Fluoroelastomers, properties

Report 32 Fluoroelastomers - Properties and Applications, D. Cook and M. Lynn, 3M United Kingdom Pic and 3M Belgium SA. 

D. F. Lohr and J. A. Beckman, "PNF Phosphonitrilic Fluoroelastomer Properties and Applications, a publication by Firestone. 

Chemicals. Both organic and inorganic fluorine-containing compounds, most of which have highly speciali2ed and valuable properties, are produced from HF. Typically these fluorinated chemicals are relatively complex, sometimes difficult to manufacture, and of high value. These materials include products used as fabric and fiber treatments, herbicide and pharmaceutical intermediates, fluoroelastomers, and fluorinated inert Hquids. Other products include BF, SF, and fluoborates. 

During the vulcanization, the volatile species formed are by-products of the peroxide. Typical cure cycles are 3—8 min at 115—170°C, depending on the choice of peroxide. With most fluorosihcones (as well as other fluoroelastomers), a postcure of 4—24 h at 150—200°C is recommended to maximize long-term aging properties. This post-cure completes reactions of the side groups and results in an increased tensile strength, a higher cross-link density, and much lower compression set. 

The fluoroelastomers possess good mbber properties with the added advantages of being nonburning, hydrophobic, and solvent- and fuel-resistant. In addition to these, because of flexibiHty down to about —60° C, these polymers have been used in seals, gaskets, and hoses in army tanks, in aviation fuel lines and tanks, as well as in cold-climate oil pipeline appHcations. These polymers have also found appHcation in various types of shock mounts for vibration dampening (14,17). 

Fluoroelastomers excel compared to aU other elastomers in heat, chemical, flame, weathering, fuel, and o2one resistance. In addition oU, oxygen, and water resistance ate very good. The fluoroelastomers, however, ate attacked by amines and some highly polar solvents. The abrasion resistance and low temperature properties ate adequate for most appHcations. 

The excellent properties of these fluoroelastomers come with a high price tag. Kalrez, for example, is extremely expensive ( 33—44/kg). These materials are used in automotive appHcations (seals, gaskets, fuel hose lines, engine parts, etc), where they can withstand under-hood temperatures. They are also used in equipment for oil and gas production and chemical processing. U.S. consumption in 1988 was 3100 t (76). 

Fluoroelastomer (Vitou, Fluorel 2141, Kel-F) 450 Can be used at high temperatures with many fuels, lubricants, hydraulic fluids, solvents, highly resistant to ozone, weathering. Good mechanical properties. 

In attempts to further improve the stability of fluorine-containing elastomers Du Pont developed a polymer with no C—H groups. This material is a terpolymer of tetrafluoroethylene, perfluoro(methyl vinyl ether) and, in small amounts, a cure site monomer of undisclosed composition. Marketed as Kalrez in 1975 the polymer withstands air oxidation up to 290-315°C and has an extremely low volume swell in a wide range of solvents, properties unmatched by any other commercial fluoroelastomer. This rubber is, however, very expensive, about 20 times the cost of the FKM rubbers and quoted at 1500/kg in 1990, and production is only of the order of 1 t.p.a. In 1992 Du Pont offered a material costing about 75% as much as Kalrez and marketed as Zalak. Structurally, it differs mainly from Kalrez in the choice of cure-site monomer. 

The rubber has a very low of -68°C, excellent hydrolytic stability and excellent resistance to ozone, solvents and acids. In addition the rubber does not bum even in an oxidising atmosphere. Although its properties are virtually unchanged in the range -75 to + 120°C it does not possess the heat resistance of other fluoroelastomers. This polymer was marketed by Firestone in the mid-1970s as PNF rubber, but in 1983 the Ethyl Corporation obtained exclusive rights to the Firestone patents and the polymer is now marketed as Eypel F. 

Over the past 40 years there have been a number of developments that have resulted in the availability of rubbery materials that are thermoplastic in nature and which do not need chemical cross-linking (vulcanisation or setting) to generate elastomeric properties (see also Section 11.8 and 31.2). This approach has been extended to the fluoroelastomers. 

Fluoroelastomer-based nanocomposites were prepared using various nanoclays and their different properties were studied [93-98]. 

Maiti and Bhowmick reported exciting results that a polar matrix like fluoroelastomer (Viton B-50) was able to exfoliate unmodified clay (Cloisite NA ) as well as the modified one (Cloisite 20A) [93]. They studied morphology, mechanical, dynamic mechanical and swelling properties of fluoroelastomer nanocomposites. The unmodified-clay-filled systems showed better properties than the modified ones (Table 2.3). 

Fluoroelastomers Novikova et al. [32] reported unproved physico-mechanical properties of fluoro mbbers by reinforcement with chopped polyamide fibers. Other fiber reinforcements are covered by Grinblat et al. [33]. Watson and Francis [34] described the use of aramid (Kevlar) as short fiber reinforcement for vulcanized fluoroelastomer along with polychloroprene mbber and a co-polyester TPE in terms of improvement in the wear properties of the composites. Rubber diaphragms, made up of fluorosilicone mbbers, can be reinforced using aramid fiber in order to impart better mechanical properties to the composite, though surface modification of the fiber is needed to improve the adhesion between fluorosUicone mbber and the fiber [35]. Bhattacharya et al. [36] studied the crack growth resistance of fluoroelastomer vulcanizates filled with Kevlar fiber. 

Abstract In this paper the synthesis, properties and applications of poly(organophos-phazenes) have been highlighted. Five different classes of macromolecules have been described, i.e. phosphazene fluoroelastomers, aryloxy-substituted polymeric flame-retardants, alkoxy-substituted phosphazene electric conductors, biomaterials and photo-inert and/or photo-active phosphazene derivatives. Perspectives of future developments in this field are briefly discussed. 

The first phenomenon observed is the improved resistance of these materials to combustion, in a way that they may be classified as intrinsically self-extinguishing substrates. For instance, the LOI value for PTFEP is reported to be 48 [452], which is much higher than reported for classical organic plastics [283], while phosphazene fluoroelastomers have been considered as fire-retardant materials since the very beginning of their preparation and utilization [562]. Similarly to aryloxy- and arylamino- substituted POPs [389,390] (vide infra),it may be expected that the flame-resistance properties of phosphazene fluoroelastomers could be successively exported to stabihze organic macromolecules when blended with these materials. 

In the case of poly(alkoxyphosphazenes) (IV) or poly(aryloxyphos-phazenes) (V) a dramatic change in properties can arise by employing combinations of substituents. Polymers such as (NP CHjCF ) and (NP CgH,).) are semicrystalline thermoplastics (Table I). With the introduction of two or more substituents of sufficiently different size, elastomers are obtained (Figure 4). Another requirement for elastomeric behavior is that the substituents be randomly distributed along the P-N backbone. This principle was first demonstrated by Rose (9), and subsequent work in several industrial laboratories has led to the development of phosphazene elastomers of commercial interest. A phosphazene fluoroelastomer and a phosphazene elastomer with mixed aryloxy side chains are showing promise for military and commercial applications. These elastomers are the subject of another paper in this symposium (10). 

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