PTFE, properties

FEP is closely related to PTFE but has a lower melt viscosity and may therefore be processed by conventional processes and possesses most of the PTFE properties. It is a tough, resilient material with an Izod impact value of 2.9 ft-lb/in. at -70F, no break at 73F, and 95,000 ft-lb/in. at 170F. FEP is noninflammable and melts at 545 to 563F. It has excellent chemical and solvent resistance and is largely used in such electrical applications as terminal blocks and valve and tube holders. FEP is also used for a variety of non-stick applications in food processing equipment. 

PTFE is available either as the homopolymer or modified with small amounts (typically less than 1% by weight) of a comonomer. The comonomer can have the benefit of improving processability by decreasing the molecular weight. Crystallization is also inhibited. The modifier is used at a low enough level that the desirable PTFE properties are maintained. 

In addition to tire standard model systems described above, more exotic particles have been prepared witli certain unusual properties, of which we will mention a few. For instance, using seeded growtli teclmiques, particles have been developed witli a silica shell which surrounds a core of a different composition, such as particles witli magnetic [12], fluorescent [13] or gold cores [14]. Anotlier example is tliat of spheres of polytetrafluoroetliylene (PTFE), which are optically anisotropic because tire core is crystalline [15]. 

The dynamic mechanical properties of PTFE have been measured at frequencies from 0.033 to 90 Uz. Abmpt changes in the distribution of relaxation times are associated with the crystalline transitions at 19 and 30°C (75). The activation energies are 102.5 kj/mol (24.5 kcal/mol) below 19°C, 510.4 kJ/mol (122 kcal/mol) between the transitions, and 31.4 kJ/mol (7.5 kcal/mol) above 30°C. 

Table 3. Typical Mechanical Properties of Molded and Sintered PTFE Resins ...

Chemical Properties. Vacuum thermal degradation of PTFE results in monomer formation. The degradation is a first-order reaction (82). Mass spectroscopic analysis shows that degradation begins at ca 440°C, peaks at 540°C, and continues until 590°C (83). 

In air, PTFE has a damage threshold of 200—700 Gy (2 x 10 — 7 x 10 rad) and retains 50% of initial tensile strength after a dose of 10" Gy (1 Mrad), 40% of initial tensile strength after a dose of 10 Gy (10 lad), and ultimate elongation of 100% or more for doses up to 2—5 kGy (2 X 10 — 5 X 10 rad). During irradiation, resistivity decreases, whereas the dielectric constant and the dissipation factor increase. After irradiation, these properties tend to return to their preexposure values. Dielectric properties at high frequency are less sensitive to radiation than are properties at low frequency. Radiation has veryHtde effect on dielectric strength (86). 

Different resins have been developed for use in different reduction—ratio appHcation ranges (111,112). The powders suitable for high reduction—ratio appHcations, such as wire coatings, are not necessarily suitable for the medium reduction—ratio appHcations, such as tubings, or the low reduction—ratio appHcations, such as thread-sealant tapes or pipe liners. AppHcations and processing techniques are being used, which utilize the unique combination of properties offered by PTFE in fine powder form (113—115). 

The PTFE micropowders are commonly used in plastics, inks, lubricants, and finishes such as lacquer. Lubricants containing micropowders are used for bearings, valve components, and other moving parts where sliding friction must be minimized or eliminated. Nonstick finishes that require good release properties, for example, in the food and packaging industry, commonly use PTFE micropowders. 

Properties. The crystallinity of FEP polymer is significantly lower than that of PTFE (70 vs 98%). The stmcture resembles that of PTFE, except for a random replacement of a fluorine atom by a perfluoromethyl group (CF ). The crystallinity after processing depends on the rate of cooling the molten polymer. The presence of HFP ia the polymer chain teads to distort the highly crystallized stmcture of the PTFE chaia and results ia a higher amorphous fractioa. 

The degree to which radiation exposure affects FEP resins is determined by the energy absorbed, regardless of the type of radiation. Changes in mechanical properties depend on total dosage, but ate independent of dose rate. The radiation tolerance of FEP in the presence or absence of oxygen is higher than that of PTFE by a factor of 10 1. 

Mech nic lProperties. Extensive Hsts of the physical properties of FEP copolymers are given in References 58—63. Mechanical properties are shown in Table 3. Most of the important properties of FEP are similar to those of PTFE the main difference is the lower continuous service temperature of 204°C of FEP compared to that of 260°C of PTFE. The flexibiUty at low temperatures and the low coefficients of friction and stabiUty at high temperatures are relatively independent of fabrication conditions. Unlike PTFE, FEP resins do not exhibit a marked change in volume at room temperature, because they do not have a first-order transition at 19°C. They ate usehil above —267°C and are highly flexible above —79°C (64). 

Electrica.1 Properties. Because of excellent electrical properties, FEP is a valuable and versatile electrical insulator. Within the recommended service temperature range, PTFE and EEP have identical properties as electrical insulators. Volume resistivity, which is >10 H/cm, remains unchanged even after prolonged soaking in water surface resistivity is >10 H/sq. 

Copolymeis of ethylene [74-85-1] and tetiafluoioethylene [116-14-3] (ETFE) have been alaboiatory curiosity for more than 40 years. These polymers were studied in connection with a search for a melt-fabricable PTFE resin (1 5) interest in them fell with the discovery of TFE—HFP (FEP) copolymers (6). In the 1960s, however, it became evident that a melt-fabricable fluorocarbon resin was needed with higher strength and stiffness than those of PTFE resins. Earlier studies indicated that TFE—ethylene copolymers [11939-51 -6] might have the right combination of properties. Subsequent research efforts (7) led to the introduction of modified ethylene—tetrafluoroethylene polymer [25038-71-5] (Tefzel) by E. I. du Pont de Nemours Co., Inc, in 1970. 

Because of its excekent combination of properties, processibkity, and relatively low price compared to other fluoropolymers, PVDF has become the largest volume fluoropolymer after PTFE consumption in the United States has grown from zero in 1960 to about 6200 metric tons in 1991 (186). About 49% of the consumed volume is PVDF modified by copolymerization with 5—12-wt % HFP to enhance flexibkity. In 1992, Hst price for homopolymer powders was 15.32/kg, and for pekets 15.42/kg the reported market price was 14.09—14.22/kg (187). In the United States, almost ak PVDF is suppHed by Ausimont USA, Inc., Elf Atochem North America, Inc., and Solvay Polymers, Inc. Ausimont and Elf Atochem are producers Solvay is an importer of the resin. Smak amounts of resin are imported from Germany by Huls America, Inc, and from Japan by Kureha Chemical Industry Co., Ltd. PVDE producers and their trademarks are Hsted in Table 4. 

Composites. Another type of electro deposit in commercial use is the composite form, in which insoluble materials are codeposited along with the electro-deposited metal or alloy to produce particular desirable properties. Polytetrafluoroethylene (PTFE) particles are codeposited with nickel to improve lubricity (see Lubrication and lubricants). SiHcon carbide and other hard particles including diamond are co-deposited with nickel to improve wear properties or to make cutting and grinding tools (see Carbides Tool materials). 

Blends of the polysulfone tesia have been made with ABS, poly(ethylene terephthalate), polytetrafluoroethylene (PTFE), and polycarbonate. These ate sold by Amoco under the Miadel trademark. Additional materials ate compounded with mineral filler, glass, or carbon fiber to improve properties and lower price. 

Polymers used for seat and plug seals and internal static seals include PTFE (polytetrafluoroeth ene) and other fluorocarbons, polyethylene, nylon, polyether-ether-ketone, and acetal. Fluorocarbons are often carbon or glass-filled to improve mechanical properties and heat resistance. Temperature and chemical compatibility with the process fluid are the key selec tion criteria. Polymer-lined bearings and guides are used to decrease fric tion, which lessens dead band and reduces actuator force requirements. See Sec. 28, Materials of Construction, for properties. 

Industrial equipment is a continuing area of development for plastics. Pipes, pumps, valves and sight glasses, made from such materials as PVC, PTFE and poly-4-methylpent-l-ene, have become well established on account of their corrosion resistance. The nylons are used for such diverse applications as mine conveyor belts and main drive gears for knitting machines and paper-making equipment. These and other materials are widely used where such features as toughness, abrasion resistance, corrosion resistance, non-stick properties, electrical insulation capability and transparency are of importance. 

The inability to process PTFE by conventional thermoplastics techniques has nevertheless led to an extensive search for a melt-processable polymer but with similar chemical, electrical, non-stick and low-friction properties. This has resulted in several useful materials being marketed, including tetrafluoro-ethylene-hexafluoropropylene copolymer, poly(vinylidene fluoride) (Figure 13.1(d)), and, most promisingly, the copolymer of tetrafluoroethylene and perfluoropropyl vinyl ether. Other fluorine-containing plastics include poly(vinyl fluoride) and polymers and copolymers based on CTFE. 

The properties of PTFE are dependent on the type of polymer and the method of processing. The polymer may differ in particle size and/or molecular weight. The partiele size will influence ease of processing and the quantity of voids in the finished product whilst the moleeular weight will influenee crystallinity and... 

As with other plastics materials, temperature has a considerable effect on mechanical properties. This is clearly illustrated in Figure 13.5 in the case of stress to break and elongation at break. Even at 20°C unfilled PTFE has a measurable creep with compression loads as low as 3001bf/in (2.1 MPa). 

Table 13.1 Properties of PTFE and other fluorine-containing thermoplastics...

Property ASTM test PTFE PCTFE PVF - PVDF TFE-HFP TFE- ethylene PFA... 

The use of PTFE in a great diversity of applications may be ascribed to the following properties ... 

These materials were first introduced by Du Pont in 1956 and are now known as Teflon FEP resins. (FEP = fluorinated ethylene-propylene.) Subsequently other commercial grades have become available (Neoflon by Daikin Kogyo and Teflex by Niitechim, USSR). These copolymers may be regarded as the first commercial attempt to provide a material with the general properties of PTFE and the melt processability of the more conventional thermoplastics. 

The commercial polymers are mechanically similar to PTFE but with a somewhat greater impact strength. They also have the same excellent electrical insulation properties and chemical inertness. Weathering tests in Florida showed no change in properties after four years. The material also shows exceptional non-adhesiveness. The coefficient of friction of the resin is low but somewhat higher than that of PTFE. Films up to 0.010 in thick show good transparency. 

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