Elastomers extensibility

New methods have been proposed, which allow one to estimate the concentration dependence of liquid diffusion in elastomer and strain dependence of equilibrium swelling ratio under conditions of symmetric biaxial elastomer extension in terms of kinetic and strain curves of swelling. 

Polymer systems have been classified according to glass-transition temperature (T), melting poiat (T ), and polymer molecular weight (12) as elastomers, plastics, and fibers. Fillers play an important role as reinforcement for elastomers. They are used extensively ia all subclasses of plastics, ie, geaeral-purpose, specialty, and engineering plastics (qv). Fillets are not, however, a significant factor ia fibers (qv). 

Elongation. The extension produced by a tensile stress appHed to an elastomer, ie, elongation, is almost always reduced by fillers. Regardless of what type of filler is used, elongation decreases with increased loading above approximately 5 vol % (13). 

Low Temperature Properties. The property of solvent resistance makes fluorosihcone elastomers usefiil where alternative fluorocarbon elastomers cannot function. The abiHty to retract to 10% of their original extension after a 100% elongation at low temperature is an important test result. Eluorosihcones can typically pass this test down to —59°C. The brittle point is approximately —68°C. 

Hydrocarbon resins are used extensively as modifiers in adhesives, sealants, printing inks, paints and varnishes, plastics, road marking, flooring, and oil field appHcations. In most cases, they ate compounded with elastomers, plastics, waxes, or oils. Selection of a resin for a particular appHcation is dependent on composition, molecular weight, color, and oxidative and thermal stabiHty, as weU as cost. A listing of all hydrocarbon resin suppHers and the types of resins that they produce is impractical. A representative listing of commercially available hydrocarbon resins and their suppHers is included in Table 6. 

Flame and Smoke Retardants. Molybdenum compounds are used extensively as flame retardants (qv) (93,94) in the formulation of halogenated polymers such as PVC, polyolefins, and other plastics elastomers and fabrics. An incentive for the use of molybdenum oxide and other molybdenum smoke and flame retardants is the elimination of the use of arsenic trioxide. Although hydrated inorganics are often used as flame retardants, and thought to work by releasing water of crystallization, anhydrous molybdenum oxides are effective. Presumably the molybdenum oxides rapidly form... 

Polypropylene sheet has been used most extensively however, thermoplastic polyester, polycarbonate, and nylon versions are available (see Elastomers, synthetic Polycarbonates). Continuous strand glass fiber mat is the typical reinforcement. The limited number of sheet suppHers reduces potential for competitive pricing. 

Principal uses include automotive V-belts, industrial and hydraulic hose, specialty roofing, heels and soles in footwear, wine coveting, and a wide variety of coated fabric uses, eg, rafts. Chloroprene elastomers are also used extensively in adhesives (qv). It is estimated that about 77,000 t of chloroprene are used each year in the United States. The two main suppHers of chloroprene elastomers in the United States are DuPont and Bayer. In addition, Distiguil (France) sells polymers through the A. Schulman Company. 

DuPont—Dow is the primary suppHer of these polymers. There is an estimated 18,000 t of these elastomers used per year. The main uses of CPE are in constmction, automotive, and electrical appHcations. These include power steering hose, electrical cords used in low voltage appHcations (extension cords, ignition wire), pond liners, and as a plastic modifier to improve impact modification. 

Epichlorohydrin. Commercial polyester elastomers include both the homopolymer and the copolymer of epichl orohydrin with ethylene oxide. The very polar chloromethyl groups create basic resistance to oil for these polymers, and they have been extensively used in fuel lines however, the desire for lower fuel permeation is causing a search to be made for other polymers (10) (see Elastomers, synthetic-polyethers). 

There are seven principal classes of accelerators and several miscellaneous products that do not fit into these classes. In addition, many proprietary blends of several accelerators are sold which are designed as cure packages for a specific appHcations. Choosing the best cure system is a responsibiUty of the mbber chemist and requites extensive knowledge of each accelerator type and its appHcabiUty in each elastomer. Table 5 shows a rule of thumb comparison of the scorch/cure rate attributes for the five most widely used classes of accelerators used in the high volume diene-based elastomers. 

Tellurium dimethylthiocarbamate in combination with mercaptoben2othia2ole, with or without tetramethylthiuram disulfide, is the fastest known accelerator for butyl mbber. It is used extensively in butyl tubes for buses and similar vehicles and in other butyl appUcations (see Elastomers, synthetic Rubber, natural). 

The amine groups thus formed can also react vigorously with the isocyanate groups to continue the chain extension and cross-linking reactions. Hence, ia the systems there are simultaneous foaming, polymerization, and cross-linking reactions, which produce foam elastomers (or plastics). 

Pinch The industrial equivalent of controlling flow bv pinching a soda straw is the pinch valve, Mves of this tvpe use fabric-reinforced elastomer sleeves that completely isolate the process fluid from the metal parts in the valve. The valve is actuated bv applying air pressure directly to the outside of the sleeve, causing it to contract or pinch. Another method is to pinch the sleeve with a linear actuator with a specially attached foot. Pinch valves are used extensively for corrosive material service and erosive sliirrv senice. This type of valve is used in applications with pressure drops up to 10 bar (145 psi),... 

An extensity factor—the total amount of surface area of filler per unit volume in contact with the elastomer. 

In addition to the somewhat sophisticated triblock thermoplastic elastomers described above, mention should be made of another group of thermoplastic diene rubbers. These are physical blends of polypropylene with a diene rubber such as natural rubber. These may be considered as being an extension to the concept of thermoplastic polyolefin rubbers discussed in Section 11.9.1 and although extensive experimental work has been carried out with these materials they do not yet appear to have established themselves commercially. 

In Chapters 3 and 11 reference was made to thermoplastic elastomers of the triblock type. The most well known consist of a block of butadiene units joined at each end to a block of styrene units. At room temperature the styrene blocks congregate into glassy domains which act effectively to link the butadiene segments into a rubbery network. Above the Tg of the polystyrene these domains disappear and the polymer begins to flow like a thermoplastic. Because of the relatively low Tg of the short polystyrene blocks such rubbers have very limited heat resistance. Whilst in principle it may be possible to use end-blocks with a higher Tg an alternative approach is to use a block copolymer in which one of the blocks is capable of crystallisation and with a well above room temperature. Using what may be considered to be an extension of the chemical technology of poly(ethylene terephthalate) this approach has led to the availability of thermoplastic polyester elastomers (Hytrel—Du Pont Amitel—Akzo). 

The water reaction evolves carbon dioxide and is to be avoided with solid elastomers but is important in the manufacture of foams. These reactions cause chain extension and by the formation of urea and urethane linkages they provide sites for cross-linking, since these groups can react with free isocyanate or terminal isocyanate groups to form biuret or allophanate linkages respectively (Figure 27.5). 

It may also be argued that plasticised PVC may be considered as a thermoplastic elastomer, with the polymer being fugitively cross-linked by hydrogen bonding via the plasticiser molecules. These materials were, however, dealt with extensively in Chapter 12 and will not be considered further here. The ionomers are also sometimes considered as thermoplastic elastomers but the commercial materials are considered in this book as thermoplastics. It should, however, be kept in mind that ionic cross-linking can, and has, been used to fugitively crosslink elastomeric materials. 

JKR type mea.surement.s on monolayers depo.sited on. soft elastomers. The recent interest in the JKR experiments has been stimulated by the work of Chaudhury and coworkers [47-50J. In a 1991 paper, Chaudhury and White-sides [47] reported their extensive studies on the measurement of interfacial work of adhesion and surface energies of elastomeric solids. The motivation for this work was to study the physico-organic chemistry of solid surfaces and interfaces. 

TPEs are materials that possess, at normal temperatures, the characteristic resilience and recovery from the extension of crosslinked elastomers and exhibit plastic flow at elevated temperatures. They can be fabricated by the usual techniques such as blow molding, extrusion, injection molding, etc. This effect is associated with certain interchain secondary valence forces of attraction, which have the effect of typical conventional covalent crosslinks, but at elevated temperatures, the secondary... 

For over a century plastics have successfully competed with other materials in old and new applications providing cost-performance advantages, etc. In fact within the plastic industry there is extensive competition where one plastic competes with another plastic. Examples include many such as thermoplastic elastomers vs. thermoset... 

International plastics selector , 9th edition, Int. Plastics Selector, San Diego, CA (1987). Thermoplastics, thermosets, elastomers, and key property areas critical to plastics are extensively specification defined. 

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