Ebonite Rubber

Since the discovery of piezoelectricity on certain asymmetrical crystals like quartz by J. and P. Curie in 1880, the piezoelectricity of various crystals has been extensively studied on account of its importance in science and technology (Cady, 1964 Mason, 1950). Early work on the piezoelectricity of polymeric materials is found in the paper by Brain (1924) who investigated the piezoelectricity of various dielectrics including ebonite, rubber, and celluloid. In 1965, Harris (1965), Allison (1965), and Hauver (1965) investigated both experimentally and theoretically the shock-induced polarization of plastics. 

Do not yield ebonite rubbers with high sulphur loadings. 

The anode gaskets and rings are of soft and ebonite rubber, respectively. The inlet box is of rubber lined mild steel construction having a feed brine (sodium chloride) distributor and mercury seal. 

Since the flow causes sliding abrasion at a low angle of incidence in the piping, the rubber which can be suggested for this application is a low durometer hardness (40 on the Shore A scale) natural rubber. For lower flow rates at ranges of 1,200 litres per minute up to 4,000 litres per minute, a hard rubber or a semi-ebonite rubber can be used since the abrasive wear of the finely meshed particles will be negligible. 

Many moulded components are affixed on the rubber-lined surface such as anode sleeves in mercury cells used in caustic soda industry. These moulded components are either made from natural soft or ebonite rubbers or Neoprene rubber compounds. While moulding, the flow characteristics of the rubber compound and shrinkage need to be taken into consideration. Some aspects of mould designs are described next. 

In extensions of this work on vulcanisation, which normally involved only a few per cent of sulphur, both Goodyear and Hancock found that if rubber was heated with larger quantities of sulphur (about 50 parts per 100 parts of rubber) a hard product was obtained. This subsequently became known variously as ebonite, vulcanite and hard rubber. A patent for producing hard rubber was taken out by Nelson Goodyear in 1851. 

In this chapter brief consideration has been given to the major tonnage mbbers. Derivatives of natural mbber such as ebonite are discussed in Chapter 30 and thermoplastic rubbers are reviewed in Chapter 31. Other important speciality mbbers (with their ASTM designations) include ... 

The resins act as a plasticiser during processing but they cross-link while the rubber is vulcanising to give a harder product with improved oxidation resistance, oil resistance and tensile strength. The addition of sufficient resin will lead to an ebonite-like product. 

The detailed structure of ebonite is not known but it is believed that the same structures occur in the rigid material as have been suggested for vulcanised rubber. There will, however, be far more S-containing structures per unit volume and the ratios of the various structures may differ. The curing reaction is highly exothermic. 

Ebonite compositions may be prepared without difficulty either in an internal mixer or on a two-roll mill. In addition to the rubber and sulphur, fillers are invariably present in commercial mixes. These materials have the important function of diluting the rubber phase. Because of this the exotherm will be... 

The ebonite compound before cure is a rather soft plastic mass which may be extruded, calendered and moulded on the simple equipment of the type that has been in use in the rubber industry for the last century. In the case of extruded and calendered products vulcanisation is carried out in an air or steam pan. There has been a progressive reduction in the cure times for ebonite mixes over the years from 4-5 hours down to 7-8 minutes. This has been brought about by considerable dilution of the reactive rubber and sulphur by inert fillers, by use of accelerators and an increase in cure temperatures up to 170-180°C. The valuable effect of ebonite dust in reducing the exotherm is shown graphically in Figure 30.3. 

Figure SO.3. Variation of internal temperature during cure of ebonite stocks containing 0, 20, 50 and 100 parts of ebonite dust per 100 parts (rubber and sulphur). (After Scott, see bibliography)...

Ebonite, or hard rubber as it is often known, is black in colour and has a specific gravity, in the absence of mineral fillers, of about 1.18. 

The terms ebonite and hard rubber are now extended to cover hard produets made from synthetic rubbers. SBR is now replacing the natural materials in many ebonite applications whilst nitrile rubber ebonites are of interest where oil resistance is required. 

Hard products may also be made by vulcanising rubber (natural or synthetic) using only about two parts of sulphur per 100 parts of rubber. In these cases either the so-called high-styrene resins or phenolie rubber compounding resins are ineorporated into the formulation. These compounds are processed using the methods of rubber technology but, like those of ebonite, the produets are more akin to plastics than to rubbers. Examples of the usage of these materials are to be found in battery boxes, shoe heels and ear washer brushes. 

Ebonite media are manufacmred from partially vulcanized rubber, which is crushed, pressed and vulcanized. These media are resistant to acids, salt solutions and alkalies. They may be used for filtration at temperamres ranging from -10 to + 110 C. 

Soft rubber is obtained by adding 2-4% sulfur by adding extra sulfur (25-40%), the rubber can be made into ebonite, which is a hard, brittle material, having a wider range of chemical resistance than soft rubber. Soft ordinary rubber is chemical and erosion resistant, but its thermal resistance is not high (about 80 C). 

Standard butyl rubber, which is a copolymer of isobutylene with about 2% of isoprene vulcanises in the same manner as natural rubber but, as it only contains a small proportion of polyisoprene, the cross-link percentage is much reduced. It is therefore not possible to make ebonite from a butyl rubber. The same vulcanisation chemistry, with some modifications, applies to ethylene-propylene terpolymers and brominated butyl rubber. 

Polychloroprene and acrylonitrile-butadiene rubber compounds have satisfactory chemical resistance but, except for phosphoric acid, are not suitable for mineral acids at higher concentrations. However, they have good resistance to oils, acrylonitrile-butadiene rubber being the better, and so are often used in oil-contaminated aqueous environments. Generally, abrasion resistance is only fair. Normal maximum working temperature is about 100°C. Acrylonitrile-butadiene rubber ebonites are sometimes used especially where solvent contamination occurs, but are normally very brittle and so should be used with care. 

Unless test coupons are produced alongside the lining, the only method of testing the vulcanisation state is with a hand hardness meter. A Shore A or IRHD meter is used for soft rubber linings and a Shore D meter for ebonites. The usual specification is that the hardness has to conform to 5° of the specified hardness. There is no quantitative non-destructive test for the strength of the bond between the lining and the substrate and so such tests are usually carried out in the laboratory on a sample prepared from the materials used. 

Initially, vulcanization was accomplished by heating elemental sulfur at a concentration of 8 parts per 100 parts of rubber (phr) for 5 h at 140°C. The addition of zinc oxide reduced the time to 3 h. Accelerator in concentrations as low as 0.5 phr have since reduced time to 1-3 min. As a result, elastomer vulcanization by sulfur without accelerator is no longer of commercial significance. An exception is the use of about 30 or more phr of sulfur, with httle or no accelerator, to produce molded products of hard mbber called ebonite. 

Butyl Rubber and Halo-Butyl Rubber Ethylene Propylene Rubber (q) Hard Rubber (Ebonite) (h) Soft Natural Rubber (h) Neoprene (i) Nitrile Rubber Chlorosulphonated Polyethylene Polyurethane Rubber (v) Silicone Rubbers (k)... 

Natural rubber which has been reduced to an easy flowing consistency by prolonged mastication in the presence of peptising agents. Suitably compounded, DPR may be cast into moulds and vulcanised ebonite products from DPR are also possible. 

Also known as vulcanite and (mainly in the USA) hard rubber . The hard, horn-like product obtained when natural rubber and some synthetic rubbers such as nitrile (NBR) are vulcanised with a high proportion of sulphur or organic nonsulphur vulcanising agent. Butyl rubber and polysulphide rubber do not form ebonites. Ebullioscopy... 

A form of cellular rubber in which the cells are non-intercommunicating, self-contained units. It has low thermal conductivity. Expanded rubber is buoyant and does not absorb water and was therefore initially used in both the soft rubber and ebonite forms in the construction of lifebuoys and other marine buoyancy equipment. The most commonly used polymer is now polyurethane for both flexible and rigid systems. 

To convert an elastomer into ebonite, the glass transition temperature, Tg, has to be raised to above 20 °C, or above the operating temperature of the product, in order to remain rigid in use. This is achieved by crosslinking the rubber with a large amount of sulphur. Typically, 25 to 50 phr is used for natural rubber ebonites. Ebonites can be produced from NR, BR, IR, SBR and NBR. Rubbers with low unsaturation, e.g., HR and EPDM, do not form ebonites. 

Ebonite dusts are used in the production of ebonite compounds to minimise and control the exothermic reaction of the crosslinking of large volumes of sulphur with diene rubbers. 

Gelatin film, steel, cadmium, bismuth, lead, silk, aluminum (oxidized), de Khotinsky cement, nickel. Norway iron, bees wax, ebonite disk, sheet rubber EM... 

Both linear and branched polymers are typically thermoplastics, meaning they can be melted before they undergo decomposition. However, cross-linked three-dimensional or network polymers are thermosets, meaning they decompose before they melt. The crosslink density can vary from low, such as found in a rubber band, to high, such as found in ebonite (Figure 2.3). 

Which has the higher cross-linked density (a) ebonite or (b) soft vulcanized rubber ... 

Which would tend to be more crystalline when stretched (a) unvulcanized rubber or (b) ebonite ... 

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