Fluorocarbons thermal stability

Thermal degradation studies of EB-cured terpolymeric fluorocarbon rubber [430] by nonisothermal thermogravimetry in the absence and presence of cross-link promoter TMPTA reveal that thermal stability is improved on radiation and more so in the presence of TMPTA. Initial decomposition temperature, maximum decomposition temperature and the decomposition... 

Several classes of polymers including epoxies have been developed from 2-phenyl-l,l,l,3,3,3-hexafluoropropan-2-ol and its derivatives.1 Fluorinated epoxy resins are the key intermediates for the new types ofpractical organic coatings and plastics, which have fluorocarbon properties and convenient characteristics such as hydrophobicity, oleophobicity, light stability, low friction, and, in some cases, possibly high thermal stability. 

Fluorocarbon elastomers represent the largest group of fluoroelastomers. They have carbon-to-carbon linkages in the polymer backbone and a varied amount of fluorine in the molecule. In general, they may consist of several types of monomers poly-vinylidene fluoride (VDF), hexafluoropropylene (HFP), trifluorochloroethylene (CTFE), polytetrafluoroethylene (TFE), perfluoromethylvinyl ether (PMVE), ethylene or propylene.212 Other types may contain other comonomers, e.g., 1,2,3,3,3-pentafluropropylene instead of HFP.213 Fluorocarbon elastomers exhibit good chemical and thermal stability and good resistance to oxidation. 

If solid polymer objects are fluorinated or polymer particles much larger than 100 mesh are used, only surface conversion to fluorocarbon results. Penetration of fluorine and conversion of the hydrocarbon to fluorocarbon to depths of at least 0.1 mm is a result routinely obtained and this assures nearly complete conversion of finely powdered polymers. These fluorocarbon coatings appear to have a number of potentially useful applications ranging from increasing the thermal stability of the surface and increasing the resistance of polymer surfaces to solvents and corrosive chemicals, to improving friction and wear properties of polymer surfaces. It is also possible to fluorinate polymers and polymer surfaces partially to produce a number of unusual surface effects. The fluorination process can be used for the fluorination of natural rubber and other elastomeric surfaces to improve frictional characteristics and increase resistance to chemical attack. 

The high-molecular-weight perfluoropolyethers obtained in the first step have excellent thermal stability (TGA initial decomposition >370°C) and chemical resistance and are true fluorocarbon elastomers that are, in contrast to polytetrafluoroethylene, flexible. Other methods for the synthesis of perfluoropolyethers and functionalized perfluoropolyethers are under development in our laboratories. 

During World War II, plastics and lubricating compounds of unusual chemical and thermal stability were required for many applications, in particular for pumping apparatus used to separate 235U from 23SU by diffusion of corrosive uranium hexafluoride through porous barriers. It was natural to consider the use of substances made only of carbon and fluorine (fluorocarbons) for such purposes, and considerable effort was spent on methods of preparing compounds such as Today, many such substances are in common use. 

Fluorocarbons, such as Viton, degrade the radiation stability of a proplnt compd, even though they have good thermal stability. The composite proplnts containing K perchlorate had high temp stability, but this applicability was limited by relatively poor radiation stability, as shown in Fig 22, due primarily to the high thermal-neutron cross section of chlorine (33.6 bams)... 

Teflon, a fluorocarbon polymer, is well known for chemical inertness, thermal stability at temperatures up to 290°C, and excellent electrical insulating properties. Most inorganic and many organic compounds are insoluble in it. Teflon also exhibits a relatively large hydrogen gas permeability. It, therefore, has potential as a selective osmotic membrane for hydrogen. 

The exceptional chemical resistance, resistance to ultraviolet (UV) radiation, and thermal stability can be further explained by the fact that the C-F and C-C bonds in fluorocarbons are among the strongest known in organic compounds.4... 

Perfluoroelastomers represent a special subgroup of fluorocarbon elastomers. They are essentially rubbery derivatives of PTFE and exhibit exceptional properties, such as unequaled chemical inertness and thermal stability. Currently, there are two types of known commercial perfluoroelastomers, KALREZ and PERLAST . These have ASTM designation FFKM. 

Fluorocarbon elastomers, such as copolymers of VDF and HFP, typically have a maximum continuous service temperature of 215°C (419°F). Some metal oxides may cause dehydrofluorination at a temperature of 150°C (302°F) or even lower.16 Copolymers of VDF and CTFE (e.g., Kel-F ) have a maximum long-term service temperature of 200°C (392°F). Fluorocarbon elastomers based on copolymers of VDF/HPFP (hydropentafluoropropylene) and on terpolymers of VDF/HPFP/TFE have lower thermal stability than copolymers of VDF/HFP because they have a lower fluorine content than the latter.17 A detailed study of thermal stability of fluoroelastomers was performed by Cox et al.18... 

Because of their high thermal stability and excellent resistance to solvent, fluorocarbons cannot be joined by solvent cementing, and they are very difficult to join by thermal welding methods. Because of their inertness and low surface energy, they also tend to be difficult materials to join by adhesive bonding. Surface treatment is necessary for any practical bond strength to the fluorocarbon parts. 

The thermal stability of fluorocarbon elastomers also depends on their molecular structure. Fully fluorinated copolymers, such as copolymer of TFE and PMVE (Kal-rez), are thermally stable up to temperatures exceeding 300°C (572°E). Moreover, with heat aging this perfluoroelastomer becomes more elastic rather than embrittled. Eluorocarbon elastomers containing hydrogen in their structures (e.g., Viton, Dyneon, and DAI-EL EKM) exhibit a considerably lower thermal stability than the perfluori-nated elastomer. Eor example, the long-term maximum service temperature for FKM... 

Another factor affecting thermal stability of componnds based on fluorocarbon elastomers is the curing (cross-linking) system nsed. This snbject is discussed at some length in the section on compounding. 

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