Physical properties of Fluon® unfilled and filled PTFE
Transcription
Physical properties of Fluon® unfilled and filled PTFE
Physical properties of Fluon® unfilled and filled PTFE Technical Service Note F12/13 2 Contents Summary Page 6 Introduction 6 SECTION 1. THE STRUCTURE OF PTFE Molecular conformation and crystal structure Melting behaviour Crystallinity and texture Polymer particle structure Void formation in mouldings 7 7 7 8 9 10 SECTION 2. EFFECTS OF PROCESSING ON PROPERTIES Molecular weight Crystallinity Orientation Voids 11 SECTION 3. MECHANICAL PROPERTIES - UNFILLED PTFE Compressive stress-strain relationships Tensile properties Impact behaviour SECTION 4. ELECTRICAL PROPERTIES - UNFILLED PTFE Permittivity and dielectric loss Experimental techniques D.C. conduction behaviour High voltage uses of PTFE SECTION 5. THERMAL PROPERTIES - UNFILLED PTFE Melting point Thermal expansion Thermal conductivity Specific heat and heat of fusion Thermal stability SECTION 6. SURFACE PROPERTIES - UNFILLED PTFE Coefficient of friction Angle of contact SECTION 7. OTHER PHYSICO-CHEMICAL PROPERTIES - UNFILLED PTFE Permeability Infra-red transmission 11 11 12 12 13 13 18 18 21 21 21 21 24 Refractive index Melt viscosity High energy radiation Chemical resistance Velocity of sound Page 28 28 29 29 29 SECTION 8. GENERAL - FILLED PTFE Function of filler Choice of filler Choice of Fluon® grade The Fluon® range 30 30 30 31 31 SECTION 9. MECHANICAL PROPERTIES - FILLED PTFE Compressive deformation Impact strength 32 SECTION 10. ELECTRICAL PROPERTIES - FILLED PTFE Insulating materials Conducting materials SECTION 11. THERMAL PROPERTIES - FILLED PTFE Thermal expansion Thermal conductivity SECTION 12. SURFACE PROPERTIES - FILLED PTFE Friction Wear 32 37 38 38 38 40 40 40 41 41 43 25 25 25 25 26 26 SECTION 13. OTHER PHYSICO-CHEMICAL PROPERTIES - FILLED PTFE Permeability Chemical resistance 45 45 45 SECTION 14. TYPICAL PROPERTIES OF UNFILLED AND FILLED MOULDED PTFE 46 SECTION 15. SPECIFICATIONS RELATING TO PTFE 47 SECTION 16. HANDLING PRECAUTIONS 48 SECTION 17. FURTHER INFORMATION 49 SECTION 18. REFERENCES 50 27 27 27 28 28 28 3 4 List of figures Page Page 1. Molecular conformation of PTFE 7 2. The decay of birefringence in the melt 8 sintered granular PTFE (60 % crystallinity) 3. Particles of dispersion polymer 9 using evaporated gold electrodes 4. Aggregates of particles of dispersion 9 polymer 5. Longitudinal section through 10 Longitudinal section through 10 Internal and external texture of a 10 Variation of relative density 12 13 10. Compressive creep 14 11. Isochronous stress-strain relationship 14 in compression 23 and preconditioning for sintered 22. Variation of specific volume 23. Infra-red transmission spectrum 26 Fluon® 15 G163 13. Creep in compression, at 25°C (77°F), 24. Creep in compression at 20°C (68°F), 16 17 34 Fluon® FC100-25 1000 35 compression at 20°C (68°F), and various 27. Creep in compression at 20°C (68°F): 1 at 25°C (77°F), Fluon® G163 19 36 various Fluon® grades 28. Recovery from creep in compression: stress-strain curves for PTFE 17. Effect of temperature upon tensile 25. Creep in compression at 20°C (68°F), strain levels: Fluon® FC100-25 1000 various strain levels, Fluon® G163 16. Effect of temperature upon tensile 33 FC100-25 1000 26. Isometric stress-time curves in in compression, at 25°C (77°F) and 15. Recovery from creep in compression G163 and Fluon® at various stress levels, Fluon® G163 14. Isometric stress-strain curves 29 (specimen thickness 0.05 mm (0.002 inch)) Fluon® 12. Isochronous stress-strain curves in yield stress of PTFE sintered granular PTFE with temperature Basic creep testing equipment compression, 25°C (77°F), 23 granular PTFE with crystallinity 9. 20. Plot of log10 apparent volume 21. Effect of different electrode materials granular polymer 8. 22 resistivity versus log10 time for sintered extrudate 7. 19. Loss angle versus frequency for 22 PTFE at room temperature unsintered extrudate 6. 18. Loss angle versus temperature for Fluon® 36 FC100-25 1000 loaded at various stress levels 20 29. Loss tangent versus temperature 38 at 1 kHz: glass-filled PTFE 5 Summary Introduction This Note describes the physical properties of PTFE. It should be used in conjunction with other Asahi Glass Fluoropolymers Technical Service Notes. Only rarely can the physical properties of PTFE (polytetrafluoroethylene) be expressed in simple terms. Because of its high melt viscosity PTFE is not processed by those techniques associated with most thermoplastic polymers. The techniques used with PTFE consist essentially of a cold shaping operation followed by sintering, during which the polymer particles fuse and coalesce; finally the fused polymer is cooled. One result of the fabrication methods used with PTFE is that, in many respects, the quality of the fabricated polymer is unusually dependent on the skill with which the fabrication is carried out. For this reason any table purporting to express the physical properties of PTFE as a list of figures - including such tables which appear in this Note - must be regarded as a very simple summary of a very complex subject. Three general surveys of PTFE are: Fluorine-containing polymers, Part 2: Polytetrafluoroethylene, C A Sperati and H W Starkweather, Fortschr. Jochpolym.-Forsch., 2, 1961, 465-495 Polytetrafluoroethylene, S Sherratt, Kirk-Othmer, Encyclopaedia of Chemical Technology, 9, 2nd edition, Interscience Publishers Inc., New York, 1966, 805-831. Fluoroplastics, Vol 1: Non-Melt Processible Fluoroplastics, S. Ebnesajjad, Published by Plastics Design library, 2000. ISBN1-884207-84-7 6 Section 1. The structure of PTFE MOLECULAR CONFORMATION AND CRYSTAL STRUCTURE PTFE is a linear chain polymer of great molecular length. The linearity is indicated by an analysis of the infra-red spectrum and by the fact that the powder as produced in the polymerisation reaction is very highly crystalline, with crystalline weight fractions of 0.90 to 0.95 being indicated by density, infra-red and X-ray diffraction measurements. Energy considerations also suggest that branching by chain transfer is unlikely (ref. 1). The crystal structure and chain conformation have been discussed by Bunn and Howells (ref. 2) and later by others (refs. 3, 4, 5). The crystalline melting point of sintered PTFE is about 327°C (620°F) and of unsintered material 332-346°C (630-655°F) but there are two reversible first order transitions at lower temperatures,19°C and 30°C (66°F and 86°F) (ref. 6), which together involve a 1% change in density (ref. 7). Three crystalline phases are observed at atmospheric pressure: phase I (< 19°C; 66°F), phase ll (19-30°C; 6686°F) and phase lll ( >30°C; 86°F). Below the 19°C (66°F) transition (phase l), the chain repeat distance is 16.8 Å and the CF2 groups are equally spaced along the chain which is twisted to form a helix on which successive carbon atoms lie, thirteen carbon atoms being involved in a twist of 180°, (Figure 1). Between 19 and 30°C (66 and 86°F) (phase ll) the repeat distance increases to 19.5 Å (refs. 3,8) corresponding to a twist of 15 carbon atoms in 180°. Above 30°C (86°F), (phase lll), further disorder sets in and although the molecular conformation prevailing at lower temperatures is maintained, the chains are displaced or rotated along their long axes by variable amounts which increase as the temperature is raised further. The reason for the helical structure is the necessity to accommodate the large fluorine atoms (van der Waals radius 1.35 Å). The rotation at each chain bond, with the slight opening up of the bond angles to 116°, relieves the overcrowding and permits the shortest F-F distance to be 2.7 Å (ref. 9). Further studies by various authors (refs.10,11,12,13,14) have examined the effect of pressure on the room temperature transitions and the melting point. A study of pressures above-atmospheric revealed a 2% increase in density below 19°C (66°F). This fourth crystalline phase has been labelled phase lll by Weir (ref. 10). A triple point exists at about 70°C (158°F) and 4.5 kilobars. The heats of transition were also determined by Yasuda and Araki (ref. 11); dilatometric and calorimetric studies have in addition been reported by other workers (refs. 6,15, 16,17). Figure 1. Molecular conformation of PTFE MELTING BEHAVIOUR PTFE has a crystalline melting point at atmospheric pressure of about 332-346°C (630-655°F) for unsintered and about 327°C (620°F) for sintered material. The heat of melting has been estimated by Lupton (ref. 18) as about 685 cal/mole of CF2 groups and leads to an estimate of the entropy of melting of 1.14 cal/degK mole. This value is low by comparison with polyethylene (2.29 cal/degK mole) and arises from the fact that the stiff long molecules retain a good deal of side-by-side order in the melt. Indeed, if the depolarisation of light is used to detect the course of melting, a finite amount of depolarisation is observed to remain above the melting point (ref. 19) (Figure 2). The decay of this residual depolarisation is sensitive to molecular weight, time and temperature. Bunn (ref. 20) has ascribed the high melting point to the rigidity of the fluorocarbon chain, small rotations being hindered by the slightly overcrowded fluorine atoms. 7 Figure 2. The decay of birefringence in the melt CRYSTALLINITY AND TEXTURE The crystallinity and texture of polytetrafluoroethylene have received a good deal of study. Estimations of the degree of crystallinity have been made by X-ray (ref. 21), infra-red (refs. 22, 23) and density methods. For 100% crystalline PTFE relative densities of 2.347 at 0°C (32°F) and 2.302 at 25°C (77°F) can be calculated from the X-ray crystallographic data (ref. 5). The density decrease of about 2% between these temperatures includes the decrease of about 1% arising from the transition at 19°C (66°F). The relative density of amorphous PTFE is not affected by this transition and values around 2.00 are obtained by measuring the density at room temperature (preferably 23°C; 73°F) for a number of samples of varying crystallinity, and then extrapolating to zero crystallinity (refs. 8, 24, 25). If the degree of crystallinity is estimated as a result of Xray or infra-red methods it is then possible to calculate a theoretical density. Differences between this theoretical density and the experimentally measured value can be used to assess the void content of a sample. Neither the X-ray nor the infra-red method measures an absolute crystallinity. Each measures ‘disorder’ by a different criterion and, in addition to this, each is subject to purely instrumental limitations, so that even for one of the methods the same value would not necessarily be determined on two different instruments. Tests show the degree of crystallinity measured by the infra-red method is systematically higher than the X-ray crystallinity, the discrepancy being of the order of 5% at 90% increasing to 10% at 50%. For instance, the crystallinities estimated by the X-ray method range from about 90% for unsintered material, 75% for fused and slowly cooled material, to 50% for 8 fused and rapidly quenched samples. The initial high crystallinity and melting point can never be completely recovered after fusion because of the complete reorganisation of the molecular arrangement upon sintering. Crystallisation from the melt in bulk produces long bands which can be seen both in fracture surfaces produced by breakage at liquid nitrogen temperatures, and in sections of the material when viewed microscopically in polarised light (ref. 26). Their dimensions vary from 100µm x 1µm to 10µm x 0.2µm depending on the crystallisation conditions and/or molecular weight, the band width being inversely related to molecular weight (ref. 27). The bands show fine parallel striations perpendicular to the band length and it is thought that the bands are the broken edges of thick lamellar crystals. The interpretation of the striations is still uncertain and remains a subject for further investigation (ref.19). Birefringence measurements show the molecules to lie perpendicular to the bands and since the average length of the molecules is greater than the band thickness chain folding is implied. As the fusion temperature is raised or a lower molecular weight polymer is used (both of which tend to reduce the persistence of order in the melt) the band growths become irregular and tend to agglomerate into spherulitic structures. The use of very high fusion temperatures of around 450°C (842°F) results in well formed spherulites, presumably due to molecular weight reduction as a consequence of thermal degradation. Speerschneider and Li have investigated the role of the large bands in uniaxial deformation and have shown that distortion of the bands occurs at low temperatures (ref. 28). POLYMER PARTICLE STRUCTURE The particles of polymer produced in the dispersion polymerisation process are of the order of 0.2µm in size, whilst those from a granular polymerisation are hundreds of µm in size, built up from smaller particles. They are both highly crystalline - about 90 to 95%. The dispersion particles can be studied directly in a conventional transmission electron microscope, providing the electron intensity is kept low (ref. 29). On raising the electron beam intensity the particles change rapidly in appearance to become transparent with a crumpled texture. At this stage the crystallinity has disappeared and the ‘particles’ probably consist of a shell of carbon. Electron diffraction patterns and dark field micrographs suggest that the particles are composed of a pile of small single crystals (ref. 30) with the molecular axis along the axis of the brick-shaped particles (refs. 30, 31). The particles also appear to have a striated surface structure generally parallel to the long axis. A replica of some dispersion particles is shown in Figure 3. During coagulation, the dispersion particles Figure 3. Particles of dispersion polymer 1µm aggregate to form a larger particle, made up of a loose structure of agglomerates of the primary particles (Figure 4). During cold, lubricated extrusion the agglomerated particles are highly distorted, with their primary particles becoming aligned and also drawn into fibrous material. This effect is illustrated in Figure 5. If an extrudate such as that depicted in Figure 5 is sintered and cooled slowly the extrudate will appear as in Figure 6. In Figure 6 the direction of extrusion was from left to right. Granular Polymers During the early stages of polymerisation granular particles form as aggregates of smaller particles. This process continues and large irregular fibrous structures are produced. This material is then modified mechanically to reduce it to the familiar form suitable for processing. For example, Figure 7 shows the structure of a fine particle granular powder. Figure 4. Aggregates of particles of dispersion polymer 100µm 9 Direction of extrusion 1µm Figure 6. Longitudinal section through sintered extrudate 0.5µm Figure 5. Longitudinal section through unsintered extrudate VOID FORMATION IN MOULDINGS When PTFE is moulded the basis of the process is that the polymer powder is preformed and then sintered. It is therefore not surprising that mouldings can be produced which contain microscopic voids and fissures arising from the porous nature of the unsintered particles and the molecular re-arrangement caused by sintering. Correct choice of polymer grade and careful use of fabrication techniques will help to minimise the formation of voids. The homogeneity of the final moulding depends a great deal on the compressibility of the particles and their surface structure. In this respect the behaviour of the particles closely resembles that of powdered metals. Softer particles (generally more porous ones) compact more easily than harder ones and will ‘flow’ more easily to fill interparticulate voids. This leads to a higher ‘green’ strength (of the unsintered preform) and in turn to a higher sintered strength. As with powdered metals the strength both of the preform and of the final sintered moulding depends upon the mean particle size, with finer particles giving higher strengths. According to 10 10µm Figure 7. Internal and external texture of a granular polymer Rhines as reported by Goetzel (ref. 32) the important factors affecting powdered metals are the number of particle-to-particle contacts and their area. Experiments (ref. 33) suggest that, even where no voids exist, variations in internal pressure within a preform result in variations in crystallite size presumably due to the variations in melting point with pressure, for which McGeer and Duus (ref. 34) have given the relationship: Tm = a + bP Where T = °K, P = atmospheres, a = 597°K and b = 0.154°C/atm so that 16 MN/m2 (160 kgf/cm2; 1 tonf/in2) difference in internal pressure can lead to a melting point difference of the order of 25°C (45°F). Such variations in internal pressure will result either from poor packing of the powder in the mould due to poor powder flow properties or from a lack of compressibility in the individual particles. The variation in crystallite size resulting from poor packing leads to variation in translucency from area to area and lack of compressibility gives an overall white and opaque appearance in thin machined sections such as 0.25mm (0.01 inch) skived tape. Section 2. Effects of processing on properties The exact manner in which the fabrication of the polymer is carried out affects certain intrinsic qualities in the polymer which, in turn, influence some properties, notably tensile strength, elongation and dielectric strength. The intrinsic qualities of PTFE which can be affected by fabrication conditions are molecular weight, crystallinity, orientation and the presence or otherwise of voids and interfaces. These factors will now be considered in turn. MOLECULAR WEIGHT All commercial samples of PTFE (with the exception of lubricant powders) are of extremely high molecular weight; granular polymers are of somewhat higher molecular weight than dispersion polymers. Because of its insolubility, the molecular weight of PTFE can be measured only with difficulty. The best method of assessing the molecular weight of PTFE is undoubtedly by measuring the viscosity of the polymer at some temperature above its melting point. This approach demands, however, some fairly sophisticated equipment if it is to be successful and less direct methods of arriving at an idea of molecular weight are often favoured. When PTFE is cooled from a temperature above its melting point at a carefully controlled rate, the extent to which the polymer crystallises will be inversely dependent on the molecular weight. Now, assuming the moulding contains no voids, its crystallinity can be inferred from its relative density, so the relative density of a moulding prepared under precisely defined conditions (this quantity is often called the standard relative density) can be used as an index of molecular weight. The relationship: _ standard relative density = 2.612-0.058 log10 Mn _ has been given where weight Mn is the number average molecular weight . CRYSTALLINITY As polymerised, PTFE is of 90-95% crystallinity but when it is heated above its crystalline melting point the polymer becomes amorphous. In the melt state PTFE does retain some two-dimensional order but, as the three dimensional crystal structure has been destroyed, molten PTFE can properly be thought of as amorphous. On cooling, the extent to which crystallisation occurs is dependent both on the molecular weight of the polymer and on the rate of cooling, particularly at temperatures just below the melting point. Slow cooling naturally tends to increase the extent of crystallisation. Almost all fabricated PTFE displays crystallinities within the range 50 to 75% depending on the rate of cooling. The crystallinity of PTFE is best measured by X-ray diffraction or by infra-red absorption methods These respectively assess ‘order’ and ‘disorder’ within the specimen. However as the relative density of 100% crystalline PTFE at 23°C (73°F) is 2.30 while that of 0% crystalline (100% amorphous) PTFE under the same conditions is 2.00, the relative density of PTFE can be used to give a simple index of crystallinity. Clearly it is essential that the specimens used for relative density measurements be free from voids and, since such voids are less likely to occur in specimens produced from coagulated dispersion polymers, the technique is probably of greater value in this field than in that of granular polymers. The relationship between relative density and crystallinity for void-free specimens of PTFE is shown in Figure 8. The level of crystallinity in fabricated PTFE is a matter of considerable importance. In general, fabricators attempt to keep the crystallinity to a minimum as the higher the amorphous content the greater the ultimate tensile strength and the longer the flex life will be. In some instances, however, such as where gas permeability must be reduced, higher crystallinities will be desirable. The thermal stability of PTFE is so great that, if processed correctly, the polymer should suffer no significant degradation and the molecular weight of the finished product will be determined almost entirely by that of the raw polymer. 11 Figure 8. Variation of relative density with crystallinity ORIENTATION The orientation of PTFE is a measure of the extent to which the polymer chains are aligned in any particular direction. This alignment, because of their methods of processing, is more likely to occur with the coagulated dispersion polymers than with the granular or aqueous dispersion materials. VOIDS During fabrication, PTFE does not pass through the state of being a low viscosity liquid and, as a result, articles made from PTFE may possess voids and interfaces in the mass of the polymer. These faults are more likely to occur in large articles made from granular polymers than in articles of thin cross-section made from either aqueous or coagulated dispersion polymers. The problem of voids in granular mouldings can almost always be overcome by careful choice of the correct granular polymer for a particular duty and by use of the appropriate fabrication technique. For practical purposes the absence of voids in fabricated PTFE is denoted by good tensile strength, high elongation at break, low gas permeability, prolonged flex life and high dielectric strength. It is often possible to detect voids by examining a thin section - preferably less than 0.25 mm (0.01 inch) - by transmitted light when a sample free from voids will be translucent with a faintly blue colour. On the other hand a sample containing many voids will be white and opaque with a chalky appearance. If the sample is first treated with a penetrant dye† then the detection of voids is made a great deal easier. † Such as ‘Ardrox’ 996P supplied in the UK by Chemetall plc, 65 Denbigh Road, Bletchley, Milton Keynes, MK1 1PB (UK) Tel. +44 (0) 1908 649333 Fax +44 (0) 1908 361872 www.aerospace.chemetall.com in mid-Europe by Chemetall GmbH, Frankfurt a.M. Tel. +49 (0) 697165-0 and in the USA by Chemetall Oakite, 50 Valley Road, N.J. 07922, Berkeley Heights Tel. +1 908 508 2214 Fax +1 908 464 7914 Toll-free 800 526 4473 www.oakite.com 12 Section 3. Mechanical properties - unfilled PTFE Although the classical concept of modulus, which implies a linear proportionality between stress and strain, is not strictly applicable to most plastics, the term is widely used and the resulting implications should be considered. The Young’s Modulus of a metal such as steel is the ratio of stress to strain in the elastic region, and is constant. For most plastics such a region does not exist and the ratio of stress to strain will not be constant but will depend both on the time for which the stress is applied and the resulting strain. The time-dependence of strain may be defined as the ‘creep’ behaviour and a study of creep, together with the equally important phenomenon of recovery, is essential for a full understanding of the mechanical properties. An apparatus has been specially developed for studying the compressive creep of PTFE: full details of this equipment have been published elsewhere (ref. 35) but a general impression is given in Figure 9. With this equipment the stress-strain-time relationship at a constant temperature may be obtained by observing either the strain-time relationship at a constant stress (creep) (Figure 10), or the stress-strain Alternatively the isochronous curve may be obtained experimentally on a single specimen by the application of a series of stresses (σ1 to σ6 Figure 11) in successively increasing steps and measuring the strain produced ( 1 to 6 Figure 11) after the section time, t, has elapsed, allowing a recovery period of 4t by complete removal of the stress on the specimen between each successive increase (ref. 36). The isochronous stress-strain curves presented here have been obtained in this way. Isometric curves (stress-time relationships at constant strain) may also be obtained by taking constant strain sections through a family of creep curves. ∋ COMPRESSIVE STRESS-STRAIN RELATIONSHIPS relationship at a constant time (isochronous stress-strain curve) (Figure 11). The isochronous curve is derived by taking a constant time section through a family of creep curves and replotting the stress and strain values of the intersections to give the isochronous curve. The derivation is shown schematically in Figures 10 and 11. ∋ In some respects PTFE is a typical thermoplastic polymer; in others it is far from typical. Thus the mechanical properties of PTFE vary with changes in time, temperature and crystallinity in the way that one would expect of a thermoplastic. On the other hand, the fabrication methods used with PTFE can have a very large influence on the properties, particularly if unsatisfactory processing allows a particulate structure to persist into the fabricated article. PTFE is used only infrequently in tension so that it is appropriate to make measurements on samples in compression. The properties of design interest will be considered in some detail. At the termination of a creep experiment the phenomenon of recovery may be studied by removing the load on the specimen and observing the decrease of strain with time. It is convenient to present recovery data on a ‘fractional recovered strain’ versus ‘reduced time’ graph as an aid to comparison of data obtained on specimens which have either attained different maximum strains at the termination of the creep experiment or for which the times under load have not been identical. Fractional recovered strain is defined as the ratio of the strain recovered to the creep strain at the start of recovery and reduced time as the ratio of the recovered time to the creep time (ref. 37). Thus a fractional recovered strain of unity signifies complete recovery and a reduced time of unity denotes a recovery time equal to the preceding creep time. Spherical seating Figure 9. Basic creep testing equipment Fixed platen Iris diaphragm device Specimen Moving platen Pivot Beam Load Automatic loading device 13 6 5 6 4 6 3 5 5 6 4 4 5 2 3 4 3 2 3 2 1 2 1 1 Strain Stress 1 t Time - (log scale) Figure 10. Compressive creep The following information is the result of work done on behalf of AG Fluoropolymers. A complete picture of the behaviour of PTFE has not yet been obtained, and in particular, work on effects of temperature is not complete. Nevertheless, enough data are now available to provide some basic information. The data given are for Fluon® G163 preformed at a pressure of about 16 MN/m2 (160 kgf/cm2; 1 tonf/in2), and sintered at 380°C (716°F). Isochronous stress-strain behaviour Figure 12 shows the effect of time on the stress-strain relationship of Fluon® G163. The non-linearity of the curves, even at quite low strains, shows how the apparent modulus decreases with increasing strain. 14 Strain at time (t) Figure 11. Isochronous stress-strain relationship in compression Creep behaviour Figure 13 shows a family of creep curves at various stress levels, while Figure 14 shows the same information plotted as stress against time for various strain levels. It should be noted that the latter are not true stress relaxation curves, though the curves should give a very approximate indication of the decay of stress with time in a component maintained at a constant strain level. Recovery Figure 15 shows the effect of four different stress levels on the rate of recovery of strain after removal of the applied compressive load. It can be seen that the higher the stress the slower is the recovery. 1100 s (2 H ou rs 10 46 0s ec m in u te on 80 Kgf/cm 2 s) ds 8 nd ) rs 4 se co 7 10 70 Kgf/cm 2 ys s nd 1 (1 16 u ho 1000 da co 6 10 6 se 900 60 Kgf/cm 2 800 5 700 50 Kgf/cm 2 600 4 40 Kgf/cm 2 500 3 30 400 300 2 20 200 1 100 0 0 0 0.5 Strain - % 1 1.5 2 3 2.5 o 3.5 Stress - Ibf/in 2 Stress - MN/m 2 10 4 o Figure 12. Isochronous stress-strain relationship in compression, at 25 C (77 F), Fluon® G163 15 :11 60 lbf/ in 2 ) 5.0 m f/c 7M N/ m 2 (71 .4 kg 8M 4.0 2 N/m 2 :10 15 (81 lbf .6 k /in 2 ) gf/c m2 4.5 lb f/i n 2 ) 3.5 m 2 (6 1. 2 kg f/c m 2 :8 7 0 3.0 6 M N/ 2.5 ) 2 /in 25 f lb :7 2 m 2.0 f/c 0 1. (5 2 kg m N/ 5 M ) 2 /in 1.5 2 .8 (40 2 N/m cm gf/ bf 0l :58 k 4M 2 1.0 2 2 N/m cm kgf/ 6 (30. bf/in l :435 ) 3M 2 f/in ) :290 lb kgf/cm 2 m (10.2 kgf/c 1 MN/m 10 2 104 103 1 hour Time - seconds o o Figure 13. Creep in compression, at 25 C (77 F), Fluon® G163 105 106 :145 lbf/in 107 1 month 10 1 week 0 2 2) 108 1 year (20.4 2 1 16 2 6 Months 2 MN/m 1 day Strain - % 0.5 8 80 kgf/cm 2 1100 7 1000 70 kgf/cm 2 900 6 60 kgf/cm 2 800 5 50 kgf/cm 2 700 600 4 40 kgf/cm 2 500 3 30 kgf/cm 2 400 300 2 20 kgf/cm 2 200 1 10 0 Time - seconds 2 10 103 104 105 106 o 107 0 108 Stress - Ibf/in 2 0 100 1 year 6 Months 1 month 1 week 1 day 1 hour Stress - MN/m2 10 kgf/cm 2 o Figure 14. Isochronous stress-strain curves in compression, at 25 C (77 F) and various strain levels, Fluon® G163 17 0.8 2 2 0 lbf/in cm ; 29 2 2 (20.4 kgf/ f/in 2 ; 580 lb 2 MN/m 2 gf/cm lbf/in 2 (40.8 k 2 ; 870 m 2 / N m 4M kgf/c lbf/in 2 (61.2 2 ; 1160 /m m 6 MN 2 1.6 kgf/c (8 m / 8 MN Fractional recovered strain 0.6 0.4 0.2 0 10-6 10-5 Reduced time 10-4 10-2 10-3 o 10-1 1 10 102 o Figure 15. Recovery from creep in compression, at 25 C (77 F), Fluon® G163 TENSILE PROPERTIES The tensile breaking stress and breaking strain are used extensively for quality control purposes, but they are unsatisfactory quantities for design purposes for two reasons: firstly, and most importantly, PTFE should never be used at strains beyond the yield point (the point at which the load-deformation curve has a distinct change of slope) and secondly, the point of fracture is dependent on specimen shape and is therefore not useful for predicting behaviour in practice. The tensile load-extension curves obtained with specimens of PTFE depend on crystallinity, molecular weight, the size, shape and perhaps the structure of the original particles and the severity of faults remaining after fabrication. Furthermore they depend, as is usual with thermoplastics, on test temperature and straining rate. Because of these complications the data here can only be indicative of general behaviour. Figure 16 shows the general trends of behaviour in tension for PTFE as a function of temperature. These are typical curves from which the yield stress can be derived, though less precisely than is possible for most other plastics materials. The effect of temperature on the yield stress of PTFE is shown in Figure 17, which is for times to yield of approximately one minute. If the material is to be under load for any considerable length of time it should not be stressed beyond a small fraction of the yield stresses shown in Figure 17. IMPACT BEHAVIOUR The behaviour of plastics under impact conditions depends both on temperature and on the severity of the applied stress, as well as on molecular parameters such as molecular weight and fabrication effects. PTFE is no exception to these generalisations and with the wide variation in fabrication procedures available for this polymer it is impossible to give other than general data. 18 Unnotched specimens of PTFE are resistant to fracture on impact; even at temperatures as low as -196°C (320°F) well-fabricated specimens are tough. A test for judging the quality of a sample from this point of view is to measure the flexural strength of specimens which have been immersed for 15 minutes in liquid nitrogen and then tested within a few seconds of removal. In this liquid nitrogen dip test which was carried out with three point loading, a span of 38mm (1.5 inches), a thickness of 3.2mm (0.125 inch) and a rate of test of 457mm/min (18 inches/min) good specimens of PTFE do not break at the maximum load, the apparent yield stress of such a specimen being approximately 185 MN/m2 (1900 kgf/cm2; 27 000 lbf/in2). However, less well-fabricated specimens may be brittle with flexural strengths of approximately 135 MN/m2 (1400 kgf/cm2; 20 000 lbf/in2) in this test. The behaviour of notched specimens typifies the reaction of PTFE components with built-in stress concentration regions. This is shown by measurements of the Charpy impact strength: the test was carried out with three-point loading and an impact velocity of 2.44m/second (8 ft/second) at temperatures between -35 and +23°C (-31 and +73°F). One sample was cooled slowly at 25°C/hour (45°F/hour) and another cooled from the sintering temperature of 380°C (716°F) to 20°C (68°F) in two hours. The notch tip radius of the specimens was varied between 0.25mm (0.01 inch) and 2.03mm (0.08 inch), spans of 25mm (1 inch) and 38mm (1.5 inch) were used and the notch depth was held constant at 2.82mm (0.110 inch). There was no consistent difference between the impact strengths of the samples cooled at different rates. At temperatures of -20°C (-4°F) and below all notched specimens broke completely, [impact strength in the range 6 to 10 kgf/cm2 (3 to 5 ft Ibf/in2), with an 0.25mm (0.010 inch) notch], whilst at -10°C (+14°F) and above many specimens did not break completely - that is to say ‘hinge’ breaks occurred. 40 400 kgf/cm 2 -40°C (-40°F) -20°C (-4°F) 35 5000 -10°C (-14°F) 30 300 kgf/cm 2 4000 0°C (-32°F) 25 10°C (-50°F) 3000 20 200 kgf/cm 2 25°C (77°F) 15 2000 50°C (122°F) 10 100 kgf/cm 2 100°C (212°F) 1000 150°C (302°F) 5 0 0 0 Strain - % 100 200 300 Stress - Ibfin 2 Stress - MNm 2 200°C (392°F) 400 Figure 16. Effect of temperature upon tensile stress-strain curves for PTFE 19 200 2000 kgf/cm 2 25000 150 1500 kgf/cm 2 20000 15000 100 1000 kgf/cm 2 10000 50 500 kgf/cm 2 0 -220 -364 -140 -220 -60 -76 20 68 Temperature Figure 17. Effect of temperature upon tensile yield stress of PTFE 20 100 212 180 356 0 260°C 500°F Yield stress - lbf/in 2 Yield stress - MN/m 2 5000 Section 4. Electrical properties - unfilled PTFE PERMITTIVITY AND DIELECTRIC LOSS EXPERIMENTAL TECHNIQUES It has been known since 1946 (ref. 38) that because of its non-polar nature, the dielectric properties of PTFE were of an ideal character. In 1953 a careful study by Ehrlich in the USA (ref. 39) showed that the fall in permittivity from 2.0 to 1.8 in the temperature range 24 to 314°C (75 to 597°F) could be accounted for entirely in terms of density changes by the Clausius-Mossotti formula. No changes of permittivity with frequency were detected and scarcely resolved loss angle† values less than 200µ radians were recorded. In 1955 Mikhailov and co-workers in the USSR (ref. 40) found a loss peak in the -80 to -40°C (-112 to -40°F) range at audio and radio frequencies which was correlated in its temperature/frequency location with dynamic mechanical loss behaviour. From studies of the effect of changes of crystallinity by quenching and slow cooling they concluded that the relaxation losses were attributable to amorphous regions of the polymer. In 1959 Krum and Muller (ref. 41) (of Marburg) reported higher dielectric loss values than those found by earlier workers and found more detailed correlation with mechanical properties and effects of crystallinity changes. Eby and Sinnott in the USA (ref. 42) have suggested, however, that these higher loss values must be due to polar impurities. The results of measurement done on behalf of AG Fluoropolymers are presented in Figure 18 where the variation of the loss angle with temperature is given for the range -140 to +240°C (-220 to +464°F) and in Figure 19 as loss angle versus frequency at room temperature. These data, which were obtained using the experimental techniques described in the next column of this page, confirm and extend the findings of Ehrlich and Mikhailov and support Eby and Sinnott’s contention that Krum and Müller’s higher loss values must be due to polar impurities. The dielectric loss of PTFE is sufficiently low to allow the permittivity to be calculated with an accuracy of better than 0.5% using the Clausius-Mossotti formula: -1 +2 = Kd ∋ ∋ where = permittivity ∋ d = relative density Measurements of permittivity and dielectric loss in the audio frequency range (178 Hz - 31.6 kHz) were made using a fully-shielded, three-terminal conjugate Schering bridge; a resonance substitution method, based on that published by Hartshorn and Ward (ref. 43) but suitably modified to give a higher resolution (ref. 44), was used for the radio frequency region (105-108 Hz). A modified version of the re-entrant cavity resonator method of Parry (ref. 45) was used for the 108 - 109 Hz range; an H01 cavity resonator was used at 9 x 109 Hz: this made use of the Bleaney, Loubser and Penrose (ref. 46) method of avoiding unwanted modes. D.C. CONDUCTION BEHAVIOUR In attempting to study the d.c. conduction behaviour of PTFE, the current measured was that which occurs after the application of a d.c. voltage step. In Figure 20 the results for a typical sintered sample, using evaporated gold electrodes, are expressed as log (apparent volume resistivity) as a function of time of polarisation. It will be seen that steady state conduction was not established clearly in the time of the experiments (which was 15 minutes). On the diagram are shown lines of constant loss angle which can be calculated by means of a Fourier transform assuming a constant permittivity of 2.0. The short time values are consistent with the low frequency values (= 20 µ radians) measured by a.c. methods. In fact it is considered that such d.c. step response results are equivalent to a low frequency extension of the a.c. frequency range (refs. 47, 48, 49). The apparent resistivity is to be thought of as a very low frequency relaxation loss phenomenon rather than a steady state charge transport phenomenon, although the onset of conduction may be apparent above 160°C (320°F). Figure 21 shows that such currents may be removed by heat treatment in the presence of electrodes; apparent resistivity values of > 1018 ohm m have been obtained from such experiments without showing evidence of steady state conduction (ref. 47). However, much lower values are often obtained if unsatisfactory electrodes are used or if temperature stability or polarising voltage stability are not good enough to exclude V dC dT or C dV dT terms for the current. K = constant, 0.119 From which it can been seen that: = 1 + 2 Kd 1 - Kd ∋ thus, at a relative density of 2.174 the permittivity is 2.05. † Loss angle in µ radians is very nearly equal to loss tangent (tan δ) x l06, ie 100µ radians = loss tangent of 0.0001) 21 240 200 31600 Hz 5620 Hz 1000 Hz 178 Hz 32 Hz 160 120 Loss angle - radians 80 40 0 -140 -140 -220 -184 -80 -112 -40 -40 0 32 40 104 80 176 120 248 200 392 160 320 240 464 °C °F Temperature Figure 18. Loss angle versus temperature for sintered granular PTFE (60% crystallinity) using evaporated gold electrodes 300 Sintered granular polymer, 60% crystallinity Unsintered coagulated dispersion polymer 93% crystallinity 200 Loss angle - radians 100 0 1 2 log10 Frequency - HZ 3 4 5 6 Figure 19. Loss angle versus frequency for PTFE at room temperature 22 7 8 9 10 18.5 150°C 302°F 160°C 320°F 141°C 286°F s 18.0 na id ar 5 m mho - )j/E( ytivitsiser emulov tnerappA 01gol = el g n 171°C 340°F as s s a na id sn 17.0 ar id a r 00 5 05 = = elg elg n n l ol as s as so 16.5 19.6°C 67.3°F ol 17.5 0 log10 Time - seconds 2 1 3 Figure 20. Plot of log10 apparent volume resistivity versus log10 time for sintered granular PTFE 18 17 16 Evaporated gold electrodes (Heated 40 hours at 280°C;536°F) 15 m mho - )j/E( ytivitsiser emulov tnerappA 01gol 14 Tinfoil electrodes (as received) 13 12 11 10 9 -6 -4 log10 Time - seconds -2 0 2 4 Figure 21. Effect of different electrode materials and preconditioning for sintered granular PTFE 23 HIGH VOLTAGE USES OF PTFE With regard to high voltage applications it has been known for a long time that in the presence of surface discharges failure occurs by erosion, as PTFE is a nontracking material. Parr and Scarisbrick (ref. 50) have compared the behaviour of a wide range of polymeric insulators by the IEE tracking test using electrolyte, and by an ASTM dust-fog test (D21 32-62T). They found that PTFE was one of the erosion class which showed a long life, i.e. >1000 hours in the dust-fog test. Thus PTFE has useful surface characteristics for exploitation in outdoor applications. For bulk insulation high quality fabrication will be required in order to produce structures with the very low level of porosity and internal voiding demanded by high voltage applications (ref. 51). Tests by means of electronic discharge detectors (ref. 52) can be made to ensure freedom from the damaging discharges which may occur in voids. Alternatively it is possible to reduce the discharges by impregnating the PTFE with dielectric liquids or with a high pressure gas so as to fill, at least partially, any voids in the polymer. In consequence, values for dielectric strength obtained from tests conducted in oil may be misleadingly high for poorly fabricated PTFE due to impregnation of any voids present by the oil. 24 Section 5. Thermal properties - unfilled PTFE MELTING POINT The melting point of ‘as polymerised’ PTFE increases with increasing molecular weight and Wunderlich (ref. 52a) has shown that PTFE also superheats, i.e. the apparent melting point increases with increasing heating rate. Melting points determined by Differential Scanning Calorimetry* on ‘as polymerised’ powders at a heating rate of 16°C/minute (28.8°F/minute) vary from about 332°C (630°F) for low molecular weight coagulated dispersion polymer to about 346°C (655°F) for high molecular weight granular material. Measurements made at different heating rates indicate that, owing to the superheating effect, these values may be up to 10°C (18°F) higher than would be obtained at infinitely slow heating rates. The influence of molecular weight on melting point is much reduced after the polymer has been sintered (once melted). Most sintered polymers melt in the range 325330°C (617-626°F) when reheated at 16°C/minute (28.8°F/minute). The way in which the melting point of sintered PTFE varies with applied pressure was studied by McGeer and Duus (ref.34) who reported the following values: 1 atmosphere 69 atmospheres 207 atmospheres 615 atmospheres 324°C 335°C 356°C 419°C (615°F) (635°F) (673°F) (786°F) These latter workers used their data to calculate the latent heat of fusion of PTFE as 14 cal/g at 69 atmospheres and 8.4 cal/g at 207 atmospheres. The corresponding entropies of fusion are 0.0240 cal/g deg K and 0.0134 cal/g deg K. THERMAL EXPANSION If a graphical representation is made of the specific volume/temperature relationship for highly crystalline fabricated PTFE the form of the graph is shown in Figure 22. This graph clearly reveals the presence of the transition point which occurs at 19°C (66°F) with PTFE (refs. 7, 53). Work done on behalf of AG Fluoropolymers showed that from -60°C to +15°C expansion is approximately linear at 9.5 x 10-5 / °C. Work by Kirby (ref. 53) indicates that this coefficient is approximately constant down to -190°C. Above 15°C the coefficient of expansion increases with temperature. Therefore a more useful way of indicating thermal expansion is to express it as a percentage increase in length between two temperatures. Values obtained parallel to and at right angles to the direction of the moulding pressure are quoted separately as they were found to be slightly different. Temperature range °C 15 30 30 30 30 30 °F to to to to to to 30 50 100 150 200 250 59 86 86 86 86 86 to to to to to to 86 122 212 302 392 482 Parallel to direction of moulding pressure % Perpendicular to direction of moulding pressure % 0.4 0.3 0.8 1.5 2.4 3.4 0.4 0.3 0.8 1.5 2.3 3.6 THERMAL CONDUCTIVITY Over the temperature range 20-35°C (68-95°F) the thermal conductivity of PTFE is 6 x 10-4 cal/cm s °C. This result may be expressed in a variety of units: 6 x 10-4 cal/cm s °C 2.2 x 10-1 kcal/m h °C 2.6 x 10-3 joule/cm s °C 1.7 Btu in/ft2 h °F Kline (ref. 54) measured the thermal conductivity of PTFE at 0, 20, 50 and 70°C (32, 68, 122, 158°F). He reports the conductivity to be fairly constant, with a slight tendency to rise at the higher temperatures. His value is about 5.1 x 10-4 cal/cm s °C. Eiermann and Hellwege (ref. 55) studied this property over a much wider temperature range of -180 to +90°C (292 to +194°F). All their values fell within the range 5.4 to 6.1 x 10-4 cal/cm s °C. It was confirmed that the conductivity tends to rise with temperature though a sharp fall occurred at 20°C (68 F), approximately the temperature at which it has already been noted that a lattice transformation of the crystalline component of the polymer occurs. * The melting point of a polymer, as measured by DSC, is taken as the temperature at which the peak of the melting endotherm occurs. This peak is reached when the rate of melting is maximal and indicates the melting point of the bulk of the polymer. The final melting point will be slightly higher than this. 25 0.66 0.64 0.62 0.60 0.58 0.56 0.54 Specific volume 0.52 0.50 0.48 0.46 0.44 0 -50 -58 32 Temperature 50 122 100 212 150 302 200 392 250 482 300 572 350°C 662°F Figure 22. Variation of specific volume with temperature SPECIFIC HEAT AND HEAT OF FUSION The specific heat of PTFE has been determined by Marx and Dole (ref. 56). For temperatures above 40°C(104°F) they give the relationship: Cp = 0.227 + (2.50 x 10-4) T cal/g °C. The heat capacity, enthalpy and entropy of PTFE have been studied and results are reported in two papers (refs. 16, 57). THERMAL STABILITY Within its normal range of working temperatures, the upper limit of which is generally quoted as 260°C (500°F), PTFE suffers no degradation. Indeed, weight losses observed between 260 and 360°C (500 and 680°F) will be exceedingly small and due to the loss of minute amounts of moisture or gas absorbed in the polymer. At processing temperatures of about 380°C (716°F) the rate of decomposition of PTFE is still very low and it is only at temperatures in excess of 400°C (752°F) that thermal decomposition of pure PTFE becomes significant. Madorsky et al. (ref. 58) studied the pyrolysis of PTFE in a vacuum at temperatures from 423.5 to 513°C (794 to 955°F) The decomposition rates which they report at these temperatures are respectively 0.00152% per minute and 1.264% per minute. They further reported that tetrafluoroethylene was virtually the only product of decomposition. This confirmed earlier reports of 26 Lewis and Naylor (ref. 59) that when PTFE was decomposed at temperatures between 600 and 700°C (1112 and 1292°F) under pressures of 5 to 760mm Hg the products were C2F4, C3F6 and C4F8 and that the proportion of tetrafluoroethylene among the products increased with decrease in pressure and tetrafluoroethylene was the sole product at very low pressures. Cox et al. (refs. 60, 61) have studied the thermal degradation of PTFE with particular reference to the differences observed between degradation in a vacuum and in oxygen. They found that the temperature necessary to achieve a 25% weight loss in two hours was 494°C (921°F) in a vacuum and 482°C (900°F) in oxygen; they concluded, therefore, that the thermal degradation of PTFE was relatively little affected by oxidising conditions. Siegle et al. (ref. 62) have evaluated the mechanism of the depolymerisation reaction from research work done on heating thin PTFE films in a vacuum and Jellinek (ref. 63) reached similar conclusions. In the case of thicker sections, which are more likely to be met in practice, the rate of pyrolysis is controlled by diffusion of monomer as pointed out by Siegle and Muus (ref. 64). Paciorek et al. (ref. 65) studied the auto ignition of PTFE in oxygen and in air. The respective auto-ignition temperatures were 512°C (954°F) and 575°C (1067°F). In oxygen only COF2, CO2 and CF4 were formed, while in air, saturated fluorocarbons, COF2 and CO were the most abundant species. Section 6. Surface properties - unfilled PTFE COEFFICIENT OF FRICTION Although the low coefficient of friction of PTFE is widely known, it is interesting to reflect that no reference was made to this characteristic until about ten years after the discovery of the polymer. Credit for this first publication goes to Shooter and Thomas (ref. 66) who measured the coefficient of friction using a Bowden-Leben machine with loads of between 1 and 4 kg (2.2 and 8.8 Ib) and sliding velocities from 0.1 to 10mm/s (0.02 to 2 ft/min). They reported that the coefficient was 0.04. Other workers (refs 67, 68, 69) report that while Amonton’s law is fairly well obeyed at moderate loads the coefficient of friction rises steeply at very light loads, say below 100g (31/2 oz). Thompson et al. (ref. 70) who studied the coefficient at high loads found the extremely low figure of 0.016 at a load of 1360kg (3000 Ib) . The coefficient of friction is dependent also on the sliding velocity, a high speed resulting in a high coefficient. By combining a low load and a high sliding velocity of 1.89m/s (370 ft/min), Flom and Porile (ref. 71) found the high value of 0.36 for the coefficient. In their pioneer paper Shooter and Thomas (ref. 66) claimed that, at the very low speeds they used, the coefficient was independent of temperature over the range 20 to 200°C (68 to 392°F). However, later work has shown that temperature has some effect. King and Tabor (ref. 72) report that the coefficient remains steady at about 0.1 over the range 100 to -45°C (212 to -49°F). On further cooling the coefficient rises to about 0.2 but does not alter further even when the polymer is cooled to 80°C (-112°F). For the behaviour at elevated temperatures the best guide is the work of McLaren and Tabor (ref. 73) who demonstrated that the coefficient of friction fell with increase in temperature. Makinson and Tabor (ref. 74) have also examined the effect of sliding velocity and substantially agree with the variation in coefficient of friction with velocity given above. They have found that whereas at low velocities a thin continuous film of PTFE is laid down on the other slide surface (in this case glass), at higher velocities the PTFE is torn off in discrete fragments. Of less general importance than the dependence on load, velocity and temperature, but still of interest is the observation by Tabor and Williams (ref. 75) that the coefficient is influenced by the orientation of the polymer, the coefficient being about 30% higher when sliding was across the chains than when it was along them. ANGLE OF CONTACT Zisman and his co-workers have studied the contact angles made with PTFE by a wide range of liquids (refs. 76, 77, 78,79). A few of their results with common liquids are summarised: Liquid Contact angle Water n-Hexadecane Toluene Benzene Methylene iodide Carbon tetrachloride Mercury Glycerol 108° 46° 43° 46° 88°, 83° 46° 150° 100° Fox and Zisman (ref. 76) found that there was a critical surface tension (ca 17.5 to 20.5 dynes/cm) below which liquids would wet PTFE (i.e., would spread on a smooth polymer surface). 27 Section 7. Other physico-chemical properties - unfilled PTFE investigated the permeation of sulphur dioxide through a range of polymers including PTFE. PERMEABILITY Work using a sample of cast film produced from Fluon® GP1 led to the following test results for permeability: Oxygen Nitrogen Air 10.5 x 10-10 4.0 x 10-10 5.3 x 10-10 The units are cm3 of gas at NTP x cm (thickness)/cm2 (area). s. cm Hg measured at 23°C ± 1°C (73°F ± 2°F) Work published by Barton (ref. 80), who uses the same units, can be summarised as follows: Hydrogen Helium Nitrogen Oxygen Argon 2.4 7.0 3.1 1.0 5.8 x x x x x 10-9 10-8 10-10 10-9 10-10 Yasuda and Stone (ref, 81) obtained a substantially higher figure, 23.7 x 10-10 (units as above), for gaseous oxygen, and an even greater value, 91.0 x 10-10, for dissolved oxygen, while Pasternak et al. (ref. 82) obtained a much lower value, 4.2 x 10-10, in experiments with membranes in the thickness range 0.081-0.145mm (0.0032-0.0057 inch). The latter authors also give values for hydrogen (9.8 x 10-10), nitrogen (1.4 x 10-10), and carbon dioxide (11.7 x 10-10). Casper and Henley (ref. 83), using PTFE film 0.094mm (0.0037 inch) thick found a value of 11.6 x 10-10 for hydrogen, and 0.65 x 10-10 for ethane. Work on the helium permeability of fabricated PTFE items has shown that the permeability is very dependent on crystallinity (as indicated by relative density). For isostatically-moulded granular PTFE discs the helium permeability at 25°C (77°F) varied from about 30-40 x 1015 mol m s-1 N-1 at a relative density of 2.08 to about 5-15 x 10-15 moI m s-1 N-1 at a relative density of 2.15: the effect of crystallinity was much greater than that of varying the moulding pressure, or the type of PTFE polymer used. For tubing extruded from coagulated dispersion (CD) polymers, a similar effect of crystallinity on permeability was observed. At a relative density of 2.15 the permeability was about 15-25 x 10-15 mol m s-1 N-1 and this fell to about 5-10 x 1015 mol m s-1 N-1 at a relative density of 2.21. Again, no effect of CD polymer type could be detected, even though a considerable number of both homopolymers and copolymers were examined. Gerritse (ref. 84) has measured the permeability of PTFE to oxygen and nitrogen as a function of temperature in the range 50-125°C (122-257°F); for both gases the permeation rate at 125°C was about 5-6 times greater than at 50°C. Felder, Spence and Ferrell (ref. 85) 28 The permeability of PTFE to water vapour has been studied by Konovalov (ref. 86) and by Korte-Falinski (ref. 87) who both found that PTFE has a lower permeability to water vapour than almost any other plastics material examined. For PTFE films in the thickness range 0.050.20mm (0.002-0.008 inch), values were found (ref. 87) equivalent to about 0.9-1.8 g/m2 per 24 hours, per 0.025mm (0.001 inch), at 20°C (68°F). Toren (ref. 88), using a special electrolytic measuring technique, obtained a value equivalent to 2.7 g/m2 per 24 hours per 0.025mm (0.001 inch), for a PTFE film 0.08mm (0.003 inch) thick. A value of 5.4 g/m2 per 24 hours per 0.025mm (0.001 inch) at 30°C (86°F) has also been quoted (ref. 89). These somewhat variable results for water vapour permeability of PTFE may, most probably, be explained by differences in the film fabrication techniques used, as well as by different methods of measurement. INFRA-RED TRANSMISSION Figure 23 shows the infra-red transmission spectrum for PTFE. REFRACTIVE INDEX Billmeyer (ref. 90), using sodium yellow light and a sample of PTFE of density 2.12 reported a refractive index of: nD= 1.376 Using a far infra-red maser and monochromatic radiation of wave-length 337µm Chamberlain and Gebbie (ref. 91) report a figure of 1.391 ± 0.017. The refractive index of PTFE would be expected to vary with density, or more strictly with crystallinity, in accordance with the equation: n2 - 1 n2 + 2 1 x—=K d where n = refractive index d = density K = constant MELT VISCOSITY The melt viscosity of PTFE is extremely high by comparison with other polymers. The observed value will depend somewhat on the experimental method used, of which the parallel plate plastometer, the capillary rheometer and creep methods are the most important. 100 80 Transmittance - % 60 40 20 0 3 4 5 Wavelength - microns 6 7 8 9 10 11 12 13 14 15 Figure 23. Infra-red transmission spectrum (specimen thickness 0.05mm [0.002 inch]) The melt viscosity of PTFE varies with the shear stress applied to the polymer and with the temperature of the polymer but, in general, commercial samples of granular polymer display viscosities of about 1011 poise in the temperature range 360 to 380°C (680 to 716°F) and at shear stresses of about 106 dynes/cm2 (refs. 92, 93, 94). HIGH ENERGY RADIATION The effect of high energy radiation on PTFE was first noted by Liversage (ref. 95) who found that the electrical resistance of the polymer fell on exposure to X-rays. Harrington and Giberson (ref. 96), in a study of the decline in the tensile strength and elongation of PTFE when exposed to gamma radiation, showed that irradiation in a vacuum was less damaging than irradiation in air. This point was confirmed by Wall and Florin (ref. 97) and a summary of their results is given below: 1 Megarad has a measurable effect and 2-3 Megarads in air reduce strength by 40-75%. 4 Megarads reduce tensile strength to 2% of the original. A 1975 report from AERE, Harwell (ref. 99a) gives details of the effects of radiation on the mechanical and electrical properties of PTFE used in cable for the GEOS satellite. CHEMICAL RESISTANCE As might be expected of a saturated aliphatic fluorocarbon PTFE is almost completely inert chemically. Molten or dissolved alkali metals degrade PTFE by abstracting fluorine from the molecule, while at elevated temperatures fluorine and compounds capable of releasing fluorine can break the carbon skeleton and form low molecular weight fluorocarbons. Apart from these not very important exceptions, PTFE resists attack by all the acids, bases and solvents that might be encountered in industrial practice. Irradiation in air 2.4 4.1 2 0 In addition to its remarkable chemical inertness, PTFE is not dissolved by any solvent within its normal range of working temperatures. Small quantities of solvents may be absorbed by PTFE on prolonged exposure especially at elevated temperatures but this in no way impairs the usefulness of the polymer. Irradiation in a vacuum 0.7 4.1 32.0 73 51 43 Rossa (ref. 100) has given details of the effect of 79 chemicals on PTFE with, in many cases, data on weight gain. Radiation dose eV/g x 10-20 % retention of original tensile strength Two general surveys of this subject have been made (refs. 98, 99). The more recent work by Monnet and Bensa (ref. 99) gives further data on the effect of radiation dose on mechanical properties. They found that as little as 0.01 to 0.1 Megarad dose can affect mechanical properties. VELOCITY OF SOUND The velocity of sound in PTFE and the way in which the velocity changes with changes in temperature has been studied by Kravtsov (ref. 101). He showed the velocity to pass through a maximum at 20°C (68°F) in the region of the first-order transition. 29 Section 8. General-filled PTFE FUNCTION OF FILLER CHOICE OF FILLER The incorporation of fillers has the following general effects: It is this choice which presents most problems to the end user. Unfortunately no simple answer is available, mainly because the performance of different fillers cannot always be predicted reliably. Choice frequently depends upon the results of empirical testing rather than upon any understanding of the mechanism affecting properties. (1) (2) (3) (4) (5) Wear resistance is increased to a very marked extent. Resistance to ‘creep’ or deformation under load is increased by a factor of 2 to 5. Depending upon the filler used, the thermal conductivity may be increased significantly. Depending upon the filler used, thermal expansion may be reduced by a factor approaching 5. By suitable choice of fillers some control over the electrical properties of PTFE can be achieved. In addition to these advantages filled PTFE generally retains low coefficients of friction, the wide service temperature range and, depending upon the filler, the chemical inertness of unfilled PTFE. Many materials are candidates as fillers for PTFE provided they can be obtained in the appropriate particle size and will withstand the processing conditions necessary to incorporate them and subsequently to enable the compound to be fabricated. Other considerations such as availability, cost and processability further restrict the number of potential fillers to a relatively small number, as indicated in Table 1. Table 1. Fillers used with PTFE Filler Form Details Glass Usually milled fibres A minimum aspect ratio (length: dia) of 10 : 1 is generally used Carbon and graphite Usually in the form of a high purity powdered coke, or natural or synthetic graphite. Particles are generally irregular in shape although fibres are known Particle size usually less than about 60µm Metals Notably bronze as irregular or spherical particles Particle size usually less than about 60µm Others Various forms of ‘ceramic’ material including mica are used both in particulate and fibre form. Molybdenum disulphide Thermoplastics _ 40 x 10-6 inch Note: 1µm = 10-6m ~ 30 CHOICE OF FLUON® GRADE Having limited the number of potential fillers, the number of grades of filled PTFE which it is possible to manufacture is still large, when combinations and varying percentages of filler are taken into consideration. However, there are reasons why these too may be limited: where lower filler contents of 5% or 15% are justifiable. There is little case, however, for requiring intermediate filler contents. Combinations of filler can give rise to improved wear properties but this appears to be their only advantage. THE FLUON® RANGE (1) The quantity of filler should effectively be limited to 40% by volume if reasonable mechanical strengths are to be maintained. (2) The method of fabricating the filled PTFE powder can have considerable effect upon its properties and these can therefore be varied and controlled during fabrication rather than by a proliferation of diverse formulations. The Fluon® filled polymer range consists of moulding grades denoted by a prefix FC1--- It is considered reasonable therefore to limit the basic range of filled compounds to filler additions of 25% and 40% by volume although there may be exceptional cases Typical properties of the Fluon® moulding grades are given in Table 2 and compared with those of unfilled PTFE. Free-flowing moulding grades (agglomerated) are denoted by a prefix FC8--Development grades are denoted by a prefix XC e.g. XC1--- for moulding grades. Table 2. Properties of the Fluon® range Units Fillers FC168-63* FC100-15 1000 FC100-25 1000 FC160-60 FC150-25 FC140-15 Unfilled PTFE Bronze and graphite Glass fibre Glass fibre Bronze Powdered coke Graphite None FiIler by weight % 63 15 25 60 25 25 - Filler by volume % 40 13.3 22.2 27 28 15 - 3.2 2.25 2.25 3.8 2.1 2.2 2.17 Relative density Maximum tensile strength: moulded MN/m2 kgf/cm2 Ibf/in2 4.9-8.3 50-85 700-1200 17.2-240 175-245 2500-3500 12.3-19.6 125-200 1800-2800 10.3-13.7 105-140 1500-2000 11.8-15.2 120-155 1700-2200 13.7-20.6 140-210 2000-3000 20.6-29.9 210-350 3000-5000 Maximum tensile strength: extruded MN/m2 kgf/cm2 lbf/in2 - 9.2-12.7 100-130 1400-1900 6.9-10.8 70-110 1000-1600 - 10.3-13.7 105-140 1500-2000 - 13.7-17.2 140-175 2000-2500 Ultimate tensile elongation: moulded % 10-15 300-400 200-300 80-160 100-150 200-300 250-400 Ultimate tensile elongation: extruded % - 200-300 100-200 - 75-125 - 250-400 Hardness Shore D 55-65 55-60 55-70 55-65 60-65 55-65 50-55 Heat stability The weight loss at 300°C (572°F) should not normally exceed 0.1% Porosity: dye immersion All material can be made non-porous, depending upon the fabrication techniques used *British Patent No 870117, 926718 and others 31 Section 9. Mechanical properties - filled PTFE COMPRESSIVE DEFORMATION The compressive creep behaviour of filled PTFE is one of the most significant properties to the designer and user. In comparison with unfilled PTFE the compressive modulus of filled PTFE is greater and hence, for the same stress, a lower deformation will occur. This difference diminishes, however, as temperatures rise and the compressive performance of unfilled and filled PTFE draws close together at 200°C (392°F). The reason is almost certainly that the general reduction in the compressive modulus of the PTFE matrix overrides the support given by the random distribution of filler particles. Table 3 gives approximate values for the stressstrain relationship at different temperatures for Fluon® FC100-25 1000. These data are based on laboratory tests and the configuration of the test specimens will have a significant effect on the results obtained. For this reason the figures should only be taken as a very approximate guide. The room temperature creep behaviour of filled PTFE has been studied and Figures 24 and 25 show how strain varies with time and also at various stress levels for glass-filled Fluon® FC100-25 1000 and, for comparison purposes, for Fluon® G163. Figure 26 illustrates the relationship between stress and strain in a way which indicates the stress relaxation that can occur in PTFE with time. Figure 27 shows the divergence in creep behaviour between Fluon® grades containing 25%, 22% and 40% of filler by volume. Figure 27 used in conjunction with Figure 24 indicates the relative creep behaviour of Fluon® filled grades. Individual design details of specific applications are bound, however, to significantly modify the data given in Figures 24 and 27. Recovery After being subjected to a compressive load, filled PTFE will recover some of the resulting strain when the stress is removed. This recovery is slow and may not be complete. Figure 28 shows the recovery of Fluon® FC10025 1000 after the removal of applied stress at various levels. Table 3. Stress-strain relationship for Fluon® FC100-25 1000 at different temperatures and stresses to produce stated compression strain after 24 hours. Stress - kgf/cm2 at T : °C 20 60 100 140 180 220 250 1% strain 63 37 27 17 10 8 6 2% strain 89 60 47 32 20 15 11 3% strain > 89 75 61 43 28 22 17 4% strain > 89 86 71 53 36 28 22 32 10 9 8 7 6 Stress = 6.9 MN/m 2 = 70 kgf/cm 2 = 1000 lbf/in 2 5 4 3 ® on 63 G1 Flu 2 00 2 0- ® 1 0 51 0 C1 F Creep terminated n luo F 0.9 0.8 0.7 0.6 0.5 0.4 0.3 Dotted lines show possible spread as derived from 100 second isochronous stress-strain relationship 6 Months 3 weeks 1 week 1 day 1 hour Strain - % 0.2 0.1 1 10 Time - seconds 10 2 103 104 10 5 106 10 7 10 8 Figure 24. Creep in compression at 20°C (68°F) : Fluon® G163 and Fluon® FC100-25 1000 33 10 9 8 7 6 5 4 3 2 /in 40 17 = 2 f lb m 2 /c gf k 2 = 2 2 12 n 0 m N/ M 2 12 = 5 14 /i bf l m f/c 2 10 = 2 kg 2 /in /m N 60 M 10 = 2 1 lbf 11 m f/c 0.9 .6 0.8 = 2 kg 81 m N/ 2 in 8M 0.7 70 =5 2 0.6 / lbf cm gf/ k 1.2 0.5 =6 2 m N/ 6M 2 0.4 80 /in lbf =5 2 m f/c 0.3 g 8k 0. 2 m =4 N/ 4M 0.2 2 /in 2 /cm bf 0l 9 =2 6 months 2 1 month / MN 1 day 1 hour Strain - % 2 m kg 1 week f .4 0 =2 0.1 1 10 Time - seconds 10 2 103 104 10 5 106 10 7 Figure 25. Creep in compression at 20°C (68°F) at various stress levels; Fluon® FC100-25 1000 34 10 8 11 1600 1500 10 1400 9 1300 3% 1200 8 1100 2% 7 1000 1.5% 900 6 800 1% 5 700 600 4 0.5% 500 3 400 2 300 0.2% 1 10 Time - seconds 10 2 103 10 5 106 6 months 1 week 1 day 104 10 7 100 0 10 8 Stress - ib/in 2 0 1 month 1 1 hour Stress - MN/m 2 200 Figure 26. Isometric stress-time curves in compression at 20°C (68°F) , and various strain levels : Fluon® FC100-25 1000 35 2.6 2.4 Stress: 10 MN/m 2 = 102 kgf/cm 2 = 1450 lbf/in 2 e m 2.2 lu vo y rb 2.0 0 70 er -3 2% fill 0 11 -2 FC me 00 1.6 m -2 by vo lu 00 1.8 e 5% le fil 10 olu yv rb -2 5 1.4 FC 1 00 % 1.2 -63 0 -4 fille 68 1 FC 1.0 0.8 0.6 1 week 0.2 1 day 1 hour Strain - % 0.4 0 102 1 10 Time - seconds 103 104 105 106 Figure 27. Isometric stress-time curves in compression at 20°C (68°F) , and various strain levels : Fluon® FC100-25 1000 1.0 6 MN/m 2 61.2 kgf/cm 2 870 lbf/in 2 Fractional recovered strain 0.8 0.6 2 0.4 2 MN/m 2 2 :290 lbf/in (20.4 kgf/cm 0.2 12 MN/m 0 10-4 10-5 Reduced time 2 ) f/in ) 0 lb 2 cm :174 (122 kgf/ 10-3 10 MN/m 2 102 kgf/cm 2 1450 lbf/in 2 2 10-2 10 -1 1 Figure 28. Recover from creep in compression : Fluon® FC100-25 1000 loaded at various stress levels 36 10 IMPACT STRENGTH Table 4 shows the results of Charpy impact tests on various Fluon® grades, at different temperatures and different crystallinities. All specimens were sharply notched (notch tip radius = 0.25mm; 0.01 inch) but even so none of the specimens broke completely, but gave a hinge break at + 20°C (68°F). At -20°C (-4°F) all the slowcooled (high crystallinity) samples broke completely, but two of the six quenched samples (low crystallinity) gave hinge breaks. In the liquid nitrogen dip test, all specimens broke completely; strengths were always lower than at -20°C (-4°F) and again the lower crystallinity material gave increased resistance to impact. There are minor differences between the various Fluon® grades and, as expected, a low crystallinity gives maximum impact strength. The conclusion is that unfilled and filled PTFE are tough in impact, even under severe test conditions e.g. with sharp notches at -20°C (-4°F) (see Table 4). They are better than most other plastics. Table 4. Charpy impact strength (notch depth 2.80 mm: 0.11 inch; notch tip radius 0.25 mm: 0.01 inch) Median impact strength (cm kgf/cm2) + 20°C -20°C (68°F) (-4°F) Unfilled PTFE H* Fluon® Fluon® Fluon® Fluon® — H — — FC100-15 1000 FC100-25 1000 FC160-60 FC150-25 Liquid nitrogen (-180°C approx) (-290°F approx) Slow cooled Quenched Slow cooled Quenched 6.8-9.0 8.6-9.6 — — 12.0 9.4 10.9 7.3 H H 12.8 7.9 4.5 — 4.1 3.2 5.6 — 4.5 3.2 Notes: H = hinge break i.e. did not break completely. H* = specimen almost broke completely. 37 Section 10. Electrical properties - filled PTFE Although the primary objective in the development of Fluon® grades has generally been to produce materials with a range of mechanical properties, the addition of fillers does have a marked effect on the electrical properties as well. In particular, graphite - and carbon filled compounds may have a relatively high conductivity, which can assist the dissipation of static charges in applications where these are a problem. Filled PTFE is a mixture of materials, and voids - no matter how small - are always present: as with all porous materials, the properties are dependent on the nature of the environment and of any inadvertent contamination. The electrical properties are no exception and are markedly dependent on the environmental humidity. The spillage of conducting liquids, electrolytes and greases on Fluon® grades can affect the properties of the material even in otherwise dry conditions. To some extent porosity (and therefore the effects of humidity and spillage) is dependent upon the method of fabrication, but even in a relatively non-porous part, the surface is liable to be absorbent. for insulation. Tables 5, 6 and 7 give values of loss tangent, permittivity and volume and surface resistivities, measured at two levels of humidity, for Fluon® glass-filled grades. The effect of temperature on the loss tangent of some glass-filled grades is shown in Figure 29. The level of dielectric loss tends to increase as glass content increases. However, the mechanisms giving rise to dielectric behaviour of filled materials are complicated, and in general it must be assumed that these materials will exhibit Maxwell-Wagner loss processes of relatively large amplitude at low frequencies (log10 frequency < 0) in the ‘dry’ state, moving progressively to higher frequencies with increasing moisture content. Rudner (ref. 102) reports on, but does not interpret, the properties of PTFE filled with titanium dioxide using samples that had been kept at a constant low humidity with silica gel crystals present to absorb moisture. It is suspected that these losses are due to a similar mechanism. CONDUCTING MATERIALS INSULATING MATERIALS Under dry conditions, the glass-filled grades are excellent electrical insulating materials over a wide range of temperature. Their insulating properties deteriorate with increasing humidity, but even at 95% r.h. the properties are comparable with those of plasticised PVC and of some thermosetting compounds commonly used Temperature °F 50 100 200 150 No grade of filled PTFE is a good conductor when compared with, for example, copper or aluminium. However, some have sufficiently low volume and surface resistivities to be considered for use in antistatic applications: see Table 8. 250 350 300 450 400 0.030 0.028 0.026 0.024 70 00 0.022 030 0.020 FC 11 0.018 0.016 0.014 0.012 0.010 Loss tangent 0.008 000 51 -2 100 0.006 FC 0.004 0.002 0 FC100-05 0 20 40 Temperature °C 60 80 100 120 140 160 180 200 220 240 Figure 29. Loss tangent versus temperature at 1 kHz: glass-filled PTFE Notes: Form of specimen: 5 cm (2 inch) diameter disc of skived tape approx.1mm thick (0.04 inch). Electrode system: No electrodes, 3-terminal fully shielded system. Test apparatus: General Radio Capacitance Measuring Assembly, type 1620A. Electric stress: Up to 120 V/mm (3 V/0.001 inch). Field direction: Perpendicular to the plane of the sample. Relative humidity: Dried for 150 h at 0,1 mm Hg at 116°C (241°F). Accuracy of test result: Estimated to be ± 5%. 38 Table 5. Loss tangent at room temperature ‘Dry’† After 9 weeks at 95% r.h. 103 Hz 0.0001 0.00033 0.00065 0 00107 Unfilled PTFE Fluon® FC100-05 Fluon® FC100-15 1000 Fluon® FC100-25 1000 104 Hz 0.0001 0 00032 0.00063 0 00097 103 Hz 0.0001 0.14 0.32 0.39 104 Hz 0.0001 0.122 0.36 0.28 105 Hz 0.0001 0.058 0.275 0.225 106 Hz 0.0001 0.0126 0.068 0.062 † Dried for 150h at 0.1mm Hg at 116°C (241°F). Note: Samples were skived from tape 1.0mm thick veneered (0.04 inch) from blocks preformed at 700 kgf/cm2; 10 000 Ibf/in2 freely sintered for 11/2 hours at 380°C (716°F) and cooled at approximately 30°C per hour (54°F per hour). Table 6. Permittivity at 105 - 107 Hz Ambient humidity Unfilled PTFE Fluon® FC100-15 1000 Fluon® FC100-25 1000 2.02-2.09†† 2.2-2.5 2.2-2.5 95% r.h. 2.02-2.09†† 2.2-2.5 2.2-2.5 †† Depending on density Table 7. Volume and surface resistivity Unfilled PTFE Fluon® FC100-15 1000 Fluon® FC100-25 1000 Volume resistivity(1) (ohm cm) Surface resistivity(2) (ohm) Dry(3) Ambient humidity 95% r.h. >1 x 1018 >2 x 1015 >2 x 1015 1017 1015 1015 1015 1015 Notes (1) Measured on discs of skived tape approx. 50.8mm (2 inch) in diameter and 10mm (0.04 inch) thick, using evaporated aluminium electrodes. 1 min. value: 120 V/mm (3 V/0.001 inch). (2) 1 min. value at equilibrium with the environment. (3) Dried for 150 h at 0.1mm Hg at 116°C (241°F). Table 8. Volume and surface resistivity of Fluon® grades FC140-33 FC150-25 FC168-63 FC140-15 FC160-60 Filler(1) by weight % Volume resistivity(2) (ohm cm) Surface resistivity(3) (ohm) 33% 25% 63% 15% 60% 102 104 104 106 107 104 107 104 1014 109 Notes (1 ) Filler % by weight, the remainder being PTFE. (2) Volume resistivity measured at 23°C (73°F) and 50% r.h. on tape specimens 0.25 to 1.0mm (0.01 to 0.04 inch) thick clamped between disc brass electrodes. The values given are an indication only and may vary widely with fabrication methods. (3) Surface resistivity measured at 23°C (73°) and 50% r.h. on tape specimens 0.25 to 1.0mm (0.01 to 0.04 inch) thick using disc and ring brass electrodes applied by pressure only. No backing guard electrode used. With some materials the measured surface resistivity is very high even when the volume resistivity is low. This is probably because the veneering method used to prepare tape specimens may have tended to smear a fine PTFE layer on the surface. 39 Section 11. Thermal properties - filled PTFE THERMAL EXPANSION The thermal expansion of most fillers is less than that of PTFE and since the expansion of the composite will be somewhere between that of the two constituents, filled PTFE compounds expand less than unfilled PTFE. During fabrication certain fillers, notably fibres and platelets, become preferentially oriented (as do the particles of PTFE to a much lesser degree). The result is that some compounds have a markedly different expansion in the directions parallel and perpendicular to the direction of moulding. Measurements on the Fluon® range are shown in Table 9. As thermal expansion is virtually linear below 15°C (59°F) a coefficient is quoted; but since there is a transition point at about 19°C (66°F) and the expansion is far from linear above 30°C (86°F) changes in dimension are quoted as a percentage for a given temperature range. Figures for some common metals are also quoted in Table 9 (Note 2). It is very important to note that these figures are actual linear thermal expansions with virtually all stresses removed from the material. Changes in the dimensions of a specified part due to changes in temperature will differ from these figures if stresses are present. THERMAL CONDUCTIVITY The thermal conductivity of PTFE is very low, making it a good thermal insulating material. Many fillers, notably metals and metal oxides, have high thermal conductivity, but in general they are effectively encapsulated by PTFE so that the conductivity of the compounds is still relatively low. Typical figures for the Fluon® range are given in Table 10, together with those of some common metals and insulating materials. Table 10. Thermal conductivities Material Thermal conductivity 10-4 cal/cm Btu in/ft2 s deg C h deg F Unfilled PTFE Fluon® FC100-15 1000 Fluon® FC100-25 1000 Fluon® FC140-15 Fluon® FC150-25 Fluon® FC160-60 Fluon® FC140-33 Fluon® FC168-63 Aluminium Brass Iron (cast) Steel (med. carbon) Glass Still air Granulated cork Kapok 6 8 9 11 13 19 27 30 4950 2300 1520 1100 18.4 0.64 1.10 0.85 1.7 2.3 2.6 3.2 3.8 5.5 7.8 8.7 1400 650 430 310 5.2 0.18 0.31 0.24 Table 9. Linear thermal expansion: Fluon® range (in directions parallel and perpendicular to direction of moulding) Units FC100-15 1000 FC100-25 1000 FC150-25 FC160-60 FC140-15 FC168-63 Para Perp Para Perp Para Perp Para Perp Para Perp Para Perp Coefficient of expansion from -60 to +15°C (-76 to +59°F) x 10-5 per °C 9.2 6.6 9.2 4.4 6.9 6.4 6.6 6.4 8.6 6.4 Change from: 15-30°C (5°-86°F) % 0.4 0.3 0.4 0.3 0.4 0.2 0.4 0.2 0.3 0.2 0.3 30-50°C (86-122°F) % 0.3 0.2 0.3 0.1 0.2 0.2 0.2 0.1 0.2 0.2 30-100°C (86-212°F) % 0.9 0.6 0.8 0.4 0.6 0.5 0.6 0.5 0.7 30-150°C (86-302°F) % 1.7 1.0 1.5 0.7 1.2 1.0 1.1 0.9 30-200°C (86-392°F) % 2.4 1.5 2.2 1.0 1.9 1.5 1.8 30-250°C (86-482°F) % 3.5 2.2 3.2 1.4 2.7 2.4 2.5 5.4 5.2 Unfilled PTFE Para Perp 9.9 9.6 0.1 0.4 0.4 0.2 0.2 0.3 0.3 0.6 0.5 0.5 0.8 0.8 1.4 1.0 0.9 0.8 1.5 1.5 1.5 2.1 1.6 1.4 1.3 2.4 2.3 2.2 3.2 2.3 2.1 2.0 3.4 3.6 Notes: 1. All measurements made on samples taken from discs 7.30 cm dia x 1.27 cm thick (2 7/8 inch dia x 1/2 inch), preformed at 700 kgf/cm2 10 000 Ibf/in2 and sintered at 380°C (716°F). 2. Coefficients of expansion (x 10-5 per °C) of some other materials are: Aluminium 2.4 Brass 1.9 Glass 0.9 Iron (cast) 1.1 Steel (med, carbon) 1.2 40 Section 12. Surface properties - filled PTFE It is not considered meaningful to tabulate results for design properties in one large table and so each property is discussed separately and relevant values included in their correct context. All values quoted are actual results, and if applied to design calculation a relevant factor of safety should be applied. when mating areas are large, friction is primarily due to adhesion. Orientation It has been shown (see page 27) that the coefficient of friction can be affected by up to 30% depending upon the orientation of the PTFE molecules. FRICTION Most studies on the friction of PTFE have been carried out with unfilled PTFE. Whilst the exact mechanisms involved are still not fully understood (ref.103) a picture emerges in which the ‘dry’ coefficient of friction is dependent upon the pressure, the speed, the temperature, the mating surface, the orientation of the PTFE, the environment and the time of running. Coefficients from 0.016 to 0.36 have been quoted and while this work is discussed in detail on page 27 it may be summarised (with some additional information) as follows: Load and pressure The classical laws of dry friction state that the friction force is independent of the apparent area of contact, making the friction force proportional to load rather than pressure. Many investigators (eg, refs. 66-70) quote the coefficient of friction of PTFE as a function of load and show it to rise steeply at very light loads (below 5 Ib) and decrease with increasing load. R B Lewis (ref. 104) does not support this, but suggests the coefficient of friction µ is proportional to the applied pressure P (Ibf/in2) according to the formulae: µ = CP-0,2 where C = 0.12 ± 0.03 at velocities below 10mm/s (2 ft/min) C = 0.35 ± 0.10 at 50mm/s (10 ft/min) C = 0.45 ± 0.15 at 500mm/s (100 ft/min) and above Speed The coefficient of friction falls markedly at low speeds (below 50mm/s; 10 ft/min) and increases with increasing speed. Temperature The coefficient of friction appears to be stable over the range -45 to 100°C (-49 to 212°F) but to rise at lower temperatures and fall at higher temperatures (see page 25). Mating surface Work by Steijn (ref.105) showed that sliding of PTFE against steel gave lower coefficients of friction than sliding bulk PTFE against bulk PTFE. He suggests that Environment Steijn (ref.105) showed that prolonged and continuous running under dry nitrogen (5-10 parts per million of water) gave rise to intermittently high coefficients of friction but this was alleviated as soon as normally moist air (50% r.h.) was admitted. The short term tests at temperatures from -1 to + 60°C (30 to 140°F) in helium, oxygen, nitrogen and air showed no such effect and neither did tests in air at room temperature with relative humidities in the range 12 to 54%. The friction of PTFE in vacuum (10-9 mm Hg) was studied by Buckley and Johnson (ref.106) who obtained coefficients of friction of 0.25 with a load of 1 kg. They also report the coefficient to be constant over the speed range < 50mm-5 m/s (< 101000 ft/min). This high figure could well be attributed to the relatively small loads applied, but may be linked with Steijn’s observations regarding very dry atmospheres. Several investigators (refs.107, 108) have shown that the coefficient of friction is decreased dramatically by the addition of lubricants. This is not surprising since, if a full film of oil is present, the friction is virtually independent of the mating surfaces. Time of running The work of Steijn (ref. 105) shows that the coefficient of friction for PTFE on PTFE is influenced by the number of traverses, the time lapse between runs, the nature (especially velocity) of the preceding sliding and the thermal history of the sliding components. Mitchell and Pratt (ref. 109) demonstrated a similar increase in friction with time for PTFE on steel, up to a steady level (from 0.05 to 0.20 in 4 hours), and showed this to be due to a change in the surface of the PTFE rather than a change in the surface of the steel (i.e. the transfer of PTFE to the steel). Filler type and volume Thompson et al. (ref. 70) suggest that when using molybdenum disulphide (MoS2), asbestos, carbon, graphite, and copper as fillers, as the volume of filler increases the coefficient of friction increases from 0.016 (no filler) to ~ 0.030 (30% of filler), but that there is little difference in this effect between the various fillers. 41 For a similar range of fillers Milz and Sargent (ref.108) showed the coefficient to be independent both of the type of filler and its volume addition. In particular, MoS2 and graphite showed no advantage over glass fibre, asbestos and copper. Their results for all types ranged from 0.09 to 0.22 depending on velocity, load, etc. They concluded that the filler was effectively encapsulated and the friction was that of PTFE only. O’Rourke (ref.110) originally came to the same conclusion but later (ref.111) states that friction is dependent more upon the volume than the type of filler, although cadmium oxide is claimed to be an exception. At the very low temperatures of liquid oxygen and nitrogen (ref.112) and under conditions of high vacuum (ref.106) there is considerable variation in the coefficient, but this does not appear to be correlated with either filler type or volume. In practical tests with the Wankel engine (ref.113) using various grades of PTFE as a seal, the coefficient was again found to be independent of the filler, whilst in a laboratory test, Ganz and Parkhomenko (ref.107) state that the type of filler is important; however, they appear to quote the filler content as % by weight so that filler type and filler volume are not separable. They again found MoS2 and graphite fillers to give high coefficients of 0.26 to 0.34. The evidence of Mitchell and Pratt (ref.109) is that filler type has a greater effect than filler volume, with MoS2 giving a lower coefficient than unfilled PTFE. They found bronze had little effect and kieselguhr increased it by 25%. Work done on behalf of AG Fluoropolymers (see Table 11) suggests that volume of filler is not directly related to friction coefficient but fillers in general raise the coefficient under these particular test conditions by a factor of about two. It has also been suggested (refs.110,114) that the addition of MoS2 and carbon to glass fibre compounds reduces the coefficient of friction, although figures quoted show only a marginal decrease. Tests carried out on behalf of AG Fluoropolymers have not confirmed this and Buckley et al. (ref.106) found no improvement when working under vacuum. Similarly, practical tests (ref. 113) showed no advantages for adding MoS2 to glass although this combination was suggested (ref.115) as a possible means of reducing the scoring of shafts, and (ref.111) for use in very dry gases. It is conceivable that after prolonged continuous running under dry conditions, the MoS2 is not subject to the rise in friction reported for PTFE. There is therefore conflicting evidence as to the effect of filler type and volume upon the coefficient of friction of PTFE. Filler particle size and shape It is difficult to separate the effects of particle size and shape from those of filler type, since specific forms of particle tend to be used with specific types of filler (e.g. glass fibre, irregular particles of graphite and MoS2, spherical-bronze, etc.). Moreover, in much of the published work no details of filler particle are given. The most explicit work in this field is that of Speerschneider and Li (ref.116) where, with the very hard particles of alumina (Al2O3), they found spherical particles gave coefficients of friction similar to that of unfilled PTFE (0.05-0.08) whereas irregular particles gave significantly higher results (0.14-0.15). They attributed this increase to cleavage of the irregular Al2O3 which saturates the surface until the coefficient is that of Al2O3 on steel. The abrasive nature of the filler also gives a ‘rough’ surface finish to the steel, thereby giving a coefficient approximately double that of a ‘smooth’ steel surface. This effect is less likely to occur with softer fillers, and this has been found true with bronze, where no difference in friction has been found between spherical and irregular particles, although Thompson et al. (ref. 70) suggest that particle size can have an effect in extreme cases. Table 11. Dynamic coefficient of friction for various Fluon® grades Grade FC168-63 FC100-15 1000 FC100-25 1000 FC160-60 FC150-25 FC140-15 FC101-20 Coefficient of friction 0.20 0.10 0.11 0.16 0.17 0.22 0.19 Test conditions Mating surface: 420 S 37 steel in T condition (BS 970:Part 4:1970) Surface finish: 0.3µm R (CLA) BS 1134:1972 Pressure: 20 kgf/cm2 (300 Ibf/in2) Speed: 0.25m/s (50 ft/min) 42 Other parameters (load, speed etc.) The statements made in the first part of this section for the effects of load, speed, temperature, etc. upon the coefficient of friction of unfilled PTFE in general hold good for filled PTFE, although O’Rourke (ref.111) shows that the coefficient of glass-filled PTFE does not rise at low loads, whilst other investigations (refs.108, 112) suggest that it does. Environments Work with filled PTFE at low temperature and in contact with liquid oxygen and nitrogen (ref.112) shows the coefficient to rise with the passage of time (e.g. 0.18 to 0.43 in 23 hours), which tends to confirm the work of Steijn with unfilled PTFE (ref.105). This same effect at room temperature has been found by work done on behalf of AG Fluoropolymers and by Mitchell and Pratt (ref.109) although actual coefficients are lower (0.07 to 0.20 in 20 hours). There is some evidence therefore that the coefficient of friction increases in the presence of liquid oxygen or nitrogen. High coefficients (0.2 to 0.4) were also found by Buckley et al. (ref.106) for filled PTFE under high vacuum, but some of the fillers, notably copper, silver and powdered coke gave coefficients lower than for unfilled PTFE under the same conditions. The reasons for these effects are not known: the effects may be due to temperature or environment, or the mechanisms may be similar to that experienced with graphite where the low coefficient of friction is attributed to the presence of adsorbed gases at the crystallite interfaces where cleavage occurs (ref. 103). WEAR Wear mechanisms The mechanisms responsible for the wear of PTFE are not fully understood, but it is generally thought that adhesion and the freeing of transferred wear fragments, either in terms of surface energy or by virtue of fatigue, are of major importance (refs. 103, 104, 109, 117). It is known that when PTFE is rubbed against other materials a transfer takes place (refs. 116, 118) and it is believed that the wear process involves the laying down and subsequent removal of such transferred layers. An ideal situation is given (ref. 117) as having a highly oriented mono-molecular layer of PTFE bonded to the metal surface which then rubs against as smooth a mating surface of PTFE as possible. What is not clear is exactly how and why fillers and conditions affect both the initial laying down and subsequent removal of the PTFE particles. It is suggested that a minimum temperature at the interface is required to promote adequate bonding and that certain fillers function by causing frictional heat (ref. 117). It is also clear that surface finish will affect this transfer, and whilst there is wide agreement that too rough a mating surface will cause rapid wear (refs. 111, 117, 119), one school of thought suggests that too smooth a surface finish leads to high wear rates, (ref. 111 ) while others suggest that is not so (refs. 117, 119). The answer may be that although too fine a finish may well inhibit good transfer, many filled compounds are sufficiently abrasive to roughen the mating surface adequately. However, if the filler or environmental conditions are too abrasive, rapid wear will occur through ploughing. The entrapment of wear debris can have a similar affect, (ref. 109). It has been suggested that chemical reactions at the interface may be important. Buckley and Johnson (ref. 106) consider that wear is related to the decomposition mechanism and hence to the temperature at the interface, while Hargreaves and Tantam (ref. 112) suggest lead oxide can be an oxygen carrier to other metals, giving selective oxidation of roughnesses on the mating surface. Mitchell and Pratt (ref. 109) have noted the formation of copper fluoride at the interface of bronze-filled PTFE, presumably caused by local degradation of the PTFE and bronze. They do not, however, attribute the reduction in wear accompanying the formation of copper fluoride to the chemical action, but rather to the fact that the area of contact at the interface increases with time, which reduces the interface temperature. Vinogradov (ref. 120) did however attribute a reduction in friction between copper and PTFE to the formation of the solid lubricant copper fluoride. Load and speed (Pressure x Velocity) The most widely quoted formula for the wear of filled PTFE is that of Archard and Hirst (refs. 121, 122) which states that the volume wear (W) is proportional to the relative speed at the interface (V), the load supported (M) and time run (T), ie, W ∝ MVT or using the ‘wear factor’ K W= KMVT (Equation 1) By dividing by an area (A), a linear wear (R) is obtained such that W M R = — = KVT—; A A M but — is the pressure applied (P) A . . . R = KTPV (Equation 2) Equation 2 suggests that the wear rates of materials can be classified in at least three ways: 43 (1) By quoting the maximum PV value the material can withstand (termed limiting PV value). This is found experimentally either by determining the maximum load that can be applied at constant velocity while still maintaining temperature and/or frictional torque equilibrium, or by determining the PV value at which the wear rate suddenly increases. (2) By quoting the PV value which gives a specified wear rate. This is generally quoted as the PV value to give 0.127mm (0.005 inch) wear in 1000 hours, and is determined from specific wear tests. (3) By determining the constant K in Equation 2. This is known variously as the ‘wear factor’ or ‘K-value’. Work has been carried out to determine these factors for various filled PTFE materials (refs. 109, 111). However, during these and subsequent investigations (ref. 104) it has been shown that there are two major errors in accepting results derived from Equation 2: (a) K is not necessarily a constant for a given material, but will vary with the load applied, the velocity, the length of time run, the temperature and other factors such as clearance and conditions at the interface. (b) The method of determining the factors is invariably to test specimens. The conditions of test have a considerable effect upon the results and universal values cannot be obtained from one series of tests. Temperature R B Lewis (ref. 104) suggests that each material has two _ 7) and severe wear (K > wear rates (metric), mild wear (K ~ 35) which is attributed to a rise in temperature at the interface. The actual temperature at which the transition occurs is reported to depend upon the load. He concludes that the PV value at which transition begins depends upon the application geometry, ambient temperature, and manner and amount of cooling, whilst the slope of the transition depends upon the application parameters and properties of the compositions. The mild wear is reported to be characterised by wear of the surface layers whilst severe wear is characterised by bulk removal of material. Similar conclusions were drawn by Summers. Smith (ref.123) who considered the composite to be hard granules in a ‘cement’ of softer materials suggests that the mild wear region corresponds to a gradual attrition of the hard granules whilst the change to severe wear occurs when the ‘cement’ becomes softened by heat and the granules are plucked bodily out of the matrix. From work carried out by Mitchell and Pratt (ref.109) and work done on behalf of AG Fluoropolymers, it is concluded that the entrapment of wear debris as well as surface temperature is a very important factor in determining whether severe wear occurs or not. 44 For example, although the difference in running conditions between a thrust washer and a piston ring is mainly considered to be one of interface temperature, it is also true that wear debris is far less likely to become entrapped in the piston ring. It is also true that differences in wear rate can be attributed to differences in behaviour (abrasive or otherwise) when trapped wear debris is present. Nevertheless, whatever the mechanisms, it is generally accepted (refs.104, 106, 113, 117) that an increase in interface temperature increases the wear rate. Mating surface and material At room temperatures and above it is generally agreed that a hard, approximately 900 VPN (Vickers Pyramid Number), mating surface is beneficial. Softer materials can be used providing the filler will not abrade them. The materials with good dry bearing properties of their own (e.g. bronze) are preferred to the softer more easily damaged materials (e.g. aluminium). There is some divergence of opinion as to the suitability of chromium plating. Pratt (ref.117) shows chromium plating to be advantageous whereas O’Rourke et al. (refs.111,124) show it to give poor results. The answer might well be that the fillers used by Pratt were less abrasive than those used by O’Rourke The surface finish of a material is generally quoted as a mean centre line average - CLA - or Ra (BS1134-2: 1990) of the ‘peaks and valleys’ of its surface as detected by traversing a diamond stylus across it. This does not fully specify a surface however, since a turned and a ground surface of the same Ra value will be different. It is now generally accepted that a ground surface is superior to a turned surface and that above 0.75µm the wear rate of the filled PTFE will increase. The existence of a lower limit is still in dispute and so the best compromise is to use a ground surface finish of 0.2-0.4µm. Lubrication ‘Lubricant’ is a very general term and it used to be stated that any liquid will act as a lubricant and be beneficial to PTFE. To some extent this is true in that, if hydrodynamic conditions are established, no wear will take place, but filled PTFE may run under conditions of boundary lubrication. Hydrocarbon oils are generally advantageous, with a significant reduction in wear rates. This is not so with water. O’Rourke (ref.111) confirmed that the wear factor increased for unfilled and various filled PTFE compounds when running against steel with water boundary lubrication. Work done on behalf of AG Fluoropolymers has shown that boundary lubrication with water gave a reduction of wear life of 50% when filled PTFE ran against steel. Section 13. Other physico-chemical properties - filled PTFE PERMEABILITY CHEMICAL RESISTANCE The permeability of filled PTFE is very dependent upon methods of fabrication. Since there is no chemical bonding between PTFE and the fillers used, the permeability is generally greater than that of unfilled PTFE. As the filler content increases, particularly above 10% by volume, special care, or special techniques, have to be adopted to ensure minimum permeability. Specific measurements have not been made, but from porosity tests it is concluded that permeabilities can be made close to that of unfilled PTFE if the correct method of fabrication is used. PTFE is one of the most chemically resistant materials known, and fillers can only worsen this position. Table 12 gives a list of the probable suitability of the Fluon® range for use with various common chemicals. As noted below this table, some of the information was obtained from direct experimentation whilst other data were predicted from a knowledge of the chemistry of the individual constituents. As with unfilled PTFE, chemical attack on the filled PTFE should not be confused with chemical attack on adjacent parts resulting from permeability of the filled PTFE. Table 12. Suitability of Fluon® range for use with various chemicals at 50°C (122°F) NB. This table is intended solely as a general guide to material selection. Because exposure conditions can vary considerably in different applications, the user is strongly advised to undertake tests under conditions relevant to the specific application. Chemical Fluon® Grade FC168-63 FC100-15 1000 FC100-25 1000 FC150-25† FC140- 15† FC160-60 50% H2SO4 U S* PS U Conc. HCl U PU* PS U Conc. HNO3 U PU* PS U 40% NaOH PS PU* PS PS 0.880 NH4OH U S* PS U Benzene PS S* PS PS Phenol PS S* PS PS Trichloroethylene PS S* PS PS Ethanol PS S* PS PS Fluorine - PU PS - Chlorine PS(dry) PS PS PS (dry) Bromine - PS PS - HF PS∆ U PS PS∆ SO2 - PS PS - Mercury U PS PS U Notes S= Satisfactory U = Unsatisfactory PS = Not tested, but probably satisfactory PU = Possibly unsatisfactory † FC150-25 and FC140-15 will be attacked only by oxidation, although there may be a slight reduction in weight when in contact with other chemicals, due to attack on the very small quantities of impurities (less than 2%) inherently present in the filler. * The results of tests in which samples of tape 50.8mm (2 inches) square and 0.38mm (0.015 inch) thick were used in order to give the maximum surface area to weight ratio. The samples were dried, weighed and then immersed in the various liquids at 50°C (122°F). After a period of four weeks the samples were removed from the liquids, washed, dried and re-weighed to determine whether attack had occurred. Materials listed as ‘satisfactory’ showed no change in weight over the four week period and those showing some change are listed as ‘possibly unsatisfactory. Over the four week period the average change in weight of the ‘possibly unsatisfactory’ materials was 7%. The tensile properties were measured before and after the chemical resistance tests: no statistically significant changes in tensile properties were recorded in any of the tests, including those in which weight losses occurred. ∆ Up to 70°C (160°F). 45 Section 14. Typical properties of Fluon® unfilled and filled moulded PTFE Property Units Unfilled †FC100-25 1000 †FC160-60 Relative density - 2.1-2.2 2.25 3.8 Filler by weight and type - - 25% glass fibre 60% bronze Maximum tensile strength MN/m2 kgf /cm2 Ibf/in2 20.6-34.3 210-350 3000-5000 12.3-19.6 125-200 1800-2800 10.3-13.7 105-140 1500-2000 Elongation at break % 250-400 200-300 80-160 Compressive modulus for 1% deformation (20°C,1 day) MN/m2 kgf/cm2 1 bf /in2 392 4000 55,000 588 6000 85,000 736 7500 105,000 Impact strength at -20°C (Charpy, notched) cm kg/cm2 ft Ib/in2 8 4 9 45 11 55 Hardness Shore D 60-65 70-75 70-75 Volume resistivity ohm cm > 1018 1015 107 Surface resistivity ohms 1017 1015 109 Permittivity at 23°C, lO5-107 Hz: dry 95% r.h. - 2.05 2.05 2.35 2.35 Conducting filler Conducting filler 0.0001 0.0001 0.001 0.3-0.4 Conducting filler Conducting filler 1.8 1.0 1.5 1.1 Loss tangent at 23°C and 103 -104 Hz: dry 95% r.h. Linear thermal expansion 20-150°C: parallel to direction of moulding perpendicular to direction of moulding % % 1.9 1.8 Thermal conductivity 10-4 cal/cm s °C Btu in/ft2 h °F 6 1.7 9 2.6 19 5.5 Continuous service temperature °C °F -250 to +260 -420 to +500 -250 to +260 -420 to +500 -250 to +260 -420 to +500 Coefficient of friction (dynamic) - 0.06 0.12 0.13 Resistance to weathering - Excellent Excellent Excellent Chemical resistance - Fluon® is chemically inert and unaffected by all known chemicals except alkali metals, fluorine under certain conditions, and some fluorine compounds at elevated temperatures. Filled Fluon® has inferior chemical resistance because of the presence of fillers. The data presented are based on experiments which are believed to be accurate and reliable. Additional data are available on request. † The Fluon® range contains compositions of PTFE with fillers such as glass-fibre, bronze, powdered coke and graphite. 46 Section 15. Specifications relating to PTFE Fluoropolymer raw materials can be designated and specified using ISO 12086-1 and -2:1995. Virgin PTFE semi-finished products can be designated and specified using ISO 13000-1 and -2:1997. In addition there are numerous national specifications covering raw materials, semi-finished and finished articles which change continually. Please contact Asahi Glass Fluoropolymers UK Ltd for details. 47 Section 16. Handling precautions Within its working temperature range PTFE is a completely inert material, but when heated to its sintering temperature it gives rise to gaseous decomposition products or fumes which can produce unpleasant effects if inhaled. Fumes can be produced during processing: for example, when the material is heated to sinter it, or when brazed connections are being made to cable insulated with PTFE. The inhalation of these fumes is easily prevented by applying local exhaust ventilation to atmosphere as near to their source as possible. Smoking should be prohibited in workshops where PTFE is handled because tobacco contaminated with PTFE will during burning give rise to polymer fumes. It is therefore important to avoid contamination of clothing, especially the pockets, with PTFE and to maintain a reasonable standard of personal cleanliness by washing hands and removing any PTFE particles lodged under the fingernails. 48 Section 17. Further information The following is a comprehensive list of Technical Service literature for Fluon® PTFE available from the AG Fluoropolymers sales office. F1 The Moulding of PTFE granular powders F2 The Extrusion of PTFE granular powders F3/4/5 The Processing of PTFE coagulated dispersion powders F6 Impregnation with PTFE aqueous dispersions F8 Processing of filled PTFE powders F9 Finishing processes for polytetrafluoroethylene F11 Colouring of polytetrafluoroethylene F12/13 Physical properties of unfilled and filled polytetrafluoroethylene F14 Isostatic compaction of PTFE powders F15 Cast Film from Fluon® PTFE dispersion GP1 FTI500 Fluon® - A Guide to Applications, Properties & Processing FTI800 Potential Material & Equipment Suppliers Information contained in this publication (and otherwise supplied to users) is based on our general experience and is given in good faith, but we are unable to accept responsibility in respect of factors which are outside our knowledge or control. All conditions, warranties and liabilities of any kind relating to such information, expressed or implied, whether arising under statute, tort or otherwise are excluded to the fullest extent permissible in law. The user is reminded that his legal responsibility may extend beyond compliance with the information provided. Freedom under patents, copyright and registered designs cannot be assumed. Fluon® grades are general industrial grades. It is the responsibility of the purchaser to check that the specification is appropriate for any individual application. Particular care is required for special applications such as pharmaceutical, medical devices or food. Not all grades are suitable for making finished materials and articles for use in contact when foodstuffs. It is advisable to contact the AG Fluoropolymers sales office for the latest position. Users of Fluon® are advised to consult the relevant Health and Safety literature which is available from the AG Fluoropolymers sales office. Users of any other materials mentioned in this publication are advised to obtain Health and Safety information from the suppliers. This edition ©AGFP September 2002 49 Section 18. References 1 Free energies of formation of fluorocarbons and their radicals. Thermodynamics of formation and depolymerisation of polytetrafluoroethylene, W M D Bryant, J.Poly. Sci., 56, 1962, 277-296 2 Structures of molecules and crystals of fluorocarbons, C W Bunn and E R Howells, Nature, 174, 4429, 18th September, 1954, 549-551 3 Crystal structure of polytetrafluoroethylene, R H H Pierce, E S Clark, J F Whitney and W M D Bryant, Abstracts of 130th Amer. Chem. Soc. meeting, Atlantic City, September, 1956, 9S 4 Unusual features in the crystal structure of polytetrafluoroethylene, E S Clark and L T Muus, Abstracts of 132nd Amer. Chem. Soc. meeting, New York, September, 1957, 5T 5 Partial disordering and crystal transitions in polytetrafluoroethylene, E S Clark and L T Muus, Zeit. Krist.,117, 1962, 119-127 6 Volume-temperature relationships for the room temperature transition in ‘Teflon’*, F A Quinn, D E Roberts and R N Work, J. App. Phys., 22, 8, August 1951, 1085-1086 7 A room-temperature transition in polytetrafluoroethylene, H A Rigby and C W Bunn, Nature, 164, 4170, 1st October 1949, 583 8 Fluorine-containing polymers, Part 2: Polytetrafluoroethylene, C A Sperati and H W Starkweather, Fortschr. Hochpolym. - Forsch., 2, 1961, 465-495 12 Transitions and melting of polytetrafluoroethylene (‘Teflon’) under pressure, C W F T Pistorius, Polymer, 5, 1964, 315-317 13 The pressures of some solid-solid transitions, G C Kennedy and P N La Mori, J. Geophys. Res., 67, 1962, 851-856, Chem. Abstr., 57, 1962, 4119 a 14 Behaviour of polytetrafluoroethylene (‘Teflon’) under high pressures, R I Beecroft and C A Swenson, J. App. Physics, 30, 11, November 1959, 1793-1798 15 Thermal expansion of Ftoroplast IV (fluoroplast, ‘Teflon’) between 190 and 325°, l E Leksina and S I Novikova, Soviet Phys. Solid State, 1, 1959, 453-459, Chem. Abstr., 54, 1960, 16914 f 16 Calorimetric properties of polytetrafluoroethylene (‘Teflon’) from 0 to 365°K, G T Furukawa, R E McCoskey and G J King, J. Res. Nat. Bur. Stand., 49, 4, October 1952, 273-278 17 Specific heat of synthetic high polymer, Part 5: A study of the order-disorder transition In polytetrafluoroethylene, P Marx and M Dole, J. Amer. Chem. Soc., 77, 1955, 4771 -4774 18 Effect of pressure on the specific volume of polymer melts, J M Lupton, Abstracts of 134th Amer. Chem. Soc. meeting, Chicago, September, 1958, 37T-38T 19 R P Palmer, lCI Plastics Division, unpublished work 20 The melting points of chain polymers, C W Bunn, J. Poly. Sci., 16, 1955, 323-343 21 E R Howells, ICI Plastics Division, unpublished work 9 Chain configurations in crystals of simple linear polymers, C W Bunn and D R Holmes, Disc. Faraday Soc., 25, 1958, 95-103 10 Transitions and phases of polytetrafluoroethylene (‘Teflon’). C E Weir, J. Res. Nat. Bur. Stand., 50, 2, February 1953, 95-97 11 Effect of pressure on the room-temperature transition of polytetrafluoroethylene and its heat of transition, T Yasuda and Y Araki, J App. Poly. Sci., 5,15,1961, 331-336 *Trade mark of E I du Pont de Nemours and Company (Inc) 50 22 An independent measurement of the amorphous content of polymers, R G J Miller and H A Willis, J. Poly. Sci., 19, 1956, 485-494 23 The molecular structure of perfluorocarbon polymers. Infra-red studies on polytetrafluoroethylene, R E Moynihan, J. Amer. Chem. Soc., 81, 1959, 1045-1050 24 Physical properties of fluorocarbon plastics, Part 2: Relations between crystallinity and room temperature transition effects in PTFE, Toshihiko Kuroda and Hiroshi Sakami - Nagoya Kogyo Gijutsu Shikensho Hokoku 7,1-8 (1958), Chem. Abstr., 57, 4828h 25 Structure of polytetrafluoroethylene, G Butenuth, Verhandlungsber. Kolloid - Ges., 18, 1958,168-179, Chem. Abstr., 52, 14213 i 306 38 Polytetrafluoroethylene,W E Hanford and R M Joyce, J. Amer. Chem. Soc., 68, 1946, 2082-2085 39 Dielectric properties of ‘Teflon’ from room temperature to 314°C and from frequencies of 102 to 105 c/s, P Ehrlich, J. Res. Nat. Bur. Stand., 51, 4, October 1953, 185-188 26 The fine structure of polytetrafluoroethylene, C W Bunn A J Cobbold and R P Palmer, J. Poly. Sci., 28, 1958, 365-376 40 Dielectric losses of polytetrafluoroethylene, G P Mikhailov, S P Kabin and A L Smolyanskii, Zhur. Tekh. Fiz., 25, 1955, 2179-2182, Chem. Abstr., 50, 1956, 3026f 27 Some observations on the structure of polytetrafluoroethylene, C J Speerschneider and C H Li, J. App. Physics, 33, 5, May 1962, 1871-1875 41 Vorbehandlung and dielektrisches Verhalten Hochpolymere, F Krum and F H Muller, Koll. Zeits. 164, 1959, 81-107 28 A correlation of mechanical properties and microstructure of polytetrafluoroethylene at various temperatures, C J Speerschneider and C H Li, J. App. Physics, 34,10, October 1963, 3004-3007 42 Transitions and relaxations in polytetrafluoroethylene, R K Eby and K M Sinnott, J. App. Physics, 32, 9, September 1961, 1765-1771 43 Hartshorn and Ward, J. Inst. Elec. Engrs, 1936, 79, 597 29 Dispersions de polytetrafluorethylène, E Grimaud, J. Sanlaville and M Troussier, J. Poly. Sci., 31, 1958, 525-527 30 A J Cobbold and R P Palmer, ICI Plastics Division, unpublished work 31 Polymer single crystals, P H Geil, Interscience Publishers, New York, 1963, 483 32 Treatise on powder metallurgy, 2, S. Goetzel 33 W G Rodway, ICI Plastics Division, unpublished work 34 Effect of pressure on the melting point of ‘Teflon’ polytetrafluoroethylene resin. P L McGeer and H C Duus, J. Chem. Phys., 20, 1952, 1813-1814 35 Uniaxial compressive creep of polytetrafluoroethylene, D A Thomas, Polymer Engineering and Science, 9, 1969, 415-422 36 Experimental technique in uniaxial creep testing, D A Thomas and S Turner, Interscience Publishers Inc, New York, Testing of polymers, Vol 4 37 S Turner, Polymer Engineering and Science, 6, 1966, 44 Barrie, Proc. Inst. Elec. Engrs, 112, 2, February 1965 45 Parry, Proc. Inst. Elec. Engrs, 98, Part 3, 54, July 1951, 303 46 Bleaney, Loubser and Penrose, Proc. Phys. Soc., 59, Part 2, March 1947, 185 47 Reddish, l U P A C Symposium, Montreal, August 1961 48 Reddish, Society of Chemical Industry Symposium, April 1958, published proceedings 49 Reddish and Barrie, l U P A C Symposium, Wiesbaden, 1958 50 D J Parr and R M Scarisbrick, Proc. Inst. Elec. Engrs, 112, August 1965, 1625 51 Effects of fabrication on the properties of ‘Teflon’ resins, P E Thomas. J F Lontz, C A Sperati and J L McPherson, S P E Journal, 12, June 1956, 89-96 52 G Mole, E R A reports V/T115,1952 and V/T149, 1962 52a Superheating of linear high polymers: PTFE, E 51 Helmuth, B Wunderlich and J H Rankin, Appl. Polymer Symposium No 2,1966, 101-109 53 Thermal expansion of polytetrafluoroethylene (‘Teflon’) from -190°C to +300°C, R K Kirby, J. Res. Nat. Bur. Stand., 57, 2, 1956, 91-94 54 Thermal conductivity studies of polymers, D E Kline, J. Poly. Sci., 50, 1961, 441-450 55 Thermal conductivity of high polymers from -180 to +90°C K.Eiermann and K H Hellwege J Poly Sci., 57, 1962, 99-106 56 Specific heat of synthetic high polymers, Part 5: A study of the order-disorder transition in polytetrafluoroethylene, P Marx and M Dole, J. Amer. Chem. Soc., 77, 1955, 4771-4774 57 Relative enthalpy of polytetrafluoroethylene from 0 to 440°C, T B Douglas and A W Harman, J. Res. Nat. Bur. Stand., 69A, 2, 1965, 149-157 58 Thermal degradation of tetrafluoroethylene and hydrofluoroethylene polymers, S L Madorsky, V E Hart, S Straus and V A Sedlak, J. Res Nat. Bur. Stand., 51, 1953, 327-333 59 PyroIysis of polytetrafluoroethylene, E E Lewis and M A Naylor, J. Amer. Chem. Soc., 69, 1947, l968-l970 60 Thermal degradation of fluorine containing polymers, Part 1: Degradation in vacuum, J M Cox, B A Wright and W W Wright, J. App. Poly. Sci., 8, 1964, 2935-2950 61 Thermal degradation of fluorine containing polymers, Part 2: Degradation in oxygen, J M Cox, B A Wright and W W Wright, J. App. Poly. Sci., 8, 1964, 29512961 62 The molecular structure of perfluorocarbon polymers, Part 2: Pyrolysis of polytetrafluoroethylene, J C Siegle, L T Muus, TungPo Lin and H A Larsen, J. Poly. Sci., A, 2, 1964, 391404 63 H G Jellinek, Paper No 16 of the 12th Canadian High Polymer Forum, Candy Alpine Inn, Ste. Marguerite, Quebec 52 64 Pyrolysis of polytetrafluoroethylene, J C Siegle and L T Muus, Abstracts of 130th Meeting of Amer. Chem. Soc., Atlantic City, 1956, 8S 65 Oxidative thermal degradation of PTFE, K L Paciorek, R H Kratzer: J Kaufman, J. Poly. Sci., 1973, 1465-1473 66 The frictional properties of some plastics, K V Shooter and P H Thomas, Research, 2, 1949, 533-535 67 The friction and deformation of polymers, M W Pascoe and D Tabor, Proc. Roy. Soc., 235A, 1956, 210224 68 The frictional properties of plastics, K V Shooter and D Tabor, Proc. Phys. Soc., 65B, 1952, 661-671 69 Frictional properties of plastics, K V Shooter, Proc. Roy. Soc., 212A, 1952, 488-491 70 The sliding friction of ‘Teflon’, J B Thompson, G C Turrell and B W Sandt, S P E Journal, 11, 4, April 1955, 13-14, 38 71 Friction of ‘Teflon’ sliding on ‘Teflon’, D G Flom and N T Porile, J. App. Physics, 26, 1955, 1088-1092 72 The effect of temperature on the mechanical properties and the friction of plastics, R K King and D Tabor, Proc. Phys. Soc., 66B, 1953, 728-736 73 Visco-elastic properties and the friction of solids, K G McLaren and D Tabor, Nature, 197, 4870, 1963, 856859 74 Friction and transfer of polytetrafluoroethylene, K R Makinson and D Tabor, Nature, 201, 4918, 1964, 464466 75 Effect of orientation on the friction of PTFE, D Tabor and D E W Williams, Wear, 4, 5, 1961, 391-400, Rubber Abs. 40, 258 76 The spreading of liquids on low energy surfaces, Part 1: Polytetrafluoroethylene, H W Fox and W A Zisman, J. Colloid Science, 5, 1950, 514-531 77 Wetting of fluorinated solids by hydrogen bonding liquids, A H Ellison, H W Fox and W A Zisman, J Phys. Chem., 57, 1953, 622-627 78 Wettability of halogenated organic solid surfaces, A H Ellison and W A Zisman, J. Phys. Chem., 58, 1954, 260-265 92 Viscosity and plasticity of polytetrafluoroethylene resin above the melting point, A Nishioka and M Watanabe, J. Poly. Sci., 24,106, 1957, 298-300 79 Wetting of low energy solids by aqueous solutions of highly fluorinated acids and salts, M K Bernett and W A Zisman, J. Phys. Chem., 63 1959, 1911-1916 93 Molecular weight of polytetrafluoroethylene, R C Doban, A C Knight, J H Peterson and C A Sperati, Abstracts of 130th Amer. Chem. Soc. Meeting, Atlantic City, September 1956, 9S 80 The permeability of some plastic materials to H2, He, N2, O2 and A, R S Barton, U K A E A Report M599, 1960. Chem. Abstr., 54, 14750h 81 H Yasuda and W Stone, J. Poly. Sci., Al, 4, 1966, 1314-1316 82 R A Pasternak, M V Christensen and J Heller, Macromolecules, 3, 1970, 366-371 83 G V Casper and E J Henley, Polymer Letters, 4, 1966, 417-421 84 Gas chromatographic measurement of the permeability of PTFE, PVC, polyethylene and nylon tubing towards oxygen and nitrogen. R G Gerritse. Journal of Chromatography, 77, 1973, 406-409 85 Permeation of sulphur dioxide through polymers. R M Felder, R D Spence, and J K Ferrell, Journal of Chemical and Engineering Data 20, 3, 1975 86 Structure of polymers and properties of films, P G Konovalov, Sbornik Stateu Vsesoyuz, Zaochnogo Politekh. Inst., Moscow, 23, 1960, 92-102, Chem. Abstr., 55, 1961, 20488b 87 Perméabilité des matières plastiques à la vapeur d’eau, M Korte-Falinski, J de Chimie Physique, 59, 1962, 27-35 94 Reactions of irradiated polytetrafluoroethylene resin, M I Bro, E R Lovejoy and G R McKay, J. App. Poly. Sci., 7, 1963, 2121-2133 95 The effects of X-rays on the insulation properties of polytetrafluoroethylene, W E Liversage, Brit. J. Radiol., 25, 1952, 434-436, Chem. Abstr., 46, 1952, 10679g 96 Chemical and physical changes in gamma-irradiated plastics, R Harrington and R Giberson, Modern Plastics, 36, November 1958, 199-221, 314, 317 97 Polytetrafluoroethylene - a radiation resistant polymer, L A Wall and R E Florin, J. App Poly. Sci., 2, 5, 1959, 251 98 The effect of radiation on PTFE, Fluon® Engineering News, ICI Plastics Division, May 1964, 4 99 A Monnet and R Bensa, Energie Nucleaire, 13, 2, March/April 1971, 123-132 99a The effects of radiation on the mechanical and electrical properties of the GEOS satellite long boom cable materials, D Verdin and P R Goggin, AERE, Harwell, July 1975 100 Fluorocarbon polymers in the Chemical Industry, B B Rossa, Praktische Chemie, 15, 2, 1964, 64-73 88 P E Toren, Anal. Chem., 37, 7, 1965, 922-923 89 Journal of ‘Teflon’, (E I du Pont de Nemours & Company Inc), European edition, 8, March/April 1970; US edition, December, 7, 1964 90 Measurements of the refractive index of films, F W Billmeyer, J. App. Physics, 18, 5, 1947, 431-434 91 Determination of the refractive index of a solid using a far infra-red maser, J E Chamberlain and H A Gebbie, Nature, 206, 4984, 1965, 602 101 Temperature dependence of sound velocity in PTFE, V M Kravtsov, Akust. Zh., 11, 3, 1965, 400 401, Chem. Abstr., 64, 3707b 102 Filled fluorocarbons - new component materials-, M A Rudner, Elec. Manuf. February 1955-80 103 Friction, lubrication and wear: a survey of work during the last decade-, F P Bowden and D Tabor, Brit. J. Appl. Phys. 17, 1966, 1521-1544 53 104 Predicting bearing performance of filled ‘Teflon’ TFE resins, R B Lewis, ASME Paper 66-WA/RP-1 105 The effect of time, temperature, and environment on the sliding behaviour of polytetrafluoroethylene, R P Steijn, ASLE Trans. 9, 1966, 149-159 106 Friction, wear and decomposition mechanisms for various polymer compositions in vacuum to 10-9 millimetre of mercury, D H Buckley and R L Johnson, NASA Tech. Note D-2073, December 1963 107 Anti-friction properties of PTFE filled with ground coke, S N Ganz and V D Parkhomenko, Soviet Plastics, January 1966, 42-43 115 A comparison of materials for use as unlubricated journal bearings, F F Simpson, Proc. l. Mech. E. 175, No.10 1961, 528-536 116 The role of filler geometrical shape in wear and friction of filled PTFE, C J Speerschneider and C H Li, Wear, 5, 1962, 392-399 117 Plastics as bearing materials, with particular reference to PTFE, G C Pratt, Plast. Inst. Trans. and Journal, 32, August 1964, 255-260 118 The friction and transfer of PTFE, K Makinson E D Tabor, Proc. Roy. Soc. 281A, 1964, 49-61 108 Frictional characteristics of plastics, W C Milz and L B Sargent, Lubrication Engng.1955 119 The wear of PTFE impregnated metal bearing materials, D C Mitchell, l. Mech. E. Conference on Lubrication and Wear, London, 1-3 October 1957 109 Friction, wear and physical properties of some filled PTFE bearing materials, D C Mitchell and G Pratt, I. Mech. E. Conference on Lubrication and Wear, London, 1-3 October 1957 120 A study of heavy metal to plastic friction duties and of the wear of hardened steel in the presence of polymer, G V Vinogradov, V A Mustafaev and Yu Ya Podolsky, Wear, 8, 1965, 358-373 110 Design properties of filled-TFE plastics J T O’Rourke, Machine Design, 13 September 1962 121 Contact and rubbing of flat surfaces, J F Archard, J. Appl. Phys. 24,1953, 981-988 111 Fundamentals of friction PV, and wear of fluorocarbon resins, J T O’Rourke, Modern Plastics, 43, September 1965, 161-169 122 The wear of metals under unlubricated conditions, J F Archard and W Hirst, Proc. Roy. Soc. 236A, 1956, 397-410 112 Performance of some plain bearing materials under boundary conditions at low temperatures, R Hargreaves and D H Tantam, Proc. l. Mech. E. 175, No. 20 1961, 941-954 123 Performances of unlubricated piston rings, D Summers-Smith, Lubrication and Wear Convention, I. Mech. E.1963, 280 113 Friction and wear tests at high rubbing speeds, VDI Zeitschrift, 109, No.16 1967, 722-727 114 Non-lubricated bearings and piston rings of tetrafluoroethylene, R B Fehr, SPE Journal, August 1960, 943-948 54 124 Internal report on DECHEMA Colloquium 17, November 1967 (Germany), 55 UK ® For fluoropolymer & AFLAS enquiries from EMEA (Europe, Middle East & Africa): AGC CHEMICALS EUROPE, LTD. PO Box 4 Thornton Cleveleys Lancashire FY5 4QD UK Telephone: +44 (0) 1253 861951 Fax: +44 (0) 1253 861950 email: [email protected] web: www.agcce.com AMSTERDAM For fluorinated chemicals & ETFE Film enquiries: AGC CHEMICALS EUROPE Commercial Centre World Trade Center Zuidplein 80, H Tower, Level 9 1077 XV Amsterdam, The Netherlands Telephone: +31 (0) 20 880 4170 Fax: +31 (0) 20 880 4188 email: [email protected] web: www.agcce.com JAPAN ASAHI GLASS CO. 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