Elastomers oxidative conditions

Figure 13.8 TG thermogram for the non-oxidative degradation of a 25 mg sample of Sylgard 184 silicone elastomer from 25-800°C at a heating rate 10°C min-1 under non-oxidative conditions. The onset of degradation was determined to be 410°C. A total -36% by wt of the material was volatilized in a two-stage process.

Thermal Oxidative Stability. ABS undergoes autoxidation and the kinetic features of the oxygen consumption reaction are consistent with an autocatalytic free-radical chain mechanism. Comparisons of the rate of oxidation of ABS with that of polybutadiene and styrene—acrylonitrile copolymer indicate that the polybutadiene component is significantly more sensitive to oxidation than the thermoplastic component (31—33). Oxidation of polybutadiene under these conditions results in embrittlement of the mbber because of cross-linking such embrittlement of the elastomer in ABS results in the loss of impact resistance. Studies have also indicated that oxidation causes detachment of the grafted styrene—acrylonitrile copolymer from the elastomer which contributes to impact deterioration (34). 

Peduoropolyethers, which constitute special class of fluoropolymer, are useful as lubricants,1 elastomers,2 and heat-transfer fluids under demanding conditions. Several commerical products are available, which are generally prepared by ring-opening polymerization of hexafluoropropylene oxide or by the random copolymerization oftetrafluoroethylene and hexafluoropropylene with oxygen under ultraviolet irradiation.3 Direct fluorination of hydrocarbon ethers has been reported4 but must be done very slowly under carefully controlled... 

Processing Stability. As with elastomers or other rubber modified polymers, the presence of double bonds in the elastomeric phase increases sensitivity to thermal oxidation either during processing or end use. Antioxidants are generally added at the compounding step to ensure retention of physical properties. Physical effects can also have marked effects on mechanical properties due to orientation, molded-in stress, and the agglomeration of dispersed rubber particles under very severe conditions. Proper drying conditions are essential to prevent... 

Perfluoroelastomers (FFKM), such as KALREZ, are particularly suited for extreme service conditions. They are resistant to more than 1,500 chemical substances, including ethers, ketones, esters, aromatic and chlorinated solvents, oxidizers, oils, fuels, acids, and alkali and are capable of service at temperatures up to 316°C (600°F).55 Because of the retention of resilience, low compression set, and good creep resistance, they perform extremely well as static or dynamic seals under conditions where other materials, such as metals, FKM, PIPE and other elastomers, fail. Parts from FFKM have very low outgassing characteristics and can be made from formulations, which comply with FDA regulations.56 Primary areas of application of perfluoroelastomers are paint and coating operations, oil and gas recovery,... 

Of all the known elastomers, polyorganosiloxane elastomers are the most resistant to weather effect they are insensitive to oxidation with oxygen in air and ozone, as well as to UV rays. That is why they do not age even in veiy harsh conditions. E.g., if natural rubber decomposes under the influence of ozone within 5 minutes at 20 °C and within 6 seconds at 100 °C, polydimethylsiloxane elastomer does not decompose even after 60 minutes in ozone at 100 °C. If heated in air to 320 °C, elastomers based on polydimethylsiloxanes, polydimethyl(metylphenyl)siloxanes, etc. only slowly oxidise on the other hand, natural rubber and synthetic organic elastomers decompose at once. 

The largest-volume polyether used is obtained from propylene oxide polymerized under basic conditions. Polyester polyols are produced from a number of different materials involving diacids and diols to give the ester linkage. Aliphatic polyesters generally are used for elastomers to impart chain flexibility. 

The main problem is related to exposure of these materials to high temperatures in the presence of oxygen. These conditions favor the oxidative degradation of the elastomer, which leads to opposing changes in its structure. On the one hand, chain scission can occur, and on the other hand, cross-links can be generated. If chain scission dominates, the hardness and modulus of the elastomer will decrease. If, however, cross-links are generated, both the hardness and the modulus increase and the strain at fracture will decrease. Other mechanical properties are altered by an increase in... 

Inorganic additives for rubber compounds also include materials that enhance performance under various accelerated stress conditions. Zinc oxide is an effective heat stabilizer for some types of elastomers. Iron oxide, lead compounds, barium salts, and specially treated clays, such as kaolinite, add performance margin in wet aging conditions. 

The time accelerated aging method for electric wires and cables requires a high dose rate irradiation, but the exposure to polymer in air results only the oxidation of surface when the dose rate is higher. I previously reported the methodology study of time accelerated irradiation of elastomer (2). The study showed two appropriate methods, one was irradiation in pressurized oxygen at room temperature the other was irradiation at 70°C in air. The article studied the effect of higher dose (up to 10 MGy) irradiation on ethylene-propylene-diene elastomer (EPDM) by using the time accelerated method. Irradiation at 70°C in air was chosen as the time accelerated irradiation condition because of the experimental convenience. 

Starting with the silicone elastomer hydrocephalus shunt in 1955, silicone elastomer has become widely used as a soft, flexible, elastomeric material of construction for artificial organs and implants for the human body. When prepared with controls to assure its duplication and freedom from contamination, specific formulations have excellent biocompatibility, biodurability, and a long history of clinical safety. Properties can be varied to meet the needs in many different implant applications. Silicone elastomer can be fabricated in a wide variety of forms and shapes by most all of the techniques used to fabricate thermosetting elastomers. Radiopacity can be increased by fillers such as barium sulfate or powdered metals. It can be sterilized by ethylene oxide, steam autoclave, dry heat, or radiation. Shelf-life at ambient conditions is indefinite. When implanted the host reaction is typically limited to encapsulation of... 

Factors involved in the selection of vulcanization systems must include the type of elastomer, type and quantity of zinc oxide and fatty acid, rate of vulcanization, required resistance to fatigue, and service conditions. It is also recommended that use of nitrosamine-generating accelerators be avoided. 

The solvent should be stable under all foreseeable operating conditions it should neither decompose nor oxidize, and it must not attack any of the materials of construction of the plant. When organic solvents are being used, care must be taken in choosing the correct gasket materials most common types of rubber and many synthetic elastomers, for example, swell and disintegrate after prolonged contact with chlorinated hydrocarbons. 

In addition, there are thermoplastic polyester elastomers. These are produced by equilibrium melt transesteiification of dimethyl terephthalate, 1,4-butanediol, and a poly(tetramethylene oxide) glycol (molecular weight about 10(X)). Because equilibrium conditions exist in the melt, the products are random copolymers ... 

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