Vulcanised Rubbers

Sulphur is used in the manufacture of matches and fireworks, as a dust insecticide and for vulcanising rubber. Most of the world supply of sulphur, however, is used for the manufacture of sulphuric acid (p. 296). 

Diselenium dichloride acts as a solvent for selenium. Similarly disulphur dichloride is a solvent for sulphur and also many other covalent compounds, such as iodine. S Clj attacks rubber in such a way that sulphur atoms are introduced into the polymer chains of the rubber, so hardening it. This product is known as vulcanised rubber. The structure of these dichlorides is given below ... 

In the lightly cross-linked polymers (e.g. the vulcanised rubbers) the main purpose of cross-linking is to prevent the material deforming indefinitely under load. The chains can no longer slide past each other, and flow, in the usual sense of the word, is not possible without rupture of covalent bonds. Between the crosslinks, however, the molecular segments remain flexible. Thus under appropriate conditions of temperature the polymer mass may be rubbery or it may be rigid. It may also be capable of ciystallisation in both the unstressed and the stressed state. 

A substantial part of the market for the ethylene-vinyl acetate copolymer is for hot melt adhesives. In injection moulding the material has largely been used in place of plasticised PVC or vulcanised rubber. Amongst applications are turntable mats, base pads for small items of office equipment and power tools, buttons, car door protector strips and for other parts where a soft product of good appearance is required. Cellular cross-linked EVA is used in shoe parts. 

It is somewhat difficult conceptually to explain the recoverable high elasticity of these materials in terms of flexible polymer chains cross-linked into an open network structure as commonly envisaged for conventionally vulcanised rubbers. It is probably better to consider the deformation behaviour on a macro, rather than molecular, scale. One such model would envisage a three-dimensional mesh of polypropylene with elastomeric domains embedded within. On application of a stress both the open network of the hard phase and the elastomeric domains will be capable of deformation. On release of the stress, the cross-linked rubbery domains will try to recover their original shape and hence result in recovery from deformation of the blended object. 

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. 

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. 

It was pointed out in Chapter 3 that conventional vulcanised rubbers were composed of highly flexible long chain molecules with light cross-linking... 

In general, the thermoplastic elastomers have yet to achieve the aim of replacing general purpose vulcanised rubbers. They have replaced rubbers in some specialised oil-resistant applications but their greatest growth has been in developing materials of consistency somewhat between conventional rubbers and hard thermoplastics. A number of uses have also been developed outside the field of conventional rubber and plastics technology. 

If polypropylene is too hard for the purpose envisaged, then the user should consider, progressively, polyethylene, ethylene-vinyl acetate and plasticised PVC. If more rubberiness is required, then a vulcanising rubber such as natural rubber or SBR or a thermoplastic polyolefin elastomer may be considered. If the material requires to be rubbery and oil and/or heat resistant, vulcanising rubbers such as the polychloroprenes, nitrile rubbers, acrylic rubbers or hydrin rubbers or a thermoplastic elastomer such as a thermoplastic polyester elastomer, thermoplastic polyurethane elastomer or thermoplastic polyamide elastomer may be considered. Where it is important that the elastomer remain rubbery at very low temperatures, then NR, SBR, BR or TPO rubbers may be considered where oil resistance is not a consideration. If, however, oil resistance is important, a polypropylene oxide or hydrin rubber may be preferred. Where a wide temperature service range is paramount, a silicone rubber may be indicated. The selection of rubbery materials has been dealt with by the author elsewhere. ... 

Vulcanised rubbers possess a range of very desirable properties such as resilience, resistance to oils, greases and ozone, flexibility at low temperatures and resistance to many acids and bases. However, they require careful (slow) processing and they consume considerable amounts of energy to facilitate moulding and vulcanisation. These disadvantages led to the development of thermoplastic rubbers (elastomers). These are materials which exhibit the desirable physical characteristics of rubber but with the ease of processing of thermoplastics. 

These materials have characteristics of both rubbers and thermoplastics. At room temperature they behave like cross-linked rubbers, but at elevated temperatures the cross-links effectively disappear (they are said to be heat fugitive) and the material may be processed as a thermoplastic. Unlike truly cross-linked (vulcanised) rubbers, these materials may be capable of disolution in solvents, although not necessarily at room temperature. 

Copper and silver tarnish readily in sulphide atmospheres, and copper in contact with sulphur-vulcanised rubber will sometimes react with the sulphur, devulcanising it in the process. The growth of conducting sulphide whiskers on silver is noteworthy as these whiskers may give rise to short circuits across silver-plated contacts. Ammonia has little effect on most metals, but traces will tarnish many copper alloys and cause stress-corrosion cracking of certain stressed brasses. 

Pastor-Bias M.M. and Martm-Martmez J.M., 2002, Different surface modifications produced by oxygen plasma and halogenation treatments on a vulcanised rubber, J. Adhes. Sci. Technol., 16(4), 409 28. 

Ortiz-Magan A.B., Pastor-Bias M.M., Eerrandiz-Gomez T.P., Morant-Zacares C., and Martfn-Martfnez J.M., 2001, Surface modifications produced by N2 and O2 RF-plasma treatment on a synthetic vulcanised rubber. Plasmas Polym., 6(1,2), 81-105. 

Groupes PEUGEOT SA et RENAULT, Quantitative Evaluation of Constituents in Vulcanised Rubbers by Means ofTG, Methode d Essai D40/1753 (March 1991). 

Conventional rubber compound analysis requires several instrumental techniques, in addition to considerable pretreatment of the sample to isolate classes of components, before these selected tests can be definitive. Table 2.5 lists some general analytical tools. Spectroscopic methods such as FTIR and NMR often encounter difficulties in the analysis of vulcanised rubbers since they are insoluble and usually contain many kinds of additives such as a curing agent, plasticisers, stabilisers and fillers. Pyrolysis is advantageous for the practical analysis of insoluble polymeric materials. 

Deformulation of vulcanised rubbers and rubber compounds at Dunlop (1988) is given in Scheme 2.3. Schnecko and Angerer [72] have reviewed the effectiveness of NMR, MS, TG and DSC for the analysis of rubber and rubber compounds containing curing agents, fillers, accelerators and other additives. PyGC has been widely used for the analysis of elastomers, e.g. in the determination of the vulcanisation mode (peroxide or sulfur) of natural rubbers. 

Scheme 2.3 Dunlop s deformulation of vulcanised rubbers. After Schnecko and Angerer [72]. Reproduced by permission of Hiithig GmbH...

Stabilisers are usually determined by a time-consuming extraction from the polymer, followed by an IR or UV spectrophotometric measurement on the extract. Most stabilisers are complex aromatic compounds which exhibit intense UV absorption and therefore should show luminescence in many cases. The fluorescence emission spectra of Irgafos 168 and its phosphate degradation product, recorded in hexane at an excitation wavelength of 270 nm, are not spectrally distinct. However, the fluorescence quantum yield of the phosphate greatly exceeds that of the phosphite and this difference may enable quantitation of the phosphate concentration [150]. The application of emission spectroscopy to additive analysis was illustrated for Nonox Cl (/V./V -di-/i-naphthyl-p-phcnylene-diamine) [149] with fluorescence ex/em peaks at 392/490 nm and phosphorescence ex/em at 382/516 nm. Parker and Barnes [151] have reported the use of fluorescence for the determination of V-phenyl-l-naphthylamine and N-phenyl-2-naphthylamine in extracted vulcanised rubber. While pine tar and other additives in the rubber seriously interfered with the absorption spectrophotometric method this was not the case with the fluoromet-ric method. 

Any method of vulcanising rubber products which proceeds without interruption from start to finish as compared to the method of vulcanising separate batches of products or sections of a product. Continuous vulcanisation processes include the cold curing of proofed cloth, the vulcanisation of belting and flooring, of cables and certain extruded products by either the Liquid Curing Medium, Fluid Bed, Microwave, or Hot Air techniques. 

An instrument for the determination of the hardness of vulcanised rubber. The name is usually, but not necessarily, applied to a pocket-type instrument made by the Shore Instrument and Manufacturing Co. Inc. The use of the term in the sense of hardness (a durometer of 60°) is not recommended. 

When the curve of a particular property (usually tensile strength) of vulcanised rubber plotted against time of vulcanisation shows a levelling off or only a slow fall after the maximum has been reached, the compound or compounding ingredient under test is said to be flat curing, to have flat curing characteristics or to show a plateau effect. 

An instrument for the measurement of heat buildup in vulcanised rubber by a forced vibration method. 

A dulling of the surface of vulcanised rubber articles considered to result from the action of atmospheric ozone, particularly in conditions of high humidity. It is quite different from blooming. 

A method of determining the stiffening of vulcanised rubber at low temperatures by submitting the rubber to torsion, as in BS 903-A13. 

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