CONDUCTIVE POLYMER COMPOSITIONS CONTAINING FILLERS

Abstract: The invention relates to conductive polymer composi­ tions. The compositions of the invention have improved elec­ trial stability when exposed to thermal cycling. They com­ prise a polymer component and a filler component which has a total surface area of at least 1800 m² per cc. of composition and which comprises carbon black and non-conductive par­ ticulate filler, each present in amount at least 4% by volume of the composition. In one preferred class of compositions, the polymer component is crystalline. In another preferred class the polymer is amorphous and the amount of filler is such that the composition may an elongation of at most 10% at 23°C. The compositions has have PTC, ZTC or NTC resistivity/tempera­ ture charactcristics. Figure 2 shows the resistivity/tempera­ ture characteristics of a PTC composition of the invention. The new compositions arc useful in a variety of electrical devices, including heaters, circuit control devices and temperature sensors.

Description: This invention relates to conductive polymer compositions. Conductive and semi-conductive compositions comprising carbon black dispersed in a polymer are known. They may have room temperature resistivities ranging from less than 1 ohm.cm to 108 ohm.cm or more, and may exhibit positive temperature coefficent (PTC) behavior, zero temperature coefficient (ZTC or constant wattage) behavior or negative temperature coefficient (NTC) behavior. Reference may be made, for example, to U.S. Patent Nos. 2,978,665, 3,351,882, 3,823,217, 3,861,029, 3,950,604, 4,017,715, 4,177,376 and 4,246,468, to German OLS Nos. 2,413,475, 2,746,602, 2,755,076 and 2,821,570, to J. Applied Polymer Science 19, 813-815 (1975), Klason and Kubat, and to Polymer Engineering and Science 18 649-653 (1978), Narkis et al. Recent advances in this field are described in German OLS Nos. 2,948,350, 2,948,281, 2,949,173 and 3,002,721, in the applications corresponding to U.S. Serial Nos. 41,071 (MP0295), 67,207 (MP0299) and 88,344 (MP0701), and in the applications filed contemporaneously with this application corresponding to U.S. Serial Nos. 141,987 (MP0713), 141,989 (MP0715), 141,991 (MP0720), 142,053 (MP0724) and 142,054 (MP0725). The resistivity of a conductive polymer at a particular temperature can be changed by subjecting it to thermal cycling, i.e. by exposing it to elevated temperature followed by cooling. The change is often particularly marked when the composition is first exposed to elevated temperature after it has been shaped. When the polymer is an elastomer, although initial exposure to elevated temperature often produces the greatest change, the room temperature resistivity remains very unstable, i.e. it is changed very substantially by further exposure to heat. When the polymer is crystalline, a composition having high resistivity can often be annealed above the polymer melting point to reduce its room temperature resistivity to a value which is in the range 102 to 106 ohm.cm and which is relatively stable, i.e. it is changed, but only relatively slowly, by further exposure to heat. However, even this relatively slow change in resistivity is undesirable. We have discovered that in certain compositions, as defined below, these continued changes in room temperature resistivity on thermal cycling (after an initial heat treatment) can be reduced or even substantially eliminated by inclusion of a suitable amount of a non-conductive filler. In one aspect, the invention provides a conductive polymer composition comprising a polymer component and a particulate filler component which has been dispersed in the polymer component and which comprises carbon black and a non-conductive particulate filler, said composition having a resistivity of 102 to 106 ohm.cm at 230C after having been. subjected to a thermal cycle which consists of heating the composition from 23"C to Attest and cooling the composition from Ttest to 230 C, where Attest is 100 C when the polymer is substantially free from crystallinity and is 20 C above the crystalline melting point of the polymer when the polymer is crystalline, wherein the particulate filler component has a total surface area of at least 1800 m per cc. of composition and comprises at least 4 by volume of the composition of carbon black and at least 4 by volume of the composition of at least one non-conductive particulate filler, subject to the proviso that if the polymer component is substantially free from crystallinity, the quantity of particulate filler component is such that the composition has an elongation at 23 C of at most 10Z. Where reference is made herein to heating or cooling a composition, the heating or cooling is effected in such a way that the temperature of the composition changes at the rate of 2"C per minute. The stability of the compositions to thermal cycling can be expressed as the ratio of the resistivity of the composition after the thermal cycle defined above to its resistivity after a second thermal cycle as defined. The'higher the resistivity of the composition, the more the value of this ratio differs from the ideal value of 1. However, we have found that the difference between 1 and the said ratio is consistently less than it is for comparable compositions which do not contain a non-conductive filler as defined. In another aspect the invention provides an electrical device which comprises an element composed of a conductive polymer composition as defined above and at least two electrodes which can be connected to a source of electrical power and which when so connected cause current to flow through said element, e.g. a heater, sensor or circuit control device. The polymer component used in this invention preferably has a crystallinity of at least 1%, generally at least 2%, preferably at least 5ç, particularly at least 10%, especially at least 20", as measured by x-ray diffraction. In one preferred class of compositions, the crystalline polymer component is cross-linked, the gel fraction of the polymer (as calculated from the measured gel fraction of the composition) preferably being at least 0.6, especially at least 0.75. In another preferred class, the crystalline polymer component is substantially free of cross-linking and the composition exhibits sharply NTC behavior above its melting point, that is to say, the composition, when heated from 23 C to an elevated temperature above the crystalline melting point of the polymer, Tm, has a resistivity which reaches a maximum at a temperature T and which then peak decreases in the temperature range Tpeak to (Tpeak+25) C., to a value, #min' which is less than 105 ohm.cm and less min than K x 2owe , where K is 0.35, preferably 0.2, especially 0.1, particularly 0.05.NTC behavior has been widely regarded as a disadvantage and for practical applications has been prevented by cross-linking the composition. However, we have realized that if the resistivity of such a composition falls sharply enough and far enough after reaching a peak, then the composition is of value in temperature-sensing devices and other electrical devices, especially such devices which comprise an element composed of such an NTC composition and at least one other element composed of another conductive polymer composition. Furthermore, we have discovered how to select the components of the composition in order to provide such valuable NTC behavior. It is desirable that an NTC composition of this invention should show a very sharp rise in resistivity as it is cooled from temperatures above Tm Accordingly, it is preferred that the composition, when cooled from (Tpeak + 25) C. to 23 C., has a resistivity, as it is cooled, which increases to a maximum at a temperature Speak B' and then falls to a value 23e at 230C, and which has a minimum value in the temperature range Tpeak B @@@@ @ to (Tpeak B + 25) C which is less than K1 x 23 1 where K is 0.35, preferably 0.2, especially 0.1, particularly 0.05. When the polymer component is crystalline, it generally comprises at least 40%, preferably at least 60%, especially substantially 100%, by weight of one or more polymers having a carbon-containing backbone. When the polymer component comprises more than one polymer, it is often preferred that each of the polymers should be crystalline. Suitable crystalline polymers include polyolefins, especially polyethylene (high density and low density) and polypropylene; halogenated polyolefins such as chlorinated polyethylene; copolymers which consist essentially of units derived from at least one olefin, preferably ethylene, and units derived from at least one olefinically unsaturated comonomer containing a polar group, preferably vinyl acetate, an acrylate ester, eg. methyl or ethyl acrylate, or acrylic or methacrylic acid, said comonomer-derived units preferably constituting at least 10% and generally not more than 30 by weight of the copolymer; and crystalline polymers which comprise 50 to 100%, preferably 80 to 100z ó by by weight of -CH2CHCl- or -CH2CF2- units, eg. polyvinylidene fluoride or a copolymer of vinylidene fluoride eg. with tetrafluorethylene. Other suitable crystalline polymers are disclosed in the patents and applications referred to above. The polymer component, when crystalline, generally provides up to 60, preferably 40 to 60 ó , by weight of the composition, the remainder being provided by the filler component and other non-particulate ingredients such as antioxidants. The polymer component can also be non-crystalline, but in this case, the filler component must be such that the composition has an elongation (as measured by ASTM D638) of at most 10, preferably at most 2, at 23"C and preferably of at most 50sus at 1000C. The non-crystalline polymer component preferably has an elongation of at least 25 at 23 C. Typically such polymers are elastomers or thermoplastic elastomers produced by cross-linking a composition obtained by dispersing the filler component in an elastomeric gum, ie. a non-crystalline polymer which exhibits elastomeric properties when cross-linked and which preferably has a glass transition temperature below 230 C. The non-crystalline polymers can have a carboncontaining backbone, e.g. non-crystalline chlorinated polyethylene and fluorinated elastomers such as Viton. The compositions generally contain a single carbon black, but mixtures of carbon blacks can be used. The carbon black will preferably be the sole conductive material in the composition. We have surprisingly found that, for a composition containing a particular polymer and a given volume percent of a particular carbon black based on the polymer, the presence of the non-conductive filler does not cause any great change in the resistivity of the composition at 23 C or the basic nature of its resistivity/temperature relationship (ie. PTC, ZTC or NTC). It is, therefore, possible to produce compositions having desired properties by making use of the information given in the patents and applications referred to above in order to select suitable combinations of carbon black and polymer. Thus in one preferred class of compositions, which generally exhibit constant wattage behavior, the carbon black has a particle size (D) in millimicrons and a surface area (S) in m2/g such that S/D is at least 10, preferably at least 12, especially at least 18, with D preferably being less than 27, especially less than 18, particularly less than 15, millimicrons. In another preferred class of compositions, which generally exhibit PTC behavior, the carbon black has a particle size (D) of 20 to 150 millimicrons, eg. 20 to 75 millimicrons, and a surface ares in m2/gram (S) such that S/D is not more than 10; preferably the value of the quantity S x volume of filler component D volume of polymer component is less than 1. In another preferred class of compositions, which generally exhibit NTC behavior, the carbon black has a particle size (D) in millimicrons and a surface area (S) in m2/g such that S/D is at least 10, preferably at least 12, especially at least 18, with D preferably being less than 27, especially less than 18, particularly less than 15, millimicrons. The volume of carbon black is at least 4, eg. 4 to 20, by volume of the composition, with 10 to 45 generally being used for PTC compositions, 4 to 20 ,ó for ZTC compositions and 4 to 45, preferably 4 to 20, e.g. 4-5, for NTC compositions. The non-conductive particulate fillers have resistivities of greater than 106, preferably greater than 108, and often greater than 101 , ohm.cm. The particles may be solid or, in suitable cases, hollow. Excellent results have been obtained using glass beads. Other inorganic fillers which can be used include titanium dioxide, silica and antimony trioxide. Organic particulate fillers can also be used, for example particles which are composed of an organic polymer having a softening point such that the particles remain as a discrete particulate phase during use of the composition. The non-conductive filler may have a particle size which is smaller or greater than the carbon black, for example from 0.1 to 100 microns, preferably 1 to 70 microns. It is usually convenient to use a single nonconductive filler, but mixtures of fillers can be used. The filler may have a surface coating of a wetting or coupling agent to render it more readily dispersible in the polymer component. The volume of non-conductive filler is at least 4, eg. 4 to 80 ', preferably 6 to 30, by volume of the composition. In PTC compositions, the volume of nonconductive filler is preferably less than, eg. 0.3 to 0.8 times, the volume of carbon black. In ZTC and NTC compositions the volume of non conductive filler is preferably greater than, eg. 2 to 12 times, preferably 3 to 10 times, the volume of the carbon black. The quantities and types of carbon black and nonconductive filler used should be such that they have a total surface area of at least 1800 m2 per cc. of composition, preferably at least 2000 m2/cc., especially at least 3000 m2/cc, particularly at least 4000 m2/cc, with higher values, eg. et least 8,000 m2/cc, at least 10,000 m2/cc and at least 12,000 m2/cc being particularly preferred. The particulate filler component generally provides at least 10, preferably at least 20%, particularly at least 25 0 by volume of the composition. Certain compositions containing carbon black and an arc-controlling additive such as alumina trihydrate d are among those described and claimed in an application filed contemporaneously herewith, and corresponding to U.S. Serial No. 141,989 (MP0715). The filler component can be dispersed in the polymer component in any suitable way. It is often convenient to use a master batch technique, ie. to disperse the carbon black in a part of the polymer and the non-conductive filler in another part of the polymer, and then to mix the two master batches and the remainder of the polymer. The dispersion can be shaped by molding or extrusion or another melt-shaping technique into an element of the desired shape, any cross-linking thereof being carried out after such shaping. The invention is illustrated by the following Examples. EXAMPLES 1 to 7 The ingredients used in Examples 1 to 7 and the amounts thereof are set out in Table I below. The resistivi ties of the compositions as prepared, 23 e , after a first 0 thermal cycle as defined, 21 e , and after a second thermal cycle as defined, 23 e , are shown in Table 2. Examples cycle 1, 6 and 7 are comparative Examples. EXAMPLE 1 (Comparative) The ingredients were introduced into a Banbury mixer with water-cooled rotors turning at high gear and were mixed at high gear for 4.5 minutes and at low gear for 1.5 minutes. The mixture was dump-ed, cooled and granulated. The granules were dried under vacuum at 70"C for 16 hours. A portion of the dried granules was compression molded into a slab 0.05 cm. thick. Rectangular samples 2.5 x 3.8 cm. were cut from the slab and electrodes were placed on the samples by painting 0.6 x 2.5 cm. strips of a silver-Viton composition (Electrodag 504) on both surfaces at each end of the sample. The samples were thermally conditioned by maintaining them at 1600C for 15 minutes by external heating and then cooling to room temperature. The resistivity of the composition was calculated from sample resistance measurements taken at 3"C intervals as the samples were subjected to two thermal cycles, in the first of which the sample was externally heated from 230 to 1600C and then cooled at 23"C and in the second of which the sample was externally heated from 230 to 1800 and then cooled to 230 C. Figure 1 shows the resistivity of the composition as a function of temperature during these cycles, the first cycle being shown as a broken line and the second as a solid line. EXAMPLE 2 The procedure of Example 1 was followed except that the ingredients were as shown in Table I; the rotor was steam-heated until the torque increased considerably, when the steam was turned off and water was turned on; and the ingredients were mixed at high gear for 4 minutes. Figure 2 shows the resistivity of the composition during the heating and cooling cycles, the first cycle being shown as broken line and the second as a solid line. EXAMPLE 3 This example shows the production of a planar heater comprising planar mesh electrodes having between them a PTC layer and a contiguous ZTC layer composed of a composition according to the invention. Preparation of ZTC Sheet Material Master Batch 1 was prepared from the ingredients shown in Table I. The ingredients were introduced into a Banbury mixer whose rotor had been preheated by steam and was turning at fourth gear. When the torque had increased considerably, the steam to the rotor was turned off and water was passed through the rotor to cool it. Mixing was continued at fourth gear for 2.5 mins. after the water had been turned on and for a further 2 mins. at third gear. The mixture was dumped, held on a steam-heated mill, extruded into a water bath through a 8.9 cm. extruder fitted with a pelletizing die, and chopped into pellets. The pellets were dried under vacuum at 60"C for at least 18 hours. Master Batch 2 was prepared from the ingredients shown in Table I. The ingredients were introduced into a Banbury mixer whose rotor was water-cooled and was turning at fourth gear; mixing was carried out at fourth gear for 2 mins. and at third gear for 1.75 mins. The mixture was dumped, cooled and granulated. The granules were dried under vacuum at 600 C for at least 18 hours. The final mix, containing the ingredients shown in Table I, was prepared by introducing 11,523 g. of Master Batch 1, 3,127 g. of Master Batch 2, 3,480 g. of high density polyethylene (Marlex 6003) and 77.7 g. of anti oxidant into a Banbury mixer whose rotor was water-cooled and was turning at high gear; mixing was carried out at high gear for 4 mins. and at low gear for 1 min. The mixture was dumped, held on a steam-heated mill, extruded into a water bath through a 8.9 cm. extruder fitted with a pelletizing die, and chopped into pellets. The pellets were dried under vacuum at 70"C for 24 hours, and then extruded into sheet 30 cm. wide and 0.053 cm. thick, using a Davis-Standard Extruder fitted with a 15 inch sheet die and operating at 20 RPM with a throughput of 122 cm/minute. The sheet was stored under argon. Preparation of PTC Sheet Material The ingredients shown in Table I for the PTC material were introduced into a Banbury mixer. The mixture was dumped from the Banbury and converted into sheet by the same procedure as the Final Mix. The sheet was stored under argon. Preparation of Heater Rectangles 22.2 x 22.9 cm. were cut from the ZTC sheet material and from the PTC sheet material, and dried under vacuum at 60"C for 9 hours. Two rectangles 20.3 x 22.9 cm. were cut from a sheet of fully annealed nickel mesh that had been thoroughly cleaned. The rectangles were sprayed until the nickel was completely covered, but the mesh apertures were not filled, with a composition containing 60 parts by weight of methyl ethyl ketone and 40 parts of Electrodag 502. The coated mesh rectangles were dried under vacuum for 2 hours at 100DC. The PTC, ZTC and mesh rectangles were laminated to each other by layering a fluoroglass sheet (a release sheet of a glass-fiber reinforced fluorinated polymer), a mesh electrode, a PTC layer, a ZTC layer, another mesh electrode, and another fluoroglass sheet in a mold and pressing with a 30.5 cm. press with plate temperatures of (224"C) (top) and 218"C (bottom) for 3.5 minutes at 12.5 tonnes ram pressure. The mold was then cooled in an 46 cm. cold press with air cooling at ram pressure for 5 minutes. The resulting heater blank was masked, leaving 3.8 cm. at each end unmasked. A razor was used to scrape away PTC or ZTC material (which had been pressed through the coated mesh) from the mesh on opposite sides of the heater in the unmasked area. The scraped area on each side of the heater blank was then further abraded with a grit blaster. Strips 2.5 x 25.4 cm. were cut from flat and fully annealed Cu mesh which had been thoroughly cleaned. One side of the strips was coated with a silver/silicone contact elastomer and strips were then dried in vacuum at room temperature for a minimum of 4 hours. One end of each of the strips were then bent back at a 450 angle and 0.02 x 0.5 x 15.2 cm. flat copper wire was soldered onto the bent end. One of these strips was applied to each of the abraded areas of the heater blank with the silver side down and then each side of the heater blank was covered with a 22.2 x 3.8 x 0.03 cm. polyethylene sheet. The assembly was placed between two 1.3 cm. aluminum plates and compression molded at 200"C for 3 min. at 2,300 kg. pressure, and then placed in the cold press for 10 minutes at 2,300 kg. pressure. EXAMPLE 4 2191 g. of Master Batch 1 as used in Example 3, 535 g. of Master Batch 2 as used in Example 3, 709 g. of Alathon 7.050 and 16 g. of the antioxidant were mixed in a Banbury mixer (3.3 minutes at high gear, 1 minute at low gear), to give a final mix having the composition shown in Table 1. The mixture was dumped, cooled and granulated. The granules were dried under vacuum at 60"C for at least 18 hours and then extruded into a tape using a 3/4 inch Brabender extruder and a 7.6, 0.05 cm. tape die at 40 RPM. The extruded tape was taken off on a roll stack with the top roll at 115"C and the bottom roll at 95 C. EXAMPLE 5 The ingredients listed in Table I were introduced into a steam preheated Banbury mixer turning at high gear and were mixed for approximately one minute in high gear. At this point the torque increased considerably, the cooling water was turned on, and the mixing continued at high gear for one minute, then low gear for one minute. The material was dumped, cooled, and granulated, and the granules were dried at 600C in vacuum for at least 18 hours. The granules were extruded into tape as in Example 4. EXAMPLE 6 (Comparative) 642 g. of Master Batch 2 as used in Example 3, 1836 g. of Marlex 6003 and 41 g. of antioxidant were added to a 5 lb. Banbury mixer turning at high gear. After 4.75 mins., the torque increased considerably and cooling water was turned on; mixing was continued for 1.5 minutes, and the mixture was then dumped, cooled and granulated. The granules, whose composition is shown in Table I, were dried under vacuum for at least 18 hours at 609C. The granules were extruded into tape as in Example 4. EXAMPLE 7 (Comparative) The ingredients listed in Table I were introduced into a Banbury mixer turning at high gear. After mixing for 5.6 minutes at high gear and 1.4 minutes in low gear, the mixture was dumped,- cooled and granulated. The granules were dried at 60"C in vacuum at least 18 hours. The granules were extruded into tape as in Example 4. EXAMPLES 8 to 10 The ingredients used in Examples 8 to 10 and the amounts thereof are set out in Table III below. After mixing the ingredients and compression molding the mixture into a slab as described in the Examples, rectangular samples 2.54 x 1.8 cm were cut from the slabs and silver electrodes were provided on the samples by painting 0.63 x 2.54 cm. strips of a silver-Viton composition (Electrodag 504) on both surfaces at each end of the sample. Resistance measurements were taken at 3"C intervals as the sample was subjected to two thermal cycles. In the first cycle the sample was externally heated from 23 to 1600C, maintained at 1600C for 15 minutes, and then cooled to 23"C. In the second cycle the sample was externally heated from 23 to 1800C, maintained at 1800C for 15 minutes and then cooled to 23"C. Figures 3 to 5 show the resistivities of the compositions of Examples 8 to 10 respectively during these cycles, the first cycle being shown as a broken line and the second as a solid line. EXAMPLE 8 The ingredients were mixed for 14 minutes in a Banbury mixer with steam-heated rotors turning at high gear and thereafter for 3.2 minutes with water-cooled rotors. The mixture was dumped, cooled and granulated. The granules were dried under vacuum at 70"C for 16 hours. A portion of the dried granules was compression molded into a slab 0.076 cm thick. EXAMPLE 9 The ingredients shown under Master Batch 1 in Table III were introduced into a Banbury mixer with a steam-heated rotor turning at high gear. When the torque had increased considerably, the steam to the rotor was turned off and water was passed through the rotor to cool it. Mixing was continued for 4 mins. after the water had been turned on. The mixture was dumped, cooled and granulated. The granules were dried under vacuum at 60"C for 18 hours. The ingredients shown under Master Batch 2 in Table III were introduced into a Banbury mixer with a water-cooled rotor turning at high gear, and were mixed at high gear for 3.25 min. and at low gear for 2.5 min. The mixture was dumped, cooled and granulated. The granules were dried under vacuum at 60"C for 18 hours. The final mix, containing the ingredients shown in Table III, was prepared by introducing 2,154 g. of Master Batch 1, 439 g. of Master Batch 2, 829 g. of high density polyethylene (Marlex 6003) and 18.5 g. of antir oxidant into a Banbury mixer whose rotor was water-cooled and was turning at high gear; mixing was carried out at high gear for 3.3 min. and at low gear for 1 min. The mixture was dumped, cooled and granulated. The granules were dried under vacuum at 7OCC for 16 hours, and then compression molded into a slab 0.053 cm thick. EXAMPLE 10 The procedure of Example 9 was followed except that the final mix was prepared by mixing 2,186.5 g. of Master batch 1, 461 g. of Master Batch 2, 780 g. of high density polyethylene (Marlex 6003) and 17.4 g. of antioxidant, and the samples were heat-treated, before the electrodes were provided thereon, by heating them to 200"C and then cooling them to room temperature. TABLE 1 EXAMPLE 3 EXAMPLE 1 EXAMPLE 2 HASTER BATCK 1 MASTER BATCH 2 FINAL MIX PTC g. %wt. $vol. g. %wt. %vol. g. %wt. %vol. g. %wt. %vol. g. %wt. %vol. g. %wt. %vol. Garbon Black 1 (Raven 8000) 405 15.6 9 303.8 8.7 6.75 - - - 6528 42.1 28 1317 7.2 7.6 - - Carbon Black 2 (Furnex N765) - - - - - - - - - - - - - - 7001 44 29.5 Polyethylene 1 (Harlex 6003) - - - 1590 45.5 66.25 - - - - - - 3408 19.1 10.7 8592 54 68.1 Polyethylene 2 (Alathon 7050) 2136 82.4 89 - - - 6185 27.3 49 8837 56.1 4900 26.9 15.0 - - Inert Filler (Glass Beads) - - - 1550 44.3 25 16306 72.1 50 - - - 8308 45.6 65.9 - - Antioxidant 52.5 2 2 52.5 1.5 2 138 0.6 1 276 1.8 2 203 1.2 0.8 318 2 2.3 Total Surface Area of Filler 15.100 11.400 - - 12.800 (m2/cc) NOTES: Raven 8000 (available from City Services Co.) has a particle size ( D) of 13 millimicrons, a density of 1.8 g/cc, and a surface area (s) of 935 m2/g. Furnex N765 (available from City Services Co.) has a particle size (D) of 60 millimicrons, a density of 1.8 g/cc, and a surface area (s) of 32 m2/g. Marles 6003 is a high density polyethylene with a melt index of 0.3 which is available from Phillips Petroleum Co. Alathon 7050 is a high density polyethylene with a melt index of 18.0 which is available from E,I. DuPont de Nemours & Co. The glass beads used are available from Potters Industries as Potters #num;3000 with CP-01 coating. They are spherical glass beads with a dfameter of 4-44'microns and having a surface coating of a wetting or coupling agent thereon. They have a surface area of 0.1 m2/g and a density of 2.48 g/cc. The antioxidant used was an oligomer of 4,4-thio bis (3-methyl-6-t-butyl phenol) with an average degree of polymerization of 3-4. as described in U.S. Patent No. 3,986,981. TABLE 1 (continued) Example 4 Example 5 Example 6 Example 7 g. % wt. % vol. g. % wt. % vol. g. % wt. % vol. g. % wt. % vol. Carbon Black 1 (Raven 8000) 202.5 5.9 4.5 259 7.5 5.8 270 10.7 6.0 326 12.8 7.2 Polyethylene 1 (Marlex 6003) - - - - - - 1836 72.9 76.9 - - Polyethylene 2 (Alathon 7050) 1656.5 48.0 69.0 1641 46.4 67.2 360.2 14.3 15.1 2178 85.2 90.8 Inert Filler (Glass Beads) 1550 45.0 25.0 1550 44.6 25.0 - - - - - Antioxidant 38.9 1.1 1.5 52.5 1.5 2.0 52.6 2.1 2.0 52.5 =.0 2.0 Total Surface Area (m2/cc) 7.600 9,800 10.100 12.100 TABLE II Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 230# 1.48 x 102 1.44 x 102 7.33 x 102 6.10 x 103 1.31 x 103 > 1 x 106 1.65 x 104 231# 1.31 x 102 1.37 x 102 1.06 x 103 1.50 x 103 7.28 x 102 1.17 x 104 2.18 x 103 232# 1.26 x 102 1.36 x 102 1.09 x 103 1.02 x 103 5.87 x 102 4.05 x 103 1.24 x 103 EMI24.1 <tb> <SEP> o <tb> <SEP> d <tb> <SEP> d <tb> <SEP> d <tb> <SEP> co <tb> <SEP> o <tb> <SEP> D <tb> <SEP> o <tb> 231e223 <SEP> 0.96 <SEP> 0.99 <SEP> 0.03 <SEP> 0.68 <SEP> 0.81 <SEP> 0.35 <SEP> 0.57 <tb> <SEP> a <tb> <SEP> c <tb> <SEP> o <tb> <SEP> o <tb> <SEP> N <SEP> N <tb> <SEP> N <tb> TABLE III EXAMPLES 9 AND 10 EXAMPLE 9 EXAMPLE 10 EXAMPLE 8 MASTER BATCH 1 MASTER BATCH 2 FINAL MIX FINAL MIX g. %wt %vol g. %wt %vol g. %wt %vol g. %wt %vol g. %wt $vol Carbon Black 1 (Raven 8000) 270 7.8 6 - - - 1260 42.1 28 185 5.4 4.1 194 56 4.3 Polyethylene 1 (Marlex 6003) 1608 46.2 67 - - - - - - 829 24.1 34.6 780 22.7 32.7 Polyethylene 2 (Alathon 7050) - - - 1152 26.8 48 1680 56.1 70 823.5 23.9 34.3 845 24.5 35.4 Filler (Glass Beads) 1550 44.3 25 3100 72 50 - - - 1551 45 25.0 1574 45.7 25.6 Antioxidant 52.5 1.5 2 52.5 1.2 2 52.5 1.8 2 52.2 1.5 2.0 52.2 1.5 2 Total Surface Area of Filler 10.000 - - 7,100 7.200 (m2/cc) NOTES: Raven 8000 (available from City Services Co.) has a particle size (D) of 13 millimicrons and a surface area (s) of 935 M2/g. Marlex 6003 is a high density polyethylene with a melt index of 0.3 which is available from Phillips Petroleum Co. Alathon 7050 is a high density polyethylene with a melt index of 18.0 which is available from E.I. DuPont de Nemours & Co. The glass beads used are available from Potters Industries as Potters &num;3000 with CP-01 coating. They are spherical glass beads with a diameter of 4-44 microns and having a surface coating of a wetting or coupling agent thereon. The antioxidant used was an oligomer of 4,4-thio bis (3-methyl-6-t-butyl phenol) with an average degree of polymerization of 3-4, as described in U.S. Patent No. 3,986,981

Claims: CLAIMS 1. A conductive polymer composition comprising a polymer component and a particulate filler component which has been dispersed in the polymer component and which comprises carbon black and a non-conductive particulate filler, said composition having a resistivity of 102 to 106 ohm.cm at 23"C after having been subjected to a thermal cycle which consists of heating the composition from 23"C to Attest and cooling the composition from Ttest to 230C, where Ttest is lOOaC when the polymer is substantially free from crystallinity and is 20"C above the crystalline melting point of the polymer when the polymer is crystalline, characterised in that the particulate filler component has a total surface area of at least 1800 m2 per cc. of composition and comprises at least 4 Ó by volume of the composition of carbon black and at least. 4% by volume of the composition of at least one non-conductive particulate filler, subject to the proviso that if the polymer component is substantially free from crystallinity, the quantity of particulate filler component is such that the composition has an elongation at 23 0C of at most 10%. 2. A composition according to Claim 1 characterised in that the polymer component has a crystallinity of at least 10 ó and constitutes up to 60z ó by weight of the composition; the carbon black has a particle size (D) of 20 to 150 millimicrons and a surface area (S) in m2/gram such that S/D is not more than 10; and the volume of non-conductive filler is 0.3 to 0.8 times the volume of carbon black. 3. A composition according to Claim 2 characterised in that the quantity volume of filler component S/D x volume of polymer component is less than 1. 4. A composition according to Claim 1 characterised in that the polymer component has a crystallinity of at least 10% and constitutes up to 60w ó by weight of the composition; the carbon black has a particle size (D) which is less than 27 millimicrons and a surface area (S) such that S/D is at least 12; and the volume of nonconductive filler is 2 to 12 times the volume of carbon black. 5. A composition according to Claim 1 characterised in that the polymer component has a crystallinity of at least 10% and is substantially free from crosslinking, and the carbon black (a) is present in amount 4 to 20 ó by volume of the composition and (b) has a particle size, D, which is less than 18 millimicrons and a surface area, S, in m2/gram such that S/D is greater than 12, whereby the composition, when heated, has a resistivity which reaches a maximum at a temperature Tpeak and then decreases rapidly in the temperature range Tpeak to (Tpeak + 25) C to a value, #min, which is less than 105 ohm.cm and less than 0.35 x 206 0 6. A composition according to Claim 5 characterised in that S/D is at least 18 and D is less than 15 millimicrons. 7. A composition according to Claim 4, 5 or 6 characterised in that volume of the non-conductive filler is from 2 to 12 times the volume of the carbon black. 8. A composition according to Claim 1 characterised in that the polymer component is substantially free of crystallinity and consists essentially of one or more cross-linked elastomers having a carbon-containing backbone, and the composition has an elongation at 23 C of at most 2%. 9. A composition according to any one of the preceding claims characterised in that the particulate filler component has a total surface area of at least 4,000 m2 per cc. of composition and provides at least 20 by volume of the composition. 10. An electrical device which comprises a conductive polymer element and at least two electrodes which can be connected to a power source so that current flows through the element, characterised in that the element is composed of a conductive polymer composition as claimed in any one of claims 1 to 9.

Inventors: FOUTS, ROBERT W., J.R., GOTCHER, ALAN JEFFREY, WALTY, ROBERT, WASLEY, ROBERT, WHITNEY, DAVID W.
Applicants: RAYCHEM CORPORATION
Application year: 1981
Main classification: H01B1
IPC codes: C08K3, H01B1, H01C7