Rubber Technologists Handbook

Edited by Sadhan K. De and Jim R. White

Rapra Technology Limited

Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118 http://www.rapra.net

First Published 2001 by

Rapra Technology Limited

Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK

2001, Rapra Technology Limited

All rights reserved. Except as permitted under current legislation no part of this publication may be photocopied, reproduced or distributed in any form or by any means or stored in a database or retrieval system, without the prior permission from the copyright holder. A catalogue record for this book is available from the British Library.

ISBN: 1-85957-262-6

Typeset by Rapra Technology Limited Printed and bound by Polestar Scientifica, Exeter, UK

Natural Rubber
N. M. Mathew

Hevea brasiliensis Parthenium argentatum Manihot glaziovii Castilla elastica Ficus elastica Funtumia elastica

2.1 Introduction
Natural rubber (NR) has been known to the civilised world ever since the year 1493, when Christopher Columbus found the natives of Haiti playing with balls made from the exudates of a tree called cau-uchu or weeping wood. The term rubber was coined by the English chemist Joseph Priestly for its ability to erase pencil marks. It was the French scientist Charles de la Condamine who first introduced NR to Europe in 1736 and published his observations in 1745. Industrial applications of rubber were found slowly after this. It was the discovery of vulcanisation by Charles Goodyear in 1841 that paved the way for the growth of the modern rubber industry.

2.2 Source
Natural rubber is cis-1,4 polyisoprene and is present as latex in a large variety of plants in many regions of the world. Latex containing appreciable quantities of rubber occurs in certain plant species belonging to the Moraceae, Euphorbiaceae, Apocynaceae and Compositae families as listed in Table 2.1. The most important source is the tree Hevea brasiliensis. Latexes from the other sources suffer from disadvantages such as low rubber content, high resin content and difficulties in extraction. However, Parthenium argentatum, which yields guayule rubber has gained some importance in the last two decades mainly

Table 2.1 Major plant sources of natural rubber

Family Euphorbiaceae Compositae Euphorbiaceae Moracea Moracea Apocynaceae Species Hevea brasiliensis Parthenium argentatum Manihot glaziovii Castilla elastica Ficus elastica Funtumia elastica Popular name Para rubber Guayule rubber Ceara rubber Panama rubber India rubber Lagos silk rubber

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production consumption Rubber Technologists Handbook on account of the possibility of this shrub being cultivated in the semi-arid regions of South-Western USA and Mexico. Hevea brasiliensis, the most widely exploited commercial source of NR, was introduced i nto trop i cal As i a i n 1876 by S i r Henry Wi ckham . About 10 m i ll i on hectares (100,000 km2) are currently planted with it, producing around 6.7 million tonnes of NR annually. The rubber growing areas form a belt lying a few degrees north and south of the equator. Table 2.2 gives the major producing countries and their contribution to rubber production.

Table 2.2 NR production/consumption in major producing/consuming countries

Country Thailand Indonesia Malaysia India China Vietnam Ivory Coast Sri Lanka Liberia Brazil Philippines Cameroon Nigeria Cambodia Guatemala Myanmar Others Total Production in 1999 (kilo tonnes) 2265.5 1596.2 768.9 620.1 460.0 230.0 122.0 96.6 85.0 70.0 65.0 63.0 50.0 40.0 31.3 27.2 159.2 6750.0 Country USA China Japan India Malaysia Korea France Thailand Germany Brazil Spain Canada Indonesia Taiwan Turkey Sri Lanka Others Total Consumption in 1999 (kilo tonnes) 1093.0 852.0 734.2 619.1 344.4 331.0 252.7 226.9 224.0 170.0 162.0 141.0 116.0 111.0 72.0 53.8 1186.9 6690.0

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Natural Rubber

2.3 Cultivation
Hevea brasiliensis is indigenous to the Amazonian rain forests, situated within 5 latitude and at altitudes less than 200 m. The trees evolved in this environment prefer a warm and humid weather [1, 2]. Rubber is grown predominantly in the tropics, where an equatorial monsoon climate prevails. The climatic conditions suitable for optimum growth of rubber trees include an annual rainfall of not less than 2000 mm, evenly distributed without any marked dry season and with 125 to 150 rainy days per year, a maximum temperature of 29 to 34 C and a minimum of 20 C or more with a monthly mean of 25 to 28 C, high atmospheric humidity of around 80% with moderate wind, bright sunshine amounting to about 2000 hours per year at the rate of six hours per day throughout the year [3, 4]. Rubber needs a well-drained, fairly deep, loamy soil with a pH value of 4.5 6.0. South-East Asia is particularly suited for rubber cultivation as are countries in West Africa. Although not ideally suited, rubber is successfully cultivated even up to a latitude of 25, well beyond the traditional latitude, in countries such as India and China. Rubber is planted at a typical density of 450500 trees per hectare (45005000 trees per km2). Although the plants were earlier raised directly from seeds, the present method of propagation is a vegetative one, called budgrafting, in which buds taken from a selected high yielding mother plant are grafted to seedling stocks. The buds grow into plants which will have all the characteristics of the mother plant. All the trees that are derived by vegetative propagation from a single mother tree constitute a clone. Each clone has its own characteristics of growth, yield, tolerance to diseases and climatic stresses. Propagation of rubber is also possible by tissue culture. Although tissue culture methods have been evolved by many workers [5, 6], it has not yet been used on a commercial scale. The young plants are allowed to grow in a nursery bed or preferably in polyethylene bags in the first year and then transplanted to the field. Soil fertility is maintained by the use of fertilisers and by growing leguminous cover crops. Compared to many other crops, the nutrient requirement of rubber is very limited, since nutrient removal through the crop is very low and as the cultivation practices allow for nutrient recycling through litter disintegration and nitrogen fixation by the legume cover. The trees become ready for harvesting in 57 years when they attain a girth of 500 mm at a height of 1.25 m from the bud union. The trees are affected by a number of diseases involving roots, stem and leaves. Effective control measures have been evolved for all these diseases except the South American Leaf Blight caused by the fungus Microcyclus ulei, which has caused extensive damage to the rubber plantations in South America. Fortunately Asia and Africa are free from this disease and a number of quarantine regulations are being implemented by Asian and African rubber growing countries to prevent any accidental introduction of the disease. The other major leaf diseases of rubber are abnormal leaf fall caused by different species

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Rubber Technologists Handbook of the fungus Phytophthora, powdery mildew caused by Oidium heveae, Corynespora leaf disease and Gloeosporium leaf disease. Pink disease caused by Corticium salmonicolor is a major problem affecting the stem while brown and white root diseases are the common problems affecting the root system. Copper-based fungicides are very effective in controlling most of these diseases [7]. The original plantings of rubber had an average annual yield of only 200 to 300 kg per ha (2000 to 3000 kg per km2) [8]. Now there are clones with an annual production potential of 3500 kg per ha. This substantial improvement in productivity has been achieved mainly through breeding and selection programmes carried out in different countries. The successive cycles of breeding and selection have contributed to substantial gene erosion and the genetic base of Hevea has now become very narrow. However, efforts are being made to counter this shortcoming by incorporating freshly introduced wild Hevea genotypes from Brazil. Modern molecular approaches in breeding and use of genetic engineering techniques in Hevea will definitely yield still better performing rubber clones in future.

2.4 Harvesting
Natural rubber is present in the form of latex in a system of intercellular ducts called latex vessels which exist in the bark. The maximum number of such vessels is available close to the cambium, the outermost growing region of the wood. Latex is maintained in the vessels at a higher hydrostatic pressure called turgor pressure of approximately 1 1.9 MPa [9]. To extract latex from the tree, the vessels are opened by a process called tapping. A thin shaving of bark, about 1 mm thick, is removed with a sharp knife, to a depth very close to the cambium, but without injuring it. The tapping cut is made at an angle of approximately 30 to the horizontal from high left to low right. As latex vessels run in a spiral up the trunk at an angle of 27, this severs the maximum number of vessels for a given length of cut. As turgor pressure is maximum just before sunrise, tapping is carried out early in the morning. Tapping is done at regular intervals, working down the trunk. Laticiferous bark grows again behind the descending cut so that the process can be continued indefinitely. There are variations regarding length of tapping cut and frequency of tapping. Common systems are half spiral alternate days, i.e., a cut extending halfway around the circumference, made every other day. This is abbreviated as 1/2S d/2. As high intensity tapping systems are believed to cause problems such as tapping panel dryness (TPD) in high yielding clones, lower intensity tapping systems such as 1/2S d/3 and 1/2S d/4 are being recommended. Yield varies with the clone, age of the tree, fertility and moisture content of the soil, climatic conditions, tapping system followed, skill of the tapper, etc. A tree can be economically tapped for a period of 20

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Natural Rubber 25 years, after which it is slaughter tapped, i.e., intensively tapped for about 23 years before it is replanted. The first step in the tapping process is to peel off the coagulated rubber residue from the previous tapping before removing a shaving of bark. This is collected separately as tree lace. After tapping, latex flows down the cut and is channelled into a plastic/ ceramic cup through a short metal spout. The daily task of a tapper is usually 300400 trees, which is completed late in the morning. Then the cups are emptied into buckets and the latex is then carried to the collection centre or the processing factory. If there is any spillage of latex, it is left to coagulate and is collected occasionally as tree scrap or earth scrap. Very often the tree will still be yielding at the time of latex collection. In such cases, the collection cup after emptying, is replaced on the tree to receive the late drippings. At the time of the next tapping, this latex would have spontaneously coagulated and this is collected by the tapper as cup lump. The tree scrap, earth scrap, tree lace and cup lump together make the field coagulum, which constitutes around 20% of the crop. The remaining 80% is latex. It is possible to increase the yield of latex by the use of chemical preparations called yield stimulants. The most widely used stimulant is 2-chloroethylphosphonic acid (ethephon) which was first introduced by Abraham and others [10]. Ethephon releases ethylene gas on hydrolysis, which acts as the stimulant. Ethylene is thought to act by inhibiting the plugging process which causes the latex flow to stop. Tapping at reduced frequency along with a low level of stimulation using ethephon has been suggested as an effective approach to increase productivity per tapper and thus to reduce production costs [11].

2.5 Biosynthesis of rubber

Natural rubber consists of thousands of isoprene units linked together to form a polymer. The individual steps in the synthesis of rubber from sucrose are well established by Lynen [12] and the pathway is illustrated in Figure 2.1 [13]. There are three stages: (1) generation of acetyl-coenzyme A, (2) conversion of acetyl-coenzyme A to isopentenyl pyrophosphate (IPP) via mevalonic acid and (3) polymerisation of IPP to rubber. Sucrose in latex is the primary source of acetate and acetyl-CoA essential for the biosynthesis of rubber. Acetate forms the basic precursor of rubber synthesis in all rubber yielding plants. Hevea rubber differs from the majority of isoprenoid compounds in two respects. It has a high molecular weight, which varies from one hundred thousand to a few millions, and the geometric configuration around the double bond is exclusively cis 1, 4 [14].

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Rubber Technologists Handbook

Figure 2.1 Pathway of rubber biosynthesis (adapted from Moir, [13])

2.6 Composition of latex

Natural rubber latex is a colloid with a specific gravity of 0.96 to 0.98 and a pH in the range of 6.5 to 7.0. The dispersed phase is mainly rubber and the dispersion medium is water. However, in addition to rubber and water, latex contains small quantities of

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Natural Rubber prote i ns, res i ns i nclud i ng fats, fatty ac i ds, other l i p i ds, sterol and sterol esters, carbohydrates and mineral matter. The composition of field latex (latex as obtained from the tree) is given in Table 2.3. The dominant particulate constituent of fresh latex is the rubber hydrocarbon with a size ranging from 0.02 to 3.0 +m and shape mostly spherical and strongly protected in suspension by a film of adsorbed proteins and phospholipids [15, 16]. The other particles in latex comprise lutoids and Frey-Wyssling particles. The lutoids are subcellular membrane bound bodies ranging in size from 2 to 5 +m, containing a fluid serum known as B-serum, which is a destabiliser for rubber particles. Frey-Wyssling particles are spherical, larger in size and are yellow coloured. Quebrachitol (methyl-l-inositol), sucrose and glucose are the major carbohydrates in latex. Of the total protein content of fresh latex about 20% is adsorbed on the rubber particles, an equal quantity found in the B-serum and the remainder in the latex-serum. The adsorbed proteins and the phospholipids on the rubber particles impart a net negative charge, thereby contributing to the colloidal stability of latex. Lipids in fresh latex consist of fats, waxes, sterols, sterol esters and phospholipids. Lipids associated with the rubber and non-rubber particles in latex play a key role in the stability and colloidal behaviour of latex. Most of the classic amino acids have been found in latex. Nucleotides contained in latex are important as cofactors and are intermediates in the biosynthesis of rubber. Low molecular weight thiols such as glutathione and cysteine and ascorbic acid determine the redox potential of latex.

2.7 Crop collection

The crop is collected from plantations as latex and various forms of field coagulum. Generally latex accounts for about 80% of the crop, the rest being field coagulum. The proportion of the two forms depends on the age of the trees, tapping system, climatic

Table 2.3 Chemical composition of fresh latex

Constituent Rubber Proteins Resins Minerals Carbohydrates Water Percentage 3040 11.5 1.53.0 0.70.9 0.81.0 5560

chemical composition

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Rubber Technologists Handbook conditions, clone, stimulation, time of collection and stability of latex. Latex can be processed into ribbed sheets, pale latex crepe (PLC) or sole crepe, block or technically specified rubber (TSR) and speciality rubbers and preserved field latex and latex concentrate. Field coagulum is processed as crepe rubber or TSR. Flow of latex usually stops 2 to 3 hours after tapping. The presence of proteins and carbohydrates in latex causes it to coagulate prematurely through bacterial activity. The tendency for precoagulation can be prevented using anticoagulants. These are chemicals added to latex in small quantities for preventing precoagulation for short periods. The most popular anticoagulants are ammonia, formalin and sodium sulphite. The usual dosages are 0.01, 0.02 and 0.05% in latex for ammonia, formalin and sodium sulph i te, respect i vely. Hydroxylam i ne neutral sulphate along w i th ammon i a i s recommended as anticoagulant for latex to be used for the production of constant viscosity (CV) rubber. The preferred anticoagulant is sodium sulphite if the latex is meant for sheet rubber or PLC. The different forms of field coagulum also need proper handling. Tree lace and cup lump are collected in baskets carried by the tappers. In high yielding trees, the quantity of cup lump is generally more. Field coagula are sorted and stored separately. It is preferable to process them fresh. This ensures proper dirt removal and better colour for the processed rubber. When field coagulum is to be stored, it is partially dried in smoke. Exposing it to direct sunlight or soaking in water for long periods accelerates degradation. Earth scrap is collected once a year or once in six months and may contain high levels of dirt. Latex to be processed into sheet, PLC or light coloured block rubber is brought to the processing factory as early after collection as possible. In small and medium rubber estates, field latex is carried to the factory by the tappers themselves. Large estates have latex collection centres at suitable locations in the estate. The latex brought by the tappers is weighed and collected in a bulking tank in the collection centre and suitable anticoagulants are added. Latex intended for concentration is preserved using ammonia or low ammonia-tetramethylthiuram disulphide (TMTD)-zinc oxide (LATZ) system.

2.7.1 Pre-processing of latex

Latex brought to the factory is sieved and collected in a large bulking tank. Sieving is necessary to remove contaminants such as bark shavings, leaves, sand and small clots of rubber. Stainless steel sieves of 40 and 60 mesh size are preferred. As it is necessary to find out the rubber content of latex for its further processing, dry rubber content (DRC) is measured quickly using a metrolac (hydrometer).

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Natural Rubber

2.8 Crop 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 preserved field latex and concentrated latex, ribbed smoked sheet (RSS) and air dried sheet (ADS), block rubber or TSR, PLC and estate brown crepe (EBC) and other low grade crepes made from field coagulum.

2.8.1 Preservation and concentration of latex

A number of rubber products such as gloves, condoms, 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. Apart from being a bactericide, ammonia enhances the colloidal stability of latex and deactivates certain harmful metal ions. For effective preservation of latex, ammonia is used at a concentration of 0.7 to 1.0% by weight. During storage, the higher fatty acid esters present in latex are hydrolysed into ammonium soaps, which improves the mechanical stability of latex. Though ammonia is the most effective preservative for NR latex, its pungent smell, the low zinc oxide stability of latex and longer gel time of latex foams are disadvantages. But attempts to preserve latex entirely without ammonia have not been successful. However, many low ammonia preservative systems have been developed, in which the concentration of ammonia has been reduced to around 0.2% and supplemented with secondary preservatives such as zinc diethyldithiocarbamate, a TMTD-zinc oxide combination of boric acid, etc. Of these, a combination of 0.2% ammonia, 0.0125% each of TMTD and zinc oxide and 0.05% of lauric acid (LATZ system) is the most popular. The process of latex concentration involves removal of a substantial quantity of serum from field latex, thus making latex richer in rubber. The main reasons for concentration of latex include a preference for high DRC by the consuming industry, economy in transportat i on and pur i f i cat i on of latex . The ma j or processes employed for the concentration of NR latex include evaporation, electrodecantation, creaming and centrifuging. Evaporation involves the removal of water only. Hence the ratio of nonrubber constituents to rubber and the particle size distribution remain unaffected. On

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Rubber Technologists Handbook the other hand, the other three processes involve the partial removal of non-rubber constituents and smaller rubber particles. Because of this, the range of particle size is reduced and a higher degree of purity is obtained. Centrifuging and creaming are more popularly used for the production of concentrated latex. In any dispersion, the dispersed particles cream or sediment under the influence of gravity. In the case of latex the rubber particles, being lighter than serum, tend to cream up. The velocity of creaming depends upon a number of factors and can be deduced approximately from Stokes Law [17], stated mathematically as 2g (Ds Dr) r 2 V = 9d where V is the velocity of creaming (m/s) g is the acceleration due to gravity (m/s2) Ds, Dr are the densities of serum and rubber particles, respectively (g/cm3) r is the effective radius of the particle (m) and d is the coefficient of viscosity of serum (Pa-s) In the creaming process, the creaming agent such as sodium alginate, forms an adsorbed layer over the rubber particles which reduces the Brownian movement and the intensity of the negative electric charge on the particle surface, thereby promoting temporary agglomeration of particles. Thus the effective size of the particle increases, favouring faster creaming. In the centrifugal process, when the latex enters the machine, rotating at a high speed of around 7000 rpm, the centrifugal force, which is several thousands greater than the gravitational force, replaces g and causes instantaneous separation of the latex into cream and skim. In creaming, the skim is almost clear serum and is therefore discarded. However, in the centrifugal process, the skim contains 38% rubber, which is recovered by coagulation using dilute sulphuric acid and processed as skim rubber, which is a low quality rubber. However, methods have been developed to improve the quality of skim rubber [18]. Natural rubber latex concentrate is marketed to strict technical specifications. The current ASTM specifications for latex concentrates are reproduced in Table 2.4.

2.8.2 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. Even today RSS is the predominant form of NR in countries such as Thailand and

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Natural Rubber

Table 2.4 Requirements for specified latex types (ASTM D1076-97) [19]
Type 1 Total solids, min, % Dry rubber content (DRC), min, % Total solids content minus dry rubber content, max, % Total alkalinity calculated as ammonia, as % on latex Sludge content, max, % Coagulum content, max, % KOH number, max Mechanical stability, S, min Copper content, max, % of total solids Manganese content, max, % of total solids Colour on visual inspection Odour after neutralisation with boric acid 61.5 60.0 2.0 0.60 min 0.10 0.050 0.80 650 0.0008 0.0008 A B Type 2 66.0 64.0 2. 0 Type 3 61.5 60.0 2.0

0.55 min 0.29 max 0.10 0.050 0.80 650 0.0008 0.0008 A B 0.10 0.050 0.80 650 0.0008 0.0008 A B

A - No pronounced blue or grey B - No putrefactive odour Type 1 - Centrifuged natural latex preserved with ammonia Type 2 - Creamed natural latex preserved with ammonia Type 3 - Centrifuged natural latex preserved with low ammonia with secondary preservatives

India. Fresh field latex after sieving and bulking, is diluted to 12.5 to 15% DRC. Dilution improves the colour and transparency of the sheet and makes the sheeting operation easier, and allows denser impurities in latex to sediment on standing for 1015 minutes. Sodium bisulphite is added to latex at the rate of 1.2 g per kg DRC to prevent the surface discoloration on wet sheet, occurring through enzyme catalysed oxidation of phenolic components in latex. Para-nitrophenol (PNP) is added to the latex at the rate of 1 g per kg DRC to prevent mould growth on the sheet surface during prolonged storage in humid weather. The diluted latex is then transferred to coagulation tanks or pans and coagulated with dilute formic or acetic acid. These acids are preferred on account of their volatile nature and being noncorrosive to the equipment used. However, because of their relatively high cost, alternative coagulants such as sulphuric acid and sulphamic acid have been recommended to be used under controlled conditions [20, 21, 22]. After a few hours, or the next day, the

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Rubber Technologists Handbook thick slab of coagulum is squeezed using a set of rollers to remove water and make it into sheet of approximately 3 mm thickness. The final set of rollers is grooved to introduce ribbed markings on the sheets. The ribbed markings increase its surface area and facilitate drying. The wet sheets are soaked in a 0.1% solution of PNP for a few minutes, if the latter has not been added to latex before coagulation. The sheets are then allowed to drip for a few hours before loading into the smoke house for drying. 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. Partial drying under the sun followed by smoke drying is practised widely in small holdings. Several types of smoke houses such as those with a furnace inside or outside the drying chamber, batch type or continuous type are in operation [23]. The temperature in the different regions of the smoke house is maintained in the range of 4060 C. The sheets are held on wooden or bamboo rods used for holding sheets in a smoke house (beroties) placed on trolleys which move on a central rail track in a large tunnel type smoke house. In smaller types of smoke houses, the beroties are placed on a framework inside the chamber. Drying of the sheets takes four to six days in a smoke house. The dried sheets are visually examined and graded adopting the norms prescribed by the International Rubber Qual i ty and Pack i ng Conference under the Secretar i at of the Rubber Manufacturers Association Incorporated and described in the Green Book. Grading is done on the basis of colour, transparency, presence of mould, oxidised spots, blisters, bubbles, dirt, sand and other foreign matter, degree of drying, tackiness, etc. 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. Dried sheets are packed by grade into bales of 111 kg. Wrapping of bales may be done on all sides with the same or higher grade of rubber. These bare back bales are coated with talc to prevent bale-to-bale adhesion. Appropriate markings about the manufacturer, grade, etc., of the rubber are stencilled on the bales, before these are shipped.

2.8.3 Pale latex crepe 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. It is preferred in products for which a light colour is important. Pale crepes are made from latex of selected rubber clones such as PB 86, RRIM 600, etc., which give relatively white latex containing minimum `carotenes and are less susceptible to enzymic discoloration. The latex is collected without any precoagulation and if necessary, sodium sulphite may be used as an anticoagulant. The latex is then bulked

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Natural Rubber and diluted to a DRC of 20 and the yellow pigments are bleached with 0.05% of tolyl mercaptan or its water soluble alkali metal salt [24, 25]. Alternatively, the pigments are removed by fractional coagulation. A small quantity of acetic acid or oxalic acid (approximately 1 g per kg DRC) is added to the latex which is stirred well and then allowed to remain undisturbed for 1 to 2 hours. About 10% of the rubber coagulates, and the coagulum carries the bulk of the `carotenes. The coagulum is removed and the remaining fraction of latex is processed further. In practice, a combination of bleaching and fractional coagulation is used. The treated latex is then coagulated and set into slabs which are passed several times through crepe rollers with liberal washing. The resultant thin crepes, 12 mm thick, are dried in hot air at about 3335 C for about two weeks. 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.

2.8.4 Field coagulum crepe

Among the various field coagulum materials, cup lump and tree lace 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. The selected field coagulum is soaked in water to make it soft and to remove surface dirt and is then thoroughly cleaned by passing through a battery of crepe rollers. Proper blending is carried out on the rollers to ensure uniformity. Simultaneously thorough washing is done by providing running water in every crepe roller. The crepe is dried in drying sheds at ambient or slightly elevated temperature. 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.

2.8.5 Technically specified rubbers (TSR)

The disadvantages of the conventional forms of NR such as RSS and crepes became more evident with the advent of synthetic rubbers which were marketed in compact, uniform

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Rubber Technologists Handbook and medium-sized bales wrapped in plastic film and with technical specifications to suit the requirements of the manufacturing sector. This has necessitated R&D efforts to market NR also in more attractive forms. Consequently new methods of processing and presentation were developed to market NR as technically specified rubber in compact bales, wrapped in polyethylene film and graded adopting technical specifications. Technically specified rubbers are now being produced in almost all NR producing countries and are marketed under different names (Table 2.5). The advantages of TSR include assurance of quality for important technical parameters, consistency in quality, minimum space for storage and clean and easy to handle packing. This method enables NR producers to process both latex and field coagulum using almost the same set of machinery and to minimise the processing time to less than 24 hours. Although different methods were developed to produce TSR, all these processes involve certain common steps such as coagulation of latex, processing of field coagulum, size reduction, drying, baling, testing, grading and packing. Differences among commercial processes lie in the method of coagulation or in the machinery used for crumbling the coagulum. Typical flow diagrams for processing of latex and field coagulum into TSR are given in Figure 2.2. The major challenge in TSR production is ensuring consistency in quality [26]. Introduction of a slab cutter or pre-breaker in the initial size reduction stage, use of macro- and microblending tanks, transfer of raw materials from one tank to another while under motion by bucket elevator system and loading of final crumbs to the drier boxes with a slurry pump through a vibrating perforated screen and hopper are some of the recent developments in TSR production aimed at improving consistency and reducing cost.

Table 2.5 Nomenclature of TSR in different countries

Country Malaysia Indonesia Thailand India Sri Lanka Singapore Papua New Guinea Nomenclature Standard Malaysian Rubber (SMR) Standard Indonesian Rubber (SIR) Standard Thai Rubber (STR) Indian Standard Natural Rubber (ISNR) Sri Lanka Rubber (SLR) Standard Singapore Rubber (SSR) Papua New Guinea Classified Rubber (PNGCR)

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Natural Rubber

Figure 2.2 Flow diagram for processing latex and field coagulum into technically specified rubber Since its introduction in the early 1960s, the specifications for TSR have been revised several t i mes depend i ng upon the requ i rements of the consum i ng i ndustry. The specifications as per the latest revisions adopted by ASTM are given in Table 2.6 [27]. The development of TSR has helped the rubber plantation industry to improve the competitive position of NR by improving the quality of rubber and its consistency and introducing more efficient processing methods to meet the consumer requirements.

2.9 Modified forms of NR

With the development of synthetic rubbers, the monopoly enjoyed by NR until then, in the elastomer market was broken. Subsequently, a complex balance of technical properties and cost emerged as the decisive factor in its usage. Over and above the development of TSR, different special forms of NR have evolved to make it suitable for certain specific applications. Even before the 19391945 War, NR was found suitable for different types

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NR technical grades specification Rubber Technologists Handbook

Table 2.6 Specification for NR technical grades (ASTM D2227-96)

Property Dirt retained on 45-micron sieve, max, % Ash, max, % Nitrogen, max, % Volatile matter, max, % Initial plasticity, P0, min. Plasticity retention index, PRI, min, % Colour, Lovibond scale, max. Mooney viscosity, ML(1+4) 100 C Rubber grade L 0.05 0.60 0.60 0.80 30 60 6.0 CV 0.05 0.60 0.60 0.80 60 60 5 5 0.05 0.60 0.60 0.80 30 60 10 0.10 0.75 0.60 0.80 30 50 20 0.20 1.00 0.60 0.80 30 40 -

L: light colour CV: constant viscosity The numbers 5, 10, 20 indicate the maximum permissible dirt content in the grade

of chemical modification, leading to the production of a number of polymeric materials of very interesting properties. Although many such materials lost their significance consequent to the development of totally synthet i c counterparts, some are st i ll technologically important. Moreover, the limited availability of petroleum-based feed stocks and the increasing awareness of the relevance of renewable and environmentfriendly resources such as NR, have caused renewed interest in the development of modified forms of NR [28]. Natural rubber can be modified by physical and/or chemical means. Figure 2.3 gives an outline of the major modifications of NR. Some of these such as viscosity stabilised rubber, superior processing rubber, have been produced commercially. The commercial significance of the others depends mostly on emerging market forces.

2.9.1 Physically modified forms

The physical methods of modification of NR involve incorporation of additives which do not chemically react with rubber. The additives include various rubber compounding ingredients and polymers such as synthetic rubbers and thermoplastics. Some of the commercially important materials in this group are described in the following sections.

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Natural Rubber

Figure 2.3 Modification of NR

2.9.1.1 Oil extended natural rubber (OENR)

This contains 20 to 25 phr of aromatic or naphthenic oil and is produced either in the latex stage [29] or in the dry rubber stage [30]. Extension in the latex stage is effected by adding an aqueous emulsion of the oil into latex followed by acid coagulation and processing into block rubber. In general, increasing oil content reduces tensile strength and resilience, but the vulcanisates retain good tear resistance and possess high wear resistance when blended with butadiene rubber. OENR also shows good skid resistance on wet surfaces when used in tyre tread.

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2.9.1.2 Thermoplastic natural rubber (TPNR, see also Chapter 4)

Thermoplastic natural rubber blends are prepared by blending NR and polyolefines, particularly polypropylene and polyethylene in varying proportions. As the ratio varies, mater i als w i th a w i de range of propert i es are obta i ned . Rubber-r i ch blends are thermoplastic elastomers while those with lower rubber content are impact-modified plastics. The mechanical properties of rubberthermoplastic blends depend on the proportion of the rubber and thermoplastic components. In order to get reasonably good mechanical properties, the hard phase must be continuous. The soft phase, providing elastic properties, need not be continuous, provided it is sufficiently small and adheres to the matrix under stress. The elastic properties of TPNR are considerably improved if the rubber phase is partially crosslinked during mixing, a process called dynamic vulcanisation. The effect is pronounced in relatively soft blends. The blends are prepared in internal mixers at temperatures above the melting point of the plastic component. After blending the material is immediately sheeted and then granulated. TPNR is more resistant to heat ageing than NR vulcanisates. Ozone resistance of TPNR is also very high [31]. The soft grades of TPNR can replace vulcanised rubber and flexible plastics for applications in footwear, sports goods, seals and mountings and a wide range of moulded and extruded goods. The automotive industry is the largest potential market for the hard grades in applications such as automotive bumpers and body protection strips.

2.9.1.3 Deproteinised natural rubber (DPNR)

This is a purified form of NR with low protein and mineral content. The proteins and other hydrophilic non-rubbers can absorb moisture leading to reduction in modulus and electrical resistance and increase in stress relaxation and creep. Absorption of water by unvulcanised rubber can affect its degree of crosslinking and other cure characteristics. Deproteinisation of NR reduces moisture sensitivity thereby improving consistency and modulus. The general method of deproteinisation involves treating the latex with an enzyme preparation followed by dilution and coagulation. The enzyme hydrolyses the proteins into water soluble forms which are then washed away during subsequent processing [32].

2.9.2 Chemically modified forms of NR

Being an unsaturated organic compound, natural rubber is highly reactive and several chemical reactions can be carried out in NR resulting in materials having entirely different properties. These reactions can take place by the attachment of pendant functional groups,

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Natural Rubber grafting of different polymers along the rubber molecule or through intra-molecular changes. The products of the reactions possess properties which are different from those of NR and therefore, can find use in applications where other materials are being used. Some of the important chemically modified forms of NR are described in the next sections.

2.9.2.1 Constant viscosity (CV) rubber

NR undergoes hardening during storage especially under low humidity. The increase in viscosity is caused by a crosslinking reaction involving the randomly distributed carbonyl groups on the rubber molecule [33]. The reaction can be prevented by the addition of small quantities of hydroxylamine salts to the latex before coagulation. The rubber so treated retains its original viscosity for a long time and is marketed as CV rubber. The controlled and stable viscosity favours easy and uniform processing. Premastication can be minimised or even avoided. This form of rubber is available mostly in the Mooney viscosity range of 6065. Stabilisation of viscosity is evaluated by an accelerated storage hardening test. The increase in initial plasticity should be less than eight units.

2.9.2.2 Graft copolymer rubbers

Graft copolymers are prepared from natural rubber by polymerising vinyl monomers either in latex or in solution. Methyl methacrylate (MMA) and styrene are the common monomers used for grafting onto NR. Poly(methyl methacrylate) (PMMA) graft NR has been commercially produced since the mid-1950s in Malaysia. Generally, grafting can be achieved using free radical initiation by chemical method or by irradiation. MMA graft NR is a self-reinforcing agent for NR with which it is compatible in all proportions. The graft rubber or its blends with NR can be compounded and vulcanised in the same way as rubber. The vulcanisates have excellent physical properties at high hardness levels with good hardness retention at elevated temperatures and good electrical properties. The major use of the MMA graft copolymer is in adhesives. It gives exceptionally good bond strength for bonding NR onto PVC which is particularly useful in the footwear industry. The adhesive property can also be exploited in tyre cord dipping. Polystyrene is also grafted onto NR by polymerising styrene in NR latex. Various levels of modification can be achieved according to the proportion of grafted polystyrene. The modified rubber can be blended with NR, compounded and vulcanised in the usual manner. The graft rubber containing 50 parts of styrene (SG 50) is used in microcellular soles in place of high styrene grade of SBR.

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2.9.2.3 Epoxidised natural rubber (ENR)

The mechanical properties of NR are superior to those of most synthetic rubbers. However, with regard to special properties such as oil resistance and gas permeability, NR is inferior to the special purpose synthetic rubbers. Baker and others [34] and Gelling [35] reported that epoxidation of NR in the latex stage, under controlled conditions, gives epoxidised NR with improved resistance to hydrocarbon oils, low permeability to air, increased damping and good bonding properties while retaining the high strength properties of NR. Improvement in these properties depends on the degree of epoxidation and two grades of ENR with 25 and 50 mole% epoxidation (ENR 25 and ENR 50) have gained commercial importance. ENR is produced from NR latex by performic acid formed in situ by the reaction of formic acid with hydrogen peroxide [35, 36]. The reaction is carried out under carefully controlled conditions to avoid secondary ring opening reactions. The epoxide groups are randomly distributed along the NR backbone and ENR retains the stereoregular cis-1,4 configuration of NR. A wide range of applications are envisaged for ENR including accessories for milking machines, pharmaceutical and food contact applications, shoe soles, floor coverings and high damping engine mountings. ENR 50 or its blends with suitable rubbers can be used in inner tubes for bicycles and light agricultural vehicles. ENR has considerable potential in adhesives and sealants. Varkey and others [37] have reported that ENR can be used as a reinforcement modifier for silica filled rubber vulcanisates.

2.9.2.4 Superior processing (SP) rubber

This is an intimate mixture of vulcanised and unvulcanised rubber obtained by mixing vulcanised latex with normal latex in the desired proportions, before coagulation. It can be compounded in a similar manner to ordinary grades of NR with little loss of physical properties of the final vulcanisates. Improved processing characteristics and the ability to retain dimensional stability make it an ideal material for calendered and extruded products. The SP rubber that contains 20 parts of vulcanised and 80 parts of unvulcanised NR is termed SP 20 and is generally used to replace NR completely. SP 80 contains 80 parts of vulcanised rubber and 20 parts of unvulcanised rubber. When one part of SP 80 is blended with three parts of NR, the resultant material is equivalent to SP 20. Superior processing rubbers can be used with great advantage in extrusion processes, especially at lower filler loading due to its low die swell, less affected by extrusion conditions and better surface finish and higher stock viscosities permitting easier handling and better open-steam curing characteristics. It also allows use of a wider range of extrusion temperatures and roll speeds for smooth extrusion leading to increased

30

Natural Rubber productivity. The superior processing quality and better extrusion properties of SP rubber [38] can also be imparted to synthetic rubbers like ethylene-propylene-diene terpolymer (EPDM) by blending in suitable proportions [39].

2.10 Properties of natural rubber

Natural rubber is a high molecular weight polymer having the chemical structure, cis1,4 polyisoprene. The raw rubber contains, in addition to the rubber hydrocarbon, small quantities of proteins, fats, fatty acids, carbohydrates, mineral matter. The rubber hydrocarbon content is about 94%. The physical and chemical properties of the rubber are influenced by the presence of the non-rubber substances. The properties of NR depend very much upon the degree of crosslinking. Therefore, the important properties of the raw and vulcanised rubber are discussed separately.

2.10.1 Raw rubber

Being a linear long chain polymer, NR is composed of molecules of different sizes. The weight average molecular weight ( M w ) of NR ranges from 30,000 to about 10 million. A random blend would have an M w of about 2 x 106 and a number average weight ( M n ) of 5 x 105. Subramaniam [40] demonstrated that the molecular weight distribution (MWD) of unmasticated NR is distinctly bimodal. The clonal variation in molecular weight and MWD was also studied by Subramaniam [41]. A small portion of the rubber undergoes crosslinking even in the latex present within the latex vessels of the tree. The usual concentration of this microgel is 730% and influences the melt viscosity of the rubber. The gel content of raw NR which has been stored for some time is much higher and is known as macrogel, and is responsible for the increased viscosity during storage. The presence of certain active chemical groups such as carbonyl groups on the rubber chain is believed to cause formation of branched chains. Mastication reduces the gel content. The rheological properties of NR are strongly influenced by long chain branching. The slow rate of stress relaxation of Hevea rubber compared to guayule and synthetic polyisoprene rubber has been attributed to chain branching [42]. Storage of NR at subzero temperatures causes stiffening of the rubber and the maximum rate of crystallisation occurs at 24 C. Such stiffened rubber requires thawing at 40 50 C before processing. The temperature at which the last traces of crystallinity disappears is described as the melting temperature, Tm. Although a value of 28 C has been assigned for the Tm of NR, values of 30 C and higher depending on storage temperature and duration, have been occasionally reported.

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Rubber Technologists Handbook All polymeric materials will, at some temperature, undergo a glass transition (Tg), and change from a glassy to a rubbery state. Specific volume measurements on NR have established a Tg of 72 C. While carbon black has relatively little influence on Tg of NR, plasticisers depress it considerably and crosslinking increases it.

2.10.1.1 Processing properties

The processing characteristics of NR are considered to be excellent. Although it is tough and nervy at temperatures below 100 C, it breaks down easily to a workable viscosity. The normal fabrication techniques can easily be adopted for NR. Although premastication is not required for the viscosity stabilised grades, mastication is commonly practised for the normal grades. The efficiency of mastication is temperature dependent and is the least at around 100 C [43]. Chemical peptisers allow mastication to be carried out at lower temperatures and are useful for increasing the efficiency of mastication. Rubbers with high initial viscosity tend to break down faster mostly due to the high shearing forces realised. The break down behaviour also depends on the plasticity retention index (PRI) of the rubbers and it is generally found that latex grades with high PRI values break down more slowly than field coagulum grades. It is observed that because of the faster break down behaviour of NR compared to SBR, the average viscosity of a NR mix during mixing is lower than that of a similar SBR mix, although the initial viscosity is much higher for NR. This leads to lower energy consumption for mixing the NR compound. The batch viscosity is the main factor controlling die swell and the stress developed while extruding a fully mixed compound. Thus viscosity is a useful guide to assess the processing behaviour of masticated rubbers. A masticated rubber has better extrusion properties than an unmasticated rubber of the same viscosity. The most important aspects of processability of NR are its high inherent tack and green strength. These two characteristics are of utmost importance in the manufacture of products such as tyres. Tack is important as it holds the compounds of green tyre together until moulding. Green strength is needed so that the uncured tyre will not creep and hence distort excessively before moulding or tear during the expansion that occurs upon moulding. A practical definition of tack is the ability of two similar materials to resist separation after they are brought into contact for a short time under a light pressure. The higher tack of NR compared to SBR has been attributed to its greater ability to flow under compressive load and its higher green strength. NR is an ideal material for developing high tack. It can be processed to a low viscosity and still maintain high green strength. Furthermore, the mechanism responsible for high green strength is strain crystallisation which is not active in the bond formation stage and hence does not interfere with contact and interdiffusion, but rather develops upon stretching.

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Natural Rubber

2.10.2 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 of vulcanised NR are discussed in the following sections.

2.10.2.1 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. This is undoubtedly due to its ability to undergo strain-induced crystallisation. The tensile strength of NR vulcanisates frequently exceeds 30 MPa, which is almost ten times the values reported for gum vulcanisates of non-crystallising rubbers such as styrene butadiene rubber (SBR) under similar test conditions. The effect of reinforcing fillers on the tensile strength of NR vulcanisates is not as significant as in the case of non-crystallising rubbers. Temperature is found to influence the tensile strength of NR gum vulcanisates significantly and there is a critical temperature of around 100 C, above which the strength falls abruptly, crystallisation being suppressed at that temperature. However, tensile strength of filler-reinforced NR vulcanisates is found to be less temperature dependent. Strength of NR is also characterised in terms of tear resistance. Over wide ranges, the catastrophic tearing energy is insensitive to rate and temperature for a crystallising rubber like NR [44]. It appears that in such materials the effect of crystallisation which can induce substantial hysteresis at high strains, overshadows viscoelastic effects. It is also observed that tear resistance is greatly increased by reinforcing fillers.

2.10.2.2 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. These mechanisms have been reviewed by Gent and Pulford [45]. 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

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Rubber Technologists Handbook 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.

2.10.2.3 Resistance to skidding

This is important in applications such as tyre tread. In tread compounds of the same hardness, skid resistance depends on viscoelastic properties. The highly resilient NR compounds show lower skid resistance than SBR compounds at temperatures above 0 C. The wet skid resistance of NR above 0 C can be improved by extending with oil. Treads from OENR are as good as oil extended styrene-butadiene rubber (OESBR) on wet roads and are superior on icy roads [46]. OENR blended with butadiene rubber is most suitable for treads of winter tyres.

2.10.2.4 Dynamic properties

The crack growth behaviour and fatigue of rubber vulcanisates are intimately related. The strain dependence of fatigue life of different elastomers vary widely. NR is very good at high strains, compared with non-crystallising elastomers. The difference is more pronounced under non-relaxing conditions. For a crystallising rubber, the much larger enhancement is attributed also to an effective increase on the threshold energy required for crack initiation and a reduction in the rate of growth once the threshold energy is exceeded. It is also known that the threshold energy for NR increases substantially if atmospheric oxygen is excluded and/or if certain antioxidants are incorporated in the compound. This behaviour is reflected in enhanced life, particularly in the region of the fatigue limit, that is the strain below which the fatigue life of elastomers is very long. Frequency of deformation is found to have very little influence on the fatigue life of NR vulcanisates. The effect of temperature on crack growth and fatigue is also found to be much less for NR than for non-crystallising elastomers. Resistance to crack growth can be increased by fine particle size fillers, the effect being attributable to blunting of the crack tip due to branching. The resilience of NR vulcanisates is very high, with values exceeding 90% in well-cured gum vulcanisates. However, the values, in general, are 1 2% lower than those of synthetic cis-1,4 polyisoprene, the difference being attributed to the presence of proteins in NR. In carbon black-filled vulcanisates the difference is negligible. Good resistance to flexing and fatigue together with high resilience makes NR useful in applications where cyclic stressing is involved.

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Natural Rubber

2.10.2.5 Creep, stress relaxation and set

One of the notable features of NR, compared with most other elastomers, is its good elastic behaviour. This means low creep and low stress relaxation. If the stress relaxation rate is expressed as per cent stress relaxation per decade of time, a typical NR gum vulcanisate may give a value of about 2% per decade. If carbon black is present, the rate will be higher, about 7% per decade for a 70 IRHD rubber containing 50 phr of a nonreinforcing black. However, pre-stressing of such a filled rubber can reduce the stress relaxation rate to little more than the gum value. This superior elastic behaviour of NR is a consequence of the high mobility of the molecules, which is also reflected in the relatively low glass transition temperature. Stress relaxation rates are substantially independent of the type or amount of deformation, but creep rates depend on both the rate of stress relaxation and the load-deflection characteristics. In tension the creep rate may reach double the rate of stress relaxation. In shear it is about the same and on compression it is lower. Measurement of set under compression provides a practical evaluation of either the creep or the stress relaxation of rubber and has been very useful for those purposes where a high degree of precision is not required. Compression set and creep are poorer in NR than in synthetic polyisoprene. This is mostly due to the presence of non-rubber constituents. In this respect DPNR is found to be better than the normal grades of NR. A high state of cure is found to reduce set. Creep, stress relaxation and set are important in load bearing applications such as springs. Partly because of this NR is the most widely used rubber in this field.

2.10.2.6 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 antidegradants 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. A small amount of 1 2% of combined oxygen in rubber serves to render it useless for most applications. The oxidation of rubber is believed to take place through a free-radical chain reaction. In

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Rubber Technologists Handbook order to prevent extensive degradation of rubber, it is necessary to interrupt the chain reaction and stop autocatalysis. This could be accomplished by either terminating the free radicals or by decomposing the peroxides into harmless products. Antioxidants, in fact, function this way. Amine antioxidants act both by reacting with free radicals and by decomposing peroxides. Phenolic antioxidants, on the other hand, react primarily as free radical sinks or chain stoppers. Phosphites react readily with free peroxides. The attack by oxygen on raw rubber is different from that on vulcanised rubber. In the former case an initial induction period is followed by rapid uptake of oxygen. With vulcanised rubber, there is no induction period and oxygen uptake is essentially linear with time. The net result of oxygen attack on NR is an overall decrease in all properties [47]. Heavy metal ions such as copper, manganese and iron and peroxides catalyse oxidative ageing of rubber and these are called pro-oxidants. Some of the standard antioxidants, notably the aromatic diamines are effective against metal catalysed oxidation of rubber. The effect of heat and oxygen on rubber are never separated and the practical result of heat ageing on rubber is a combination of crosslinking and an increase in the rate of oxidation. Ozone reacts readily with NR and the effect manifests itself as cracks on the surface perpendicular to the direction of stress and as a silvery film on the surface in unstressed rubber. The mechanism of ozone attack is thought to involve the reaction of ozone with the double bonds in rubber to form ozonides. These are easily decomposed to break the double bond, and under strain, cracks appear which become deeper as the reaction proceeds. Two factors influencing the rate of ozone cracking are ozone concentration and the strain in the rubber. Protection of NR stocks from ozone cracking is accomplished using antiozonants. Under static conditions physical antiozonants such as wax which forms a surface bloom can be used. Under dynamic conditions, waxes are unsuitable and hence, chemical antiozonants are employed. Blending of NR with a more saturated rubber such as EPDM has also been found to be effective in protecting NR from ozone attack [48]. Some of the important physical constants of unvulcanised and vulcanised NR are summarised in Table 2.7.

2.11 Vulcanisation
Compounding is the process of formulating NR for its final application. Vulcanisation is the most important aspect of NR processing. This is generally achieved by reaction with sulphur and accelerators at an elevated temperature. Vulcanisation transforms the linear polymer into a three-dimensional macromolecule by the insertion of a relatively few crosslinks between the polymer chains. Other aspects of compounding include incorporation of additives to protect rubber from degradation, addition of fillers to reinforce the rubber and to reduce cost, addition of oils to improve processing. Some of the requirements can

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physical constants Natural Rubber

Table 2.7 Physical constants of natural rubber*

Property Density, Mg.m-3 Coefficient of volume expansion, ` = (I/V) (bV / bT), (C)-1 Glass transition temperature, C Specific heat, Cp, Cal.g-1 (C)1 Thermal conductivity, W.m-1 (C)-1 Heat of combustion, J kg-1 Equilibrium melting temperature, C Heat of fusion of crystal, kJ.kg-1 Refractive index, nD Dieletric constant (1 kHz) Dissipation factor (1 kHz) * The figure in parentheses indicate the range Unvulcanised 0.913 (0.9060.916) 670 x 10-6 72 (74 to 69) 0.449 0.134 4.52 x 106 28 64.0 1.5191 2.372.45 0.0010.003 1.5264 2.68 0.0020.04 Pure gum vulcanisate 0.970 (0.9201.000) 660 x 10-6 63 (72 to 61) 0.437 0.153 4.44 x 106

even be conflicting and hence it is often necessary to arrive at a compromise. Over the last few decades considerable progress has been achieved in understanding the science of compounding NR, which has been reviewed by Crowther et al [49].

2.11.1 Vulcanisation with sulphur

As per the generally accepted mechanism of reaction of sulphur with NR, the first step is the formation of an active sulphurating agent from sulphur, accelerators and activators [50]. After abstracting a hydrogen atom from the rubber, a polysulphidic rubber-bound intermediate is formed which initially forms polysulphidic crosslinks. The polysulphide in the crosslinks and network-bound accelerator fragments shorten at a rate depending on the ratio of sulphur to accelerator, the cure temperature and time. Vulcanisation systems us i ng a h i gh rat i o of accelerator to sulphur wh i ch g i ve predom i nantly monosulphidic crosslinks are called efficient vulcanisation (EV) systems. Those using

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Rubber Technologists Handbook low ratio are known as conventional vulcanisation systems. A compromise between the two systems is also used as a semi-EV system. The structure of the crosslinks and the extent and type of main chain modifications have important effects on the physical properties of a vulcanisate. High levels of polysulphidic crosslinks confer high tensile and tear strength particularly in unfilled vulcanisates. High resistance to fatigue is also obtained together with high resilience and high elastic recovery at ambient temperature. However, resistance to heat and oxidation is limited as is resistance to set at elevated temperatures. In contrast, monosulphidic crosslinks give rise to high thermal stability and resistance to oxidation and reversion. However, EV vulcanisates possess marginally reduced strength, but exhibit substantially improved resistance to creep, stress relaxation and set at elevated temperature. The rate of low temperature crystallisation of such vulcanisates is higher than that of conventional vulcanisates, due to the low level of main chain modification.

2.11.2 Non-sulphur vulcanisation

These systems are reviewed by Kemperman [51] and are of far less industrial significance. Of the many systems investigated, only two have achieved practical significance, vulcanisation with organic peroxides and urethane. Vulcanisation by organic peroxides such as dicumyl peroxide, is a free radical process. The effective crosslinking can take place in the complete absence of oxygen, otherwise peroxy radicals would be formed leading to the oxidation of the rubber. Peroxide vulcanisation is, therefore, limited to products made by press moulding. The structure of peroxide vulcanisate is relatively simple compared with that of a sulphur vulcanisate, as rubber chains are crosslinked by simple carbon-carbon linkages, which are highly stable towards heat. Therefore, these vulcanisates possess extremely good thermal ageing characteristics, superior to those of even EV systems, and also lower compression set at elevated temperature. However, fatigue resistance and resistance to low temperature crystallisation are low. Another major disadvantage of the peroxide system is its lack of processing safety. Urethane vulcanising systems available under the trade name Novor, developed by Baker [52] are now being used in a variety of applications, particularly in those demanding high temperature vulcanisation and service. The crosslinks formed are mainly of the urea-urea type. The principal benefits of these systems are outstanding reversion resistance and good ageing resistance, coupled with good physical properties. It is also possible to use these systems in combination with sulphur vulcanisation to give a range of systems designed to vary in cost, cure behaviour and properties.

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Natural Rubber

2.12 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. Consumption of NR in major countries is shown in Table 2.2. Since the development of synthetic rubbers and their large-scale production since the 19391945 World War, the share of NR in the total elastomer consumption decreased from 100% in 1940 to almost 30% in 1978. However, its share has increased since then and at present is nearly 40%. This increase is mostly attributed to the large-scale switch over to radial tyre construction in the major rubber consuming countries. A higher proportion of NR is necessary in the manufacture of radial tyres. The increase in the relative price of synthetic rubbers compared to NR has also contributed to the increase in the share of NR in the overall elastomer consumption.

2.12.1 Tyres (see also Chapter 11)

Use of NR is preferred in tyres because of its high strength combined with high elasticity and outstanding tack and green strength. The repeated deformation of a tyre as it runs, together with distortion arising from acceleration, braking and particularly cornering, causes energy dissipation in the tyre because of imperfect elasticity. This leads to considerable temperature rise, which is naturally higher in the interior of the tyre and increases with increasing tyre size. Damage caused by overheating is generally separation between carcass and tread and constitutes catastrophic failure. At high temperatures, maintenance of adhesion between the plies of carcass and breaker (restraining belt of rubber and reinforcing fabric, placed around the edge of a tyre carcass to provide increased lateral stiffness and improved control and steering properties to an otherwise flexible radial tyre) and to the adjacent parts of the tyre is very important. This and the excellent tack of NR are the main reasons for the use of at least a portion of NR in the carcass. Generally a blend of NR and SBR is used in the carcass of a passenger tyre, the proportion of NR in radial tyre carcass being higher. To keep heat generation within acceptable limits, the rubber in carcass and breaker must have high resilience. In current practice a minimum of 30% NR is used in the carcass of radial passenger tyres. The formulation of carcass rubbers appears to be a compromise between technical and economic considerations. The carcass of truck tyres contains more NR and the proportion varies between 50 and 100%. The rubber in the carcass of earthmover and other giant tyres is almost exclusively NR. Aircraft tyres carry a

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Rubber Technologists Handbook heavy load for their size and suffer severe service conditions, especially when landing and hence their carcass is almost entirely NR. In a tyre, sidewalls are the most strained elements and are susceptible to flex cracking and ozone cracking. The sidewalls of radial tyres flex more than those of bias ply tyres and their formulation must take account of this fact. The flex-cracking behaviour of NR is better than SBR at higher strains and therefore, sidewalls of radial tyres incorporate substantial proportions of NR. The main requirements for treads are resistance to wear, to skidding on wet and icy surfaces and to groove cracking at the bottom of the tread profile. The thick treads of truck tyres contribute very well to heat build-up and impose an additional condition on the choice of rubber. Tread wear depends on the ambient temperature and on the severity of service and magnitudes of these two factors depend on the tread material. NR treads wear less than SBR treads at low temperature. However, when the overall tread wear ratings are considered, NR is inferior to SBR. However, blends of OENR and BR are found to be competitive with SBR-based treads of passenger tyres. Truck tyres and offthe-road tyres are exposed to coarse mechanical damage, in which large chunks of tread are torn and removed. Resistance to this type of chipping and chunking calls for high resistance to tear which can be met only by NR. The proportion of NR in the treads of large commercial tyres increases with size and roughness of service and treads made entirely of NR are not uncommon. Treads of aircraft tyres are made entirely from NR. Skid resistance of tyres is important for safety. On wet roads, skid resistance increases with the hysteresis of the tread compound and for this SBR has been preferred to NR in passenger tyres. Here again oil extension has greatly improved the position of NR and NR/BR blends. 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.

2.12.2 Engineering applications

Most engineering applications of NR involve its use as a spring. The main reasons for using NR in springs are: 1. Excellent resistance to fatigue, cut growth and tearing, 2. High resilience, 3. Low creep, 4. Low heat build-up,

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Natural Rubber 5. Reasonably good bonding with metals/fibres, 6. Wide temperature range of use, 7. Low cost, and 8. Good processability. 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. Although NR is highly resilient, the small amount of inherent hysteresis serves to dampen resonant vibrations. 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.

2.12.3 Conveyor beltings

Top grade conveyor beltings can be made from NR except for those used in underground mines (problems of inflammability). In belt manufacture good tack and adhesion are very important. Good control of compound viscosity is also important in the proper compaction of the belt carcass. 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.

2.12.4 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. 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 [53]. 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 environment.

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Rubber Technologists Handbook

References
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