatment, discharge of wastewater from rubber processing industry to
the environment may cause serious and long lasting consequences.

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1.7.1 High concentration of BOD & COD


Wastewater discharged from latex rubber processing usually contains high
level of BOD and COD. These characteristics vary from country to country due to
difference in raw latex and applied technique in the process. The main source of the
pollutants is the coagulation serum, field latex coagulation, and skim latex
coagulation. These compounds are readily biodegradable and this will result in high
oxygen consumption upon discharge of wastewater in receiving surface water.

1.7.2 Acidic effluent


It is noted that the effluent from latex rubber processing industries is basically
acidic in nature. Different extents of acid usage in the different factories attribute to
pH variation of different effluent. Due to the use of acid in latex coagulation, the
effluent discharged from latex rubber factories is acidic and re-dissolves the rubber
protein. The effluent comprises mainly of carbonaceous organic materials, nitrogen
and sulfate. The quantity of acid used for coagulation of the latex, specifically in skim
latex after centrifugation operation, is generally found to be higher than the actual
requirement.

1.7.3 High concentration of ammonia and nitrogen compounds

The high concentration of ammonia presents in the latex concentrate effluent


posed another serious threat to the environment. Most of the concentrated latex
factories in the South of Thailand discharge treated wastewater that contains high
level of nitrogen & ammonia to a nearby river or canals leading to a water pollution
problem. If high level of ammonia is discharged to water bodies, it could lead to death
of some aquatic organisms living in the water. Land treatment system has been
conducted to treat and utilize nitrogen in treated wastewater from the concentrated
latex factory.

1.7.4 High level of sulfate


The effluent from latex concentrate factories contains high level of sulfate
which originated from sulfuric acid used in the coagulation of skim latex. The high
level of sulfate in this process can cause problem in the biological anaerobic treatment
system as high levels of H2S will be liberated to the environment and generates

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malodor problem. The free H2S also inhibits the digestion process, which gives lower
organic removal efficiency

1.7.5 High level of odor


The odor causing compound such as hydrogen sulfide, ammonia, amines, can
be produced by many of wastewater treatment process. Most odor of organic nature
arises from the anaerobic decomposition of compounds containing nitrogen and
sulfur. The odor is detectable even at extremely low concentrations and makes water
unpalatable for several hundred miles downstream from the rubber plants. The
problems presents varies considerably depending on the plant site, the raw material
used, and the number of intermediary product.

1.8 Rubber Waste

In 2011, newspaper/mechanical papers recovery was about 73 percent (7


million tons), and about 57 percent of yard trimmings were recovered. Total
generation in 2011 was 250 million tons. Organic materials continue to be the largest
component of MSW. Paper and paperboard account for 28 percent and yard
trimmings and food waste account for another 28 percent. Plastics comprise about 13
percent; metals make up 9 percent; and rubber, leather, and textiles account for 8
percent. Wood follows at around 6 percent and glass at 5 percent.

The rubber, leather and textile may not seem significant, as 8.2% seems fairly
inconsequential. However, given the tremendous amount of waste produced in
general, 8.2% is a significant burden on the environment when considered in
measurements more equitable to the impact - tons of rubber discarded into landfills
yearly.

Given the unique properties of rubber materials, the overall use of rubber for a
large number of applications is constantly on the rise and becoming an ever increasing
focus of concern. Rubber materials also of increasing concern, not only in
industrialized countries but also in less developed nations, rubber products are
everywhere to be found, though few people recognize rubber in all of its applications.
Since 1920, demand for rubber manufacturing has been largely dependent on the
automobile industry, the biggest consumer of rubber products.

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Most often the image that comes to mind when the words “environment” and
“Rubber” are spoken together conjures the thought of automotive tires. About 242
million tires are discarded every year in the United States alone. Less than 7 percent
are recycled. 11 percent are incinerated for their fuel value and another 5 percent are
exported. The remaining 78 percent are either landfilled, or are illegally dumped.
According to a recent report of the US Environmental Protection Agency (U.S EPA),
this has resulted in a national stockpile of over 2 billion waste tires.

Aside from tires, rubber in its many forms is used for many, many other
applications. Rubber is used in radio and T.V sets and in telephones. Medical and
multipurpose gloves made of rubber provide a safe barrier to chemicals and infection.
Electric wires are made safe by rubber insulation. Rubber forms a part of many
mechanical devices in the kitchen. It helps to exclude draughts and to insulate against
noise. Sofas and chairs may be upholstered with foam rubber cushions, and beds may
have natural rubber pillows and mattresses. Clothing and footwear may contain
rubber: e.g. elasticized threads in undergarments or shoe soles. Most sports
equipment, virtually all balls, and many mechanical toys contain rubber in some or all
of their parts. Still other applications have been developed due to special properties of
certain types of synthetic rubber, and there are now more than 100,000 articles that
use rubber as a raw material.

With the increase in demands, the manufacturing and use of rubber and the
rubber products has increased tremendously both in the developed and less developed
countries. The use of rubber in so many applications results in a growing volume of
rubber waste.

The waste comes not only from discarded used product but also from
manufacturing. For example, the latex industry expanded over the years to meet the
world demand for examination gloves, condoms, latex thread, etc. Due to strict
specifications for latex products, as much as 15% of the products are sometimes
rejected, and these rejects create a major disposal problem for the rubber industry. At
the same time, there is a worldwide demand to reduce landfill buildup and
environmental pollution.

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The environmental movement of rubber has focused in areas outside of


disposal. Some companies, such as Styron Emulsion Polymers, have focused on
utilizing renewable energy during manufacturing to reduce greenhouse gas emissions.
Others have focused marketing efforts on promoting the value of renewable natural
rubber and claims of its “inherent biodegradability”. Ultimately, having an
environmentally-sound product is becoming an important factor for an increasing
number of consumers; the hard part is deciding the best choice for your company’s
needs, budget, and planetary commitment.

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2. REUSE OF RUBBER

2.1 Introduction

Tyres pose a big problem for the environment. Tires don’t break down,
burning them releases toxic gases, and they can release toxins and chemicals into the
dirt on which they are stored. Almost every state has introduced legislation that deals
with scrap tires, with many states banning them from landfills completely. The good
news is that rubber tires can be reused in many different ways.

2.2 Tyre reuse and recovery in developing countries

There is an enormous potential for reclamation and reuse of rubber in


developing countries. There is a large wastage of rubber tyres in many countries and
the aim of this brief is to give some ideas for what can be done with this valuable
resource. Whether rubber tyres are reused, reprocessed or hand crafted into new
products, the end result is that there is less waste and less environmental degradation
as a result. In developing countries, there is a culture of reuse and recycling. Waste
collectors roam residential areas in large towns and cities in search of reusable
articles. Some of the products that result from the reprocessing of waste are
particularly impressive and the levels of skill and ingenuity are high. Recycling
artisans have integrated themselves into the traditional market place and have created
a viable livelihood for themselves in this sector. The process of tyre collection and
reuse is a task carried out primarily by the informal sector. Tyres are seen as being too
valuable to enter the waste stream and are collected and put to use.

In Karachi, Pakistan, for example, tyres are collected and cut into parts to
obtain secondary materials which can be put to good use. The beads of the tyres are
removed and the rubber removed by burning to expose the steel. The tread and
sidewalls are separated – the tread is cut into thin strips and used to cover the wheels
of donkey carts, while the sidewalls are used for the production of items such as shoe
soles, slippers or washers.

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Fig. 2.1 Manual Separation of the Tread from the Sidewalls, Karachi, Pakistan
2.3 Recovery of rubber
2.3.1 Recovery Alternatives
There are many ways in which tyres and inner tubes can be reused or
reclaimed. The waste management hierarchy dictates that re-use, recycling and energy
recovery, in that order, are superior to disposal and waste management options. This
hierarchy is outlined in Table 2.1 below.

Table2.1 Principal rubber recycling processing paths (adapted from van Baarle)
Kind of recovery Recovery process
Repair • Retreading
• Regrooving
Product reuse Physical reuse • Use as weight
• Use of form
• Use of properties
• Use of volume

Physical • Tearing apart


• Cutting
• Processing to crumb
Material reuse
Chemical Reclamation
Thermal • Pyrolysis
• Combustion
Energy reuse • Incineration

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2.3.2 Product re-use


Damaged tyres are, more often than not, repaired. Tubes can be patched and
tyres can be repaired by one of a number of methods. Regrooving is a practice carried
out in many developing countries where regulations are slacker and standards are
lower (and speeds are lower) than in the West. It is often carried out by hand and is
labour intensive. The use of retread tyres saves valuable energy and resources. A new
tyre requires 23L of crude oil equivalent for raw materials and 9L for process energy
compared with 7L and 2L respectively for retreading. Tyres of passenger vehicles can
generally be retreaded only once while truck and bus tyres can be retreaded up to six
times. Retreading is a well established and acceptable (in safety terms) practice. The
process involves the removal of the remaining tread (producing tyre crumb – see
later) and the application and vulcanization of a new tread (the ‘camel back’) onto the
remaining carcass. In Nairobi about 10,000 tyres a week are received for retreading
(Ahmed). Secondary reuse of whole tyres is the next step in the waste management
hierarchy. Tyres are often put to use because of their shape, weight, form or volume.
Some examples of secondary use in industrialised countries include use for erosion
control, as tree guards, in artificial reefs, fences or as garden decoration. In
developing countries wells can be lined with old tyres, docks are often lined with old
tyres which act as shock absorbers, and similarly crash barriers can be constructed
from old tyres. Old inner tubes also have many uses; swimming aids and water
containers being two simple examples.

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Fig. 2.2: Following the grooves is a Labour –intensive process.

2.3.3 Material re-use

The next step in our hierarchy involves the material being broken down and
reused for the production of a new product. As mentioned earlier, in developing
countries this hand reprocessing of rubber products to produce consumer goods is
well established and the variety of products being made from reclaimed tyres and
tubes is astonishing. The rubber used in tyres is a relatively easy material to reform by
hand. It behaves in a similar manner to leather and has in fact replaced leather for a
number of applications. The tools required for making products directly from tyre
rubber are not expensive and are few in number. Shears, knives, tongs, hammers, etc.,
all common tools found in the recyclers’ workshop, along with a wide range of
improvised tools for specialised applications. Shoes, sandals, buckets, motor vehicle
parts, doormats, water containers, pots, plant pots dustbins and bicycles pedals are
among the products manufactured. Another way in which physical reuse can be
achieved is by reducing the tyre to a granular form and then reprocessing. This can be
a costly process and there has to be a manufacturer willing to purchase the granules.
Crumb rubber from the retreading process can be used in this way, as it is a good
quality granulated rubber. The reprocessing techniques used are similar to those
described in earlier chapters. Granulate tends to be used for low-grade products such

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as automobile floor mats, shoe soles, rubber wheels for carts and barrows, etc., and
can be added to asphalt for road construction, where it improved the properties of this
material.

Fig. 2.3(a) Fig. 2.3(b)

Fig 2.3 (a): coffee table made from truck tyres.

Fig 2.3 (b): Carry bag made from Bus tyres.

2.3.4 Chemical and thermal recovery


This type of recovery is not only lower in the waste management hierarchy,
but is also higher technology requiring sophisticated equipment. The applicability of
such technologies for small-scale applications in developing countries is very limited.
We will therefore look only very briefly at a couple of processes. Chemical recovery
is the process of heating waste rubber reclaim, treating it with chemicals and then
processing the rubber mechanically.

• Acid reclamation – uses hot sulphuric acid to destroy the fabric incorporated in the
tyre and heat treatment to render the scrap rubber sufficiently plastic to allow its use
as a filler with batches of crude rubber.

• Alkali recovery - Reclaimed rubber, treated by heating with alkali for 12 to 30


hours, can be used as an adulterant of crude rubber to lower the price of the finished
article. One form of thermal recovery is pyrolysis. This involves heating the tyre
waste in the absence of oxygen which causes decomposition into gases and

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constituent parts. It is a technology which is still immature in the tyre-reprocessing


field.

2.3.5 Energy recovery

Tyres consist of around 60% hydrocarbons, which is a store of energy that can
be recovered by incineration. The heat produced can be used directly in processes
such as cement making, or to raise steam for a variety of uses, including electricity
generation. Again, this technology requires sophisticated plant and its application is
limited when looking at small scale enterprise.

2.3.6 Landfill

Landfill is the final step in the waste management hierarchy. The landfill
disposal of tyres, if properly managed, does not constitute an environmental problem.
However, concerns about conserving resources and energy have seen an increasing
opposition to landfilling. Also, public sanitation and municipal waste management is
often ineffective in developing countries and scrap tyres are often found littering the
streets.

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3. RECYCLING OF RUBBER

3.1 Introduction
Rubber recycling is the process of recycling vehicles tires (or tyres) that is no
longer suitable for use on vehicles due to wear or irreparable damage (such as
punctures). These tires are among the largest and most problematic sources of waste,
due to the large volume produced, their durability, and the fact they contain a number
of components that are ecologically problematic. It is estimated that 259 million tires
are discarded annually (for years in the 1980s and 1990s).The same characteristics
that make waste tires problematic, their cheap availability, bulk, and resilience, also
make them attractive targets for recycling. Nonetheless more than half of used tires
are simply burned for their fuel value. Even in advanced countries like Germany,
55% are estimated to be burnt for fuel. Approximately, one tire is discarded per
person per year. Tires are also often recycled for use on basketball courts and new
shoe products. However, material recovered from waste tires, known as "crumb," is
generally only a cheap "filler" material and is rarely used in high volumes.

3.2 Why reclaim or recycle rubber?


Rubber recovery can be a difficult process. There are many reasons, however
why rubber should be reclaimed or recovered;

• Recovered rubber can cost half that of natural or synthetic rubber.

• Recovered rubber has some properties that are better than those of virgin rubber.

• Producing rubber from reclaim requires less energy in the total production process
than does virgin material.

• It is an excellent way to dispose of unwanted rubber products, which is often


difficult.

• It conserves non-renewable petroleum products, which are used to produce synthetic


rubbers.

• Recycling activities can generate work in developing countries.

• Many useful products are derived from reused tyres and other rubber products.

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• If tyres are incinerated to reclaim embodied energy then they can yield substantial
quantities of useful power. In Australia, some cement factories use waste tyres as a
fuel source.

3.3 Working of fields of reclaimed rubber

1) Superfine Grade - Widely used in truck tyres, tread rubber, rubber molded
products.

2) Medium Grade - Mostly used in auto tyres, rubber mats and rubber molded goods.
3) Coarse Grade - Commonly used in rubber belting, rubber sheet, tyre flaps, floor/
coir mat.

3.4 Suggestions and Stages of reclaimed rubber

1) Careful selection of raw materials.


2) Removal of all ferrous metal and non-ferrous contaminant.
3) Cleaning, cutting and grounding of material to very fine powder.
4) Depolymerisation of the powdered rubber under controlled conditions of
temperature and steam pressure.
5) This depolymerisation process is carried out in the rotary autoclaves that are
aided with suitable process oils. The powder is then strained and finally
refined to silky-smooth leaves, which are built up into sheets for ease of
handling. The end-product is then rigorously tested before approval for
dispatch.

3.5 Products and Applications

Especially in North America, the use of recycled tire rubber (“crumb rubber”)
has experienced an enormous growth in the past decade. The Table below shows a
market summary for North America (United States and Canada) for 2017 classified by
the main markets and applications.

Table 3.1 Markets and applications for recycled tire rubber in North America in 2017

Application/Market
million lbs. metric tons
Rubber Modified Asphalt (RMA) 292 132,727

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Molded Products 307 139,545


Athletic Surfaces 141 64,091
Tires/Automotive 112 50,909
Devulcanized and Surface Modified
Rubber 36 16,364
Plastic/Rubber Blends 38 17,273
Construction and Miscellaneous 70 31,818
Total 996 452,727

3.6 Crumb Rubber as Filler in Virgin Rubber Compound


Since the tire industry consumes about 65% of all rubber compounds produced
worldwide, using crumb rubber as a compounding ingredient for new tires is the most
obvious application for this recycled product. As the quality and supply of crumb
rubber has become more reliable and predictable in recent years, an increasing
number of tire manufacturers add recycled material into their compounds. If mixing
and processing methods are chosen properly, substantial savings can be achieved
without compromising quality, safety or performance characteristics. Aside from
lower material cost, adding some crumb rubber (5 – 15%) to the virgin rubber
compound offers the following advantages:

• Better mixing properties and improved form stability of uncured parts

• Improved degassing during the vulcanization process

• Improved mold release

• Increased plant efficiency due to reduced cure times

In some applications, abrasion resistance is also significantly improved.

Based on these benefits, some tire manufacturers routinely use crumb rubber as a
filler, especially for tread compounds and whenever speed and high performance is
not crucial, e.g. for farm equipment or solid rubber tires.

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3.7 Devulcanization

In chemical terms, devulcanization means reverting rubber from its thermoset,


elastic state back into a plastic, moldable state. This is accomplished by severing the
sulfur bonds in the molecular structure. With the proper devulcanization method, a
much higher percentage of crumb rubber old tires can be used as compounding.
Traditional devulcanization methods involved exposing cured rubber to elevated
temperatures for an extended period of time. However, this “thermal reclaim process”
not only severs the sulfur bonds in the polymer matrix, but also breaks the polymer
chains, causing a significant decrease in physical properties. Because of questionable
economics and environmental concerns, thermal devulcanization is rarely used today.
In recent years, a number of new and promising devulcanization methods were
developed. The following Table lists the most common devulcanization methods.

Table 3.2 Important Devulcanization Methods

Process Description Process


Thermal Rubber is exposed to elevated temperatures over an Thermal
Reclaim Process extended period of time in order to break the sulfur Reclaim
bonds as well as the polymer back bone. This process Process
was first patented by H. L. Hall in 1858, but is rarely
used today due to environmental concerns and
relatively severe degradation of the material.

Mechanical Vulcanized rubber is exposed to intense mechanical Mechanical


Devulcanization work (mastication) in order to selectively break the Devulcanization
sulfur bonds in the polymer matrix. The machines
used are two roll mills, high shear mixers and
extruders. Mechanical devulcanization method leads
to good results and may be economically viable in the
near future.
Devulcanization Technically speaking, this is a special form of Devulcanization
with Ultrasound mechanical devulcanization. First research results on with Ultrasound
this subject are encouraging.
Bacterial Fine rubber powder is exposed to an aqueous Bacterial
Devulcanization suspension with bacteria that consume sulfur and Devulcanization
sulfur compounds,e.g.,thilbacillus, rodococcus &
sulfolobus. Technically viable, but questionable
economics due to the complexity of the process.

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3.8 Surface Activation

Surface activation increases the adhesiveness of crumb rubber particles. The


increased adhesiveness makes it possible to use a larger percentage of recycled
material without the detrimental effects commonly experienced when untreated fillers
are added. This method may prove to be a good compromise between using crumb
rubber as a mere filler versus complete devulcanization. In some applications, surface
activated crumb rubber can be molded by itself, without binders or other additives.
Like with devulcanized material, the economic viability of surface activated crumb
rubber depends to a large extent on the market price of virgin rubber compound.

3.9 Molded Products

In the past few years, the increasing supply of crumb rubber and a newly
developed moisture-curing urethane binder has led to a rapid increase in the number
of products made by simple compression molding. Typically, this method is used to
produce high-volume, low-tech products, such as livestock mats, railroad crossings,
removable speed bumps and athletic mats. Using crumb rubber in combination with
urethane binder to produce molded products enables manufacturers to significantly
reduce the processing time and material costs. However, this application is limited to
products where only moderate tensile strength and abrasion resistance is required.

3.10 Pyrolysis

Pyrolysis is the thermal decomposition of an organic material under the exclusion


of ambient oxygen. The typical products of scrap tire pyrolysis are:

• Hydrocarbon gases (mostly used to fuel the process itself)

• pyrolysis oil (properties similar to that of heavy fuel oil)

• carbon black (may be used as pigment or filler)

• scrap steel

While pyrolysis of scrap tires has been proven to be technically viable, the author
is not aware of any company in the world that has operated a pyrolysis plant for a
sustained period of time.

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3.11 Wet Poured Layers

Playgrounds and athletic surfaces are frequently covered with a layer of rubber
granules in order to help prevent injuries. Many stadiums throughout the
industrialized world have running tracks that consist of recycled material. Most
commonly, a moisture- curing urethane is mixed with 4-10 mesh crumb rubber and
applied in a similar way as other poured pavements. These layers are usually softer
than hot cured, compression molded mats. In most cases, the top layers of poured in
place athletic surfaces are made of UV-resistant, colored EPDM granules.

3.12 Thermoplastic-Elastomer Compounds

Combining crumb rubber with a thermoplastic binder at high temperatures


yields a material that can be processed more like a thermoplastic compound, but still
has some of the elasticity of rubber. This is a very cost effective method of producing
high volume products such as acoustic insulation in cars, pallets, railroad crossings,
etc.

3.13 Sprayed Layers of Crumb Rubber

In combination with a moisture curing urethane binder, crumb rubber can be


sprayed onto surfaces where elastic, waterproof, corrosion resistant or vibration and
impact dampening properties are desirable. This method has a wide range of possible
application and has a good potential for growth.

3.14 Rubber Modified Asphalt (RMA)

Rubber pavements date back to around 1870. At that time, the area around St.
Pancreas Station in London was paved with a rubber compound. This rubber
pavement was widely praised because “the horses’ hooves were silent”, it also was
reported to be durable and easy to keep clean.

More widespread commercial applications of rubber modified asphalt (RMA)


pavements date back to the 1960ies and were first introduced by Charles McDonald in
Arizona. Apart form recycled tire rubber, SBS block co-polymers (thermoplastic
elastomers) are often added to the hot bitumen to improve the performance

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characteristics of asphalt pavements. Experience with thousands of highway miles


paved RMA prove the engineering merits as well as the economic benefits of using
recycled tire rubber in asphalt.

Increased resistance to rutting, reflective and thermal cracking are the main
benefits of RMA. Other advantages include better de-icing properties, reduced traffic
noise and, most importantly, a significantly increased service life and thus a lower life
cycle cost.

Fig 3.1(a) I 40 near Flagstaff, AZ paved Fig. 3.1(b) I 40 near Flagstaff, AZ


with conventional Asphalt. paved with Rubber Modified Asphalt
(RMA)
Figures 3.1(a) and 3.1(b) show two stretches of I 40 near Flagstaff, AZ. Both
pavements were laid in 1990, the pictures were taken in 1998. While the conventional
pavement (left image) is already severely cracked, the RMA pavement (right image)
is in much better shape. (Photos Courtesy of Mr. George Way, of the Arizona
Department Transportation).

The main advantages of Rubber Modifies Asphalt can be summarized as follows:

• Reduced thermal cracking (due to cold temperatures) and rutting (usually caused
by hot temperatures) can be reduced with one and the same asphalt mix. RMA
is specifically useful in areas with extreme climates, i.e. high temperatures in
summer and severe frost in winter.

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• Severely cracked pavements can be paved over with RMA or with a stress
absorbing membrane interlayer (SAMI) because the more elastic properties of
RMA or SAMI significantly reduce reflective cracking.

• Due to lower maintenance costs and increased durability, the live cycle cost of
RMA is significantly lower when compared to conventional asphalt
pavements.

• Other advantages include increased traffic safety due to a better deicing


property, increased skid resistance and fewer construction sites.

3.15. Reclaiming from rubber products

Reclaiming of scrap rubber is, therefore, the most desirable approach to solve
the disposal problem. Reclaiming of scrap rubber products, e.g. used automobile tires
and tubes, hoses, conveyor belts etc. is the conversion of a three dimensionally
interlinked, insoluble and infusible strong thermoset polymer to a two dimensional,
soft, plastic, more tacky, low modulus, processable and vulcanizable essentially
thermoplastic product simulating many of the properties of virgin rubber. Recovery
and recycle of rubber from used and scrap rubber products can, therefore, save some
precious petroleum resources as well as solve scrap/waste rubber disposal problems.
Many attempts have been made since 1910 for reclaiming of scrap rubber products.
However, reclaiming process may be broadly classified into two groups: physical
reclaiming processes and chemical reclaiming processes. In a review, Warner has
summarized various methods of devulcanization using chemical and physical
processes.

3.15.1. Reclaiming of rubbers by physical reclaiming processes

In a physical reclaiming process scrap/waste rubber products is reclaimed with


the help of external energy. Thus in physical reclaiming process three-dimensional
network of crosslinked rubber breaks down in presence of different energy source.
Due to the breaking of network structure macromolecular rubber chain is transformed
into small molecular weight fragments so that it can be easily miscible with the virgin
rubber during compounding. So reclaim rubber produced by physical reclaiming

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process may be used as a non-reinforcing filler. But if in this process a specific


amount of energy is used which is sufficient to cleave only the crosslink bonds then
after reclaiming a good quality of reclaim rubber will be obtained which will be
thermoplastic in nature and compare well with virgin rubber properties.

Different types of physical reclaiming processes are:

(i) Mechanical (ii) thermo-mechanical (iii) cryo-mechanical (iv) microwave and (v)
ultrasonic.

3.15.1.1 Mechanical reclaiming process

In mechanical reclaiming process crumb rubber is placed in an open two-roll


mixing mill and milling is carried out at high temperatures. In this process drastic
molecular weight breakdown takes place due to mechanical shearing at high
temperatures. In one patent by Maxwell a physical process of reclaiming of
vulcanized rubber and refining of the reclaimed rubber are described. The vulcanized
rubber in particulate form (e.g. ground tire) is reclaimed with reclaiming agents by
passing the rubber between an essentially smooth stator and an essentially cylindrical
rotor arranged to provide an axial shear zone in which the rubber is frictionally
propelled by the rotor action. The action may be assisted by mixing a suitable amount
of previously reclaimed rubber or of vulcanized rubber with or in advance of the
particulate vulcanized rubber, and/or by supplemental heating. In other aspects of the
invention previously reclaimed and vulcanized rubber is similarly fed and acted upon
as substitute for conventional refining operation. De and co-workers reported the
mechanical reclaiming process of vulcanized NR. The reclaimed natural rubber was
prepared by milling vulcanized sheets at about 80 C. On a two roll laboratory mill it
formed a band on the roll. Next, it was mixed with various rubber additives. In
another case, mixing of reclaim rubber (RR) with fresh rubber in various proportions
and study of their curing characteristics, mechanical properties etc. were done. But the
Mooney viscosity of the reclaimed rubber was very high (200, i.e. out of scale)
indicating that the plasticity of rubber was very low due to the presence of higher
percentage of crosslinked rubber. But the extent of reclaiming, i.e. percentage of
sol/gel fraction, molecular weight of the sol fraction, and the influence of milling
parameters on the Mooney viscosity were not reported.

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Study of the curing characteristics of the blends of fresh rubber with reclaim
rubber indicated that with increase in the reclaim rubber content the cure rate
increased but the scorch time, optimum cure time and reversion resistance decreased.
As the proportion of reclaim rubber in the blends increases modulus, abrasion loss,
compression set and hardness increase while tensile strength, elongation at break, tear
strength, resilience and flex resistance decrease. The above result shows that increase
in the proportion of reclaim rubber increases the crosslink density. As crosslink
density is very high for the NR/RR (25/75) blend so modulus is high but tensile
strength and flex properties are low. Thus reclaim rubber appeared to perform as a
non reinforcing filler in this study.

3.15.1.2. Thermo-mechanical reclaiming process

This process involves the thermo-mechanical degradation of the rubber


vulcanizate network. The vulcanizate is swollen in a suitable solvent and then
transferred to a mill to form a fine powder ( 20 mm diameter). This powder rubber is
revulcanized with curing ingredients. The products thus obtained show slightly
inferior properties to those of the original vulcanizates.

3.15.1.3. Cryomechanical reclaiming process

In the mid 1960’s, the technique of grinding scrap rubber in cryomechanical


process was developed. This reclaiming process involves placing small pieces of
vulcanized rubber into liquid nitrogen which are transferred to a ball mill and ground
in presence of liquid nitrogen to form a fine powder. The particle size of the cryo-
ground rubber varies from 30 to 100 mesh for most products.

The particle size is controlled by the immersion time in the liquid nitrogen and
by the mesh size of screens used in the grinding chamber of the mill. Generally, the
cost of the ground rubber increases as the particle size decreases. The cost of 40 mesh
ground rubber is usually in the mid to high twenty cents per pound area, while smaller
particle sizes like 80–100 mesh cost $0.30–$0.40 per pound. It has been reported that
using 5–10 phr cryogenically ground rubber in various passenger and truck tire
compounds shows some economic advantage. The economic benefit for a modest
usage (5%) in passenger tires and truck tires has been estimated at approximately
$0.10 and $0.54 per tire, respectively. At the 10% usage level the economic benefit

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correspondingly doubles. In 1991 Klingensmith evaluated the performances of


cryogenically ground butyl rubber in the tyre inner liner. He showed the effect of
mesh size on percent retention of physical properties.

3.15.1.3. Processing and mixing of cryogenically ground rubber

In the processing of cryogenically ground rubber certain particle sizes are


more suitable in specific applications.

Extrusion: 80–100 mesh cryogenically ground rubber is needed to avoid fracturing


and rough edges.

In extrusion of thick section 50–60 mesh cryogenically ground rubber can be


used depending on the surface smoothness of the final product. The optimum level of
cryogenically ground rubber to be added to fresh rubber is 5%.

Calendering: For optimum surface smoothness of products which are 0.060 HH or


less thick, the compound requires 80–100 mesh cryogenically ground rubber. Where
smoothness is not so important 30–60 mesh can be used. The optimum level of
cryogenically ground rubber in calendering is 10%.

Molding: The cryogenically ground rubber in all mesh sizes can be used because all
mesh sizes help in removing trapped air during molding. The cured rubber particles
provide a path for the air to escape by bleeding air from the part.

Mold flow: Cryogenically ground rubber generally improves mold flow. Shrinkage is
usually less for compounds containing cryogenically ground rubber. The shrinkage
reduction is proportional to the amount of cryogenically ground rubber in the
compound. So less mold flashing was found with increase in the percentage of
cryogenically ground rubber.

3.16 Comparison between Natural/Synthetic Rubber and Recycle Rubber

The Recovered rubber can cost half that of natural or synthetic rubber. It has
some properties that are better than those of virgin rubber. Producing rubber from
reclaim requires less energy in the total production process than does virgin material.
It is an excellent way to dispose of unwanted rubber products, which is often difficult.
It conserves non-renewable petroleum products, which are used to produce synthetic

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rubbers. It is brittle when cold. It is deformed by warming. It is made up of polymer


chains which move independently due to the absence of cross links. It is a poor
material when high elasticity is required. It is sticky.

Recycling activities can generate work in developing countries. Many useful


products are derived from reused tyres and other rubber products. If tyres are
incinerated to reclaim embodied energy then they can yield substantial quantities of
useful power. In Australia, some cement factories use waste tyres as a fuel source.

3.17 Applications of recycled Rubber in Engineering

The engineering definition of a rubber material is “any material that can


stretch to at least 100% of its original length, and return to its original shape without
permanent deformation”. Although the term “rubber” originated from true natural
rubber derived from trees, today the term is used to refer to a host of different
engineering materials, most of which are synthetic, and all of which exhibit the
hallmark flexibility of natural rubber.

As the example of the tire illustrates, rubber can serve a number of


engineering purposes. The range of applications can be broadly grouped into the
following functional categories:

Sealing fluids (e.g. O-Rings)


Conducting fluids (e.g. garden hose)
Storing energy (e.g. bungee cords)
Transmitting energy (e.g. drive belts)
Absorbing energy (e.g. bumpers)
Providing structural support (e.g. bridge bearings)

Although engineers may employ many other options to achieve any of these
purposes, rubber often performs with greater elegance and lower total cost than the
alternatives, and certainly with the highest degree of flexibility. In addition, rubbers
can be molded into extraordinarily complex configurations, and can be bonded to
virtually any substrate material to form a composite component, greatly enhancing the
engineer’s ability to tailor a component’s function.

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4. CONCLUSION & FUTURE SCOPE

4.1 Conclusion

In conclusion, there is a tremendous need to address the ever growing issue of


rubber waste and focus must be put on remediation of these wastes. Complete
biodegradation of these materials may be the suitable answer, provided we are able to
control the biodegradation in such a way that it does not impact the service life of
rubber products. There has been substantial focus in the past as to the inherent (or
suggested inherent) biodegradation of natural rubber; and the focus here was to
determine the ability of products to create synthetic biodegradable rubber materials

For manufacturers and brands utilizing rubber materials, this presents an


opportunity to provide environmentally focused waste management for the
foreseeable future, in a way that requires very little direct action or input other than a
slight change in materials.

4.2 Future Scope

Rubber and tyre recovery has limited but interesting potential in terms of both
waste handling and economic development in developing countries. New projects are
interesting when they are motivated by the resource value of the tyre; in most cases,
the viability of a project based exclusively on avoided disposal lies far off in the
future. In general, the higher up the value added hierarchy it is possible to go in
planning an activity, the greater the market for its products and the higher return per
investment. For example, retreading, which preserves the value added of the casing, is
higher in this hierarchy than making containers, which only preserves the value added
of the rubber. Thus, projects involving repair and retreading are likelier to prove
economically feasible than those involving secondary manufacture.

The level of technology which is appropriate for the type of entrepreneurs


dealt with in this publication remains low. High-technology capital-intensive projects
match neither the supply of tyres nor the needs of the locality and may cause an
exodus of labour.

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REFERENCES

1) Ahmed, R., Klundert, Arnold van de, Lardinois, I., Rubber Waste, Options for
Small-scale Resource Recovery, TOOL Publications and WASTE, 1996. A
book aimed at small scale rubber recyclers in developing countries.
2) Vogler,Jon, Work from Waste, Intermediate Technology Publications and
Oxfam, 1981. A classic for those wishing to recycle waste and create
employment.
3) Baarle, B. van, Het hervewerken van Rubberafval van (Reuse of Rubber from
Personenevagenbanden Passenger Vehicles), NOVEM / RIVM, The
Netherlands 1988.
4) "Rubber," Microsoft® Encarta® 98 Encyclopedia. © 1993-1997 Microsoft
Corporation. All rights reserved.
5) Scrap Tire and Rubber Recycling Terminology Booklet developed by the
ITRA Tire and Rubber Recycling Advisory Council (TRRAC) (See address in
following section). It is a valuable resource to understanding the tire industry
and tyre recycling issues.
6) Porteous, Andrew, Recycling Resources Refuse, Longman 1977.
7) http://www.itra.com/corporate/recycling/trrac.htm, International Tire and
Rubber Association (ITRA) Home Page. A wealth of information on recycling
of tyres and associated topics.
8) http://www.wrf.org.uk, Web site of the World Resource Foundation (see
previous section).
9) http://www.rapra.net, Web site of RAPRA (see previous section).
10) http://usrubber.com, US Rubber Inc. A commercial Website with an
interesting range of products from recycled rubber.

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