Classifications

• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B3/00—Ohmic-resistance heating
  • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
  • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
  • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
  • H05B3/146—Conductive polymers, e.g. polyethylene, thermoplastics
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B3/00—Ohmic-resistance heating
  • H05B3/40—Heating elements having the shape of rods or tubes
  • H05B3/54—Heating elements having the shape of rods or tubes flexible
  • H05B3/56—Heating cables

Definitions

• This invention relates to electrical devices comprising resistive heating elements, in particular self-regulating strip heaters which comprise resistive heating elements composed of a conductive polymer composition which exhibits PTC behavior.
• a substrate e.g. a pipe or a tank
• an elongate heater comprising a resistive heating element.
• an electrically insulating jacket around the resistive heating element in order to prevent electrical shorting between the resistive element and an electrically conductive substrate. While such insulating jackets provide electrical insulation and environmental protection, they may not have adequate abrasion resistance.
• braids are sometimes provided over the insulating jacket for toughness and abrasion resistance. When the braid is metallic, it can also act as a grounding braid.
• a heater which comprises a metallic grounding braid is generally more flammable than the corresponding non-braided heater
• the flammability of a heater can be reduced by using (in the insulating jacket and/or in the resistive element if it is composed of a conductive polymer) a polymer which has low flammability, for example by using a fluorinated polymer instead of a polyolefin.
• Flammability can also be reduced by incorporating flame retardants, e.g. antimony trioxide and/or halogen-containing additives, into the polymer.
• flame retardants e.g. antimony trioxide and/or halogen-containing additives
• the flammability of an elongate heater can be reduced by providing it with an additional insulating jacket, or by replacing a single insulating jacket (including one of two insulating jackets) by two or more jackets. In this way, a heater which fails the VW-1 test can be converted into one which passes the VW-1 test.
• a further insulating jacket is added to an existing heater, on top of, or underneath, the conventional jacket(s)
• the reduction in flammability is not determined by (though it may be influenced by) the flammability of the material of the further insulating jacket. Even jackets which are made of materials which would normally be regarded as flammable can be effective.
• Elongate heaters having two (or even more) insulating jackets have been used, or proposed for use, in the past, but only for purposes which do not, so far as we know, have any connection with flammability.
• Such known heaters do not, of course, per se form part of our invention.
• our invention does include heaters which make use of such known combinations of insulating jackets but which are otherwise different from the known heaters, for example through the use of hearing cores which are different from those around which such combinations have previously been placed.
• the invention includes novel heaters containing known combinations of insulating jackets which, in the prior art, were selected for reasons related to the heater core (or to one or more other components of the heater) when those reasons do not apply to the novel heaters.
• this invention provides an elongate heater which passes the
• VW-1 flame test which comprises
• (b) is composed of a first insulating material comprising an organic polymer
• the components of the heater being such that (a) a heater which is substantially identical, except that it does not contain the second insulating jacket, fails the VW-1 flame test, and (b) a heater which is substantially identical, except that it does not contain the first insulating jacket, fails the VW- 1 flame test.
• this invention provides a heater assembly for heating a substrate, said assembly comprising
• a second insulating jacket which has been formed by wrapping a preformed tape of a second insulating material or a metallized polymer tape around the first insulating jacket so that the edges of the tape overlap, the tape preferably comprising a polyester and having a thickness of less than 0.005 inch.
• the elongate heaters of the invention preferably pass the Underwriters' Laboratory VW-1 vertical-wire flame test, as hereinafter described ("Flame Test") and as published in Reference Standard for Electrical Wires, Cables, and Flexible Cords, UL 1581, No. 1080, August 15, 1983, the disclosure of which is incorporated herein by reference.
• Flume Test Underwriters' Laboratory VW-1 vertical-wire flame test
• the elongate heaters of the invention comprise a core which comprises a resistive heating element and which is surrounded by a first insulating jacket and a second insulating jacket.
• the first insulating jacket is the inner jacket and the second insulating jacket is the outer jacket. It is to be understood that the invention includes heaters in which the materials, thicknesses, etc. given for the first jacket are used for the second jacket, and vice versa.
• the heater core preferably also comprises two elongate electrodes having the resistive heating element(s) connected in parallel between them.
• a series or mixed series parallel heater can also be used.
• the resistive heating element may be in the form of a continuous strip, or in the form of a plurality of spaced-apart individual heating elements. The latter arrangement is preferred when the heating element is prepared from stiff, brittle, or rigid material.
• the electrodes are usually in the form of solid or stranded metal wires, e.g. tin- or nickel-coated copper wires, although other electrically conductive materials, e.g. conductive paints, metal foils or meshes, may be used.
• each of them is electrically and physically connected to the electrodes.
• the electrodes can be wholly or partially embedded in the material of the resistive element or attached to the surface of the resistive element
• the electrodes can be embedded therein, or, as disclosed in U.S. Patent No. 4,459,473 (Kamath), the disclosure of which is incorporated herein by reference, the continuous strip can make intermittent contact alternately with each of the electrodes, e.g. by spiral wrapping the fiber(s) around the electrodes which are separated by an optional electrically insulating spacer.
• the resistive heating element may be composed of any suitable resistive material, e.g.
• a conductive polymer composition comprises a polymeric component and, dispersed or otherwise distributed therein, a paniculate conductive filler.
• the polymeric component may be an organic polymer (such term being used to include siloxanes), an amorphous thermoplastic polymer (e.g. polycarbonate or polystyrene), an elastomer (e.g. polybutadiene or ethylene/propylene diene (EPDM) polymer), or a blend comprising at least one of these.
• crystalline organic polymers such as polymers of one or more olefins, particularly polyethylene; copolymers of at least one olefin and at least one monomer copolymerisable therewith such as ethylene/acrylic acid, ethylene/ethyl acrylate, and ethylene/vinyl acetate copolymers; melt-shapeable fluoropolymers such as polyvinylidene fluoride and ethylene tetrafluoroethylene; and blends of two or more such polymers.
• Such crystalline polymers are particularly preferred when it is desired that the composition exhibit PTC (positive temperature coefficient of resistance) behavior.
• PTC behavior is used in this specification to denote ?
• the composition also comprises a particulate conductive filler, e.g. carbon black, graphite, metal, metal oxide, or particulate conductive polymer, or a combination of these.
• the conductive polymer composition comprises inert fillers, antioxidants, stabilizers, dispersing agents, cross- linking agents, or other components. Mixing is preferably achieved by melt- processing, e.g. melt-extrusion.
• the composition may be crosslinked by irradiation or chemical means.
• Self-regulating strip heaters in which the electrodes comprise elongate wires and the resistive heating elements comprise a conductive polymer composition are particularly useful. Suitable conductive polymers for use in this invention, and heaters whose insulating jackets can be modified in accordance with the present invention are disclosed in U.S. Patent Nos.
• the heating element is in the form of a continuous strip of conductive polymer having electrodes embedded therein
• the cross-section of the strip may be of any suitable shape, e.g. rectangular, round, or dumb-bell.
• Many useful elongate heaters comprise a core which is composed of a conductive polymer composition exhibiting PTC behavior and which has a substantially constant cross-section along the length of the heater.
• the ratio of the maximum dimension of the cross-section of the heating element (often the axis of the electrodes) to the minimum dimension of the cross-section of the heating element (often the thickness of the heater) is often at most 7:1, preferably at most 3:1, particularly at most 2:1, e.g. about 1:1.
• the maximum dimension of the cross-section is often less than 1 inch (2.54 cm), e.g. less than 0.6 inch (1.5 cm) and/or the maximum area of the cross-section is less than 1.25 inch 2 (8.0 cm 2 ), e.g.. less than 0.5 inch 2 (3.2 cm 2 ).
• the first insulating jacket surrounds (and preferably contracts) the core and comprises an organic polymer.
• Suitable polymers include those which are suitable for use in a conductive polymer composition, as well as other polymers such as polyurethanes.
• the polymer composition used in the first insulating jacket is often modified by the presence of flame retardants, e.g. Al2 ⁇ 3 «3H2 ⁇ , or a mixture of Sb 2 ⁇ 3 and a brominated flame retardant, or other fillers, polymers which are relatively flexible are preferred. If it is desirable to have a good physical bond between the core and the first insulating jacket the compositions used for the core and the first insulating jacket may contain the same polymer.
• the first insulating jacket may be applied to the core using any convenient means, e.g. melt-forming, solvent-casting, or shaping of a preformed sheet of material over the core. It is generally preferred that the jacket be melt-extruded over the core by either a tube-down or a pressure extrusion process. If the heater is to be annealed, i.e. heat-treated above the crystalline melting point of the polymeric component in the core, the melting point of the organic polymer in the first insulating jacket should be higher than that of the core. Generally, the first insulating jacket has a thickness of less than 0.075 inch (0.19 cm), preferably less than 0.050 inch (0.125 cm), particularly less than 0.040 inch (0.1 cm), e.g. 0.015 to 0.030 inch (0.04 to 0.075 cm).
• a second insulating jacket surrounds the first insulating jacket. It often contacts, and may be bonded to, the first insulating jacket.
• the second insulating jacket may comprise an organic polymer which may be the same as or different from that of the first insulating jacket, or it may comprise another material such as a glass, e.g. fiberglass, a ceramic, a woven or nonwoven fabric, a metal, e.g. aluminum foil, or an insulated metal, e.g. metallized polyester.
• the second insulating jacket be an insulating material which comprises an organic polymer. For some applications, it is preferred that at least 75% by weight of the organic polymer in the second insulating jacket is the same as at least 75% by weight of the organic polymer in the first insulating jacket.
• the second insulating jacket has a thickness of less than 0.020 inch (0.04 cm), particularly less than 0.010 inch (0.025 cm), especially less than 0.006 inch (0.15 cm), most especially less than 0.005 inch (0.13 cm), e.g. 0.001 to 0.005 inch (0.002 cm to 0.013 cm).
• films of such polymers as polyesters (e.g. polyethylene terephthalate sold under the trade name MylarTM by DuPont), polyimide (e.g. films sold under the trade name KaptonTM by DuPont), polyvinylidene fluoride (e.g. films sold under the trade name KynarTM by Pennwalt), polytetrafluoroethylene (e.g.
• films sold under the trade name TeflonTM by DuPont or polyethylene.
• aluminum-coated polyester is useful, particularly for applications in which it is important that any moisture or plasticizer from an insulation layer be prevented from penetrating and damaging the core or the first insulating jacket.
• Such films in the form of a sheet i-e. preformed films or tapes, can be wrapped around the first insulating jacket, e.g. spirally with an overlapping seam which runs spirally down the heater, or as a so-called "cigarette wrap" so that there is an overlapping seam which runs straight down the heater. Under normal conditions, either spiral wrapping or cigarette wrapping is conducted without an adhesive being present so that the insulating layer does not provide a total barrier to penetration by moisture.
• the materials comprising the films can be formed over the first insulating jacket using any other suitable process, e.g. melt-extrusion such as by a tube-down process, or by solvent casting.
• the material comprising the second insulating jacket is one which has been oriented so that, under the conditions of the VW-1 test, the second jacket shrinks before it burns.
• the material of the second insulating jacket is identical to the material of the first insulating jacket
• the total thickness of first and second jackets is less than 0.025 inch (0.06 cm).
• a metallic braid may be provided over the second insulating jacket in some embodiments.
• the second insulating layer comprises a film such as a polyester film or a metallized (e.g. laminated aluminum) polyester film
• a film such as a polyester film or a metallized (e.g. laminated aluminum) polyester film
• PVC polyvinyl chloride
• foam insulation is commonly used to insulate the heater when it wrapped around a pipe or other substrate.
• Figure 1 is a cross- sectional view of an elongate heater 1 of the invention.
• a resistive heating element comprising a conductive polymer composition 3 formed around two electrodes 5,7 is surrounded by a first insulating jacket 9.
• a second insulating jacket 11 e.g. a thin film of an insulating polymer such as polyethylene, polyester, or polyimide, a thin metal foil such as aluminum, or a metallized polymer film, is wrapped around the first insulating jacket in such a way that there is a region of overlap 13.
• An optional metallic grounding braid 15 covers the second insulating jacket.
• Figure 2 is a cross-sectional view of a second elongate heater of the invention.
• the resistive heating element comprising the conductive polymer composition 3 and the two elongate electrodes 5,7 is surrounded by a thin first insulating jacket 9 and a thin second insulating jacket 11.
• a heater strip was prepared following the procedure described in Heater 1 below. For some examples, the heater strip was then wrapped with a second insulating jacket as specified. For those heaters listed as being braided, a metal braid comprising five strands of 28 AWG tin-coated copper wire was formed over the second insulating jacket or the sole insulating jacket to cover 86 to 92% of the surface. The braid had a thickness of about 0.030 inch (0.076 cm) and was equivalent to 18 AWG wire. Each heater was then tested using the Flame Test described below.
• composition 1 in Table I The ingredients listed under composition 1 in Table I were preblended and then mixed in a co-rotating twin-screw extruder to form pellets.
• the pelletized composition was extruded through a 1.5 inch (3.8 cm) extruder around two 22 AWG 7/30 stranded nickel/copper wires each having a diameter of 0.031 inch (0.079 cm) to produce a core with an electrode spacing of 0.106 inch (0.269 cm) from wire center to wire center and a thickness of 0.083 inch (0.211 cm) at a center point between the wires.
• a first insulating jacket with a thickness of 0.030 inch (0.076 cm) comprising a composition containing 10% by weight ethylene/vinyl acetate copolymer (EVA), 36.8% medium density polyethylene, 10.3% ethylene/propylene rubber, 23.4% decabromodiphenyloxide (DBDPO), 8.5% antimony oxide (Sb2 ⁇ 3), 9.4% talc, 1.0% magnesium oxide, and 0.7% antioxidant was then extruded over the core.
• the jacketed heater was irradiated to a dose of 15 Mrads.
• An indicator flag prepared from a strip of 0.5 inch (1.3 cm) wide unreinforced 60 pound kraft paper (94 g m 2 ) is positioned near the top of the heater and projects 0.75 inch (1.9 cm) toward the back surface of the enclosure.
• a Tirrill gas burner with a blue cone of flame of 1.5 inches (3.8 cm) and a temperature at the flame tip of 816°C is applied sequentially five times to a point on the front of the heater at a distance of 10 inches (25.4 cm) below the bottom edge of the paper flag.
• the period between sequential applications of the test flame is either (1) 15 seconds if the sample ceases flaming within 15 seconds, or (2) the duration of the sample flaming time if the flaming lasts longer than 15 seconds but less than 60 seconds.
• the sample In order to pass the test the sample cannot "flame" longer than 60 seconds following any of five 15-second applications of the test flame.
• the cotton underneath the sample at the bottom of the enclosure cannot be ignited during the test and the paper flag at the top of the sample cannot be damaged or burned over more than 25% of its area.
• EEA is ethylene/ethyl acrylate copolymer.
• MDPE medium density polyethylene
• CB is carbon black with a particle size of 28 nm.
• Antioxidant is an oligomer of 4,4-thio bis(3-methyl 1-6-6-butyl phenol) with an average degree of polymerisation of 3 to 4, as described in U.S. Patent No.
• Sb2 ⁇ 3 is antimony trioxide with a particle size of 1.0 to 1.8 ⁇ m.
• DBDPO is decabromodiphenyl oxide (also known as decabromodiphenylether).
• PEs 1 is clear 0.001 inch (0.0025 cm) thick polyester film available from
• PEs 2 is white 0.001 inch (0.0025 cm) thick polyester film available from
• PEs 3 is a film laminate of 0.001 inch thick polyester and 0.001 inch (0.0025 cm) thick blue polyethylene, available from Nepco Corporation as product
• Al/PEs is aluminized polyester film with a thickness of 0.001 inch (0.0025 cm).
• Al is aluminum foil with a thickness of 0.001 inch (0.0025 cm).
• TFE is a 0.002 inch thick multilaminar cast polytetrafluoroethylene film, available from Kemfab Corporation as DF100.
• PI is 0.002 inch (0.005 cm) thick polyimide film, available from DuPont as KaptonTM HN200.
• Glass is 0.005 inch thick fiberglass woven tape available from Crane as
• PE 1 is low density polyethylene film with a thickness of 1.25 inch (0.003 cm) available from Gillis and Lane.
• PE 2 is low density polyethylene film with a thickness of 0.003 inch (0.008 cm) available from Gillis and Lane.
• PVF2 is KynarTM polyvinylidene fluoride film with a thickness of 0.002 inch
• a conductive composition comprising 39% by weight ethylene/ethyl acrylate, 39% medium density polyethylene, 22% carbon black, and 1.0% antioxidant was prepared and was then extruded over two 22 AWG 7 30 stranded nickel/copper wires each having a diameter of 0.031 inch (0.079 cm) to produce a core with a generally round shape.
• the diameter of the core was approximately 0.145 inch (0.368 cm) and the electrode spacing was approximately 0.075 inch (0.191 cm) from wire center to wire center.
• a first insulating jacket with a thickness of 0.035 inch (0.089 cm) comprising thermoplastic rubber (TPRTM 8222B, available from Reichhold Chemicals) containing 30% by weight flame retardant (8% by weight Sb2 ⁇ 3 and 22% DBDPO) was then extruded over the core.
• the jacketed heater was irradiated to a dose of approximately 10 Mrads. When tested under VW-1 conditions, the heater failed.
• Example 25 A heater core was prepared following the procedure of Example 24.
• a first insulating jacket with a thickness of 0.020 inch (0.051 cm) comprising thermoplastic rubber (TPRTM 8222B, available from Reichhold Chemicals) was extruded over the core.
• a second insulating jacket with a thickness of 0.018 to 0.020 inch (0.046 to 0.051 cm) comprising the same material was then extruded over the first insulating jacket.
• the jacketed heater was irradiated to a dose of approximately 10 Mrads. This heater passed the VW-1 test
• a conductive composition comprising 29.3% by weight ethylene/ethyl acrylate, 32.4% high density polyethylene, 17.2% carbon black, 20.0% zinc oxide, 0.6% process aid, and 0.5% antioxidant was prepared and was then extruded over two 16 AWG 19-strand nickel/copper wires (each with a diameter of 0.057 inch (0.145 cm)) to produce a core with a wire spacing of 0.260 inch (0.660 cm) from wire center to wire center.
• the cross-section of the heater core between the wires was generally rectangular.
• a first insulating jacket with a thickness of 0.030 inch (0.076 cm) comprising the jacketing composition described in Example 1 was then extruded over the core.
• a tin-coated copper grounding braid was then positioned around the first insulating jacket This heater passed the VW-1 test.
• the response of the heater to thermal aging at 88°C (190°F) when in contact with different insulation layers was determined by cutting the heater to give samples 12 inches (30.5 cm) long with electrodes exposed at one end. The other end was covered with a heat-shrinkable end cap to prevent ingress of moisture or other fluids.
• the samples were each positioned on an aluminum plate with a thickness of 0.375 inch (0.95 cm), and then were covered with a sheet of insulation with a thickness of 0.38 to 0.75 inch (0.97 to 1.90 cm).
• a top aluminum plate with a thickness of 0.125 inch (0.32 cm) was positioned over the insulation layer.
• the resistance at 21°C (70°F) was measured to give the initial resistance and the samples were then placed in an air circulating oven heated to 88°C. Periodically, the samples were removed from the oven, cooled to 21°C, and their resistance was measured.
• a "normalized resistance", R was then calculated by dividing the resistance value after aging by the initial value. The results of the testing are shown
• a heater was prepared according to Example 26 except that a second insulating layer composed of 0.001 inch (0.0025 cm) thick polyester film (available from Pelcher- Hamilton Corporation as Phanex® IHC) was inserted between the first insulating layer and the grounding braid by helically wrapping it around the first insulating layer.
• the results of testing are shown in Table HI.
• a heater was prepared according to Example 27 except that the second insulating layer was composed of an aluminized polyester film with a thickness of 0.001 inch (0.0025 cm). The results of testing are shown in Table HI.
• Silicone is a 0.38 inch (0.97 cm) thick sheet of silicone foam, available from Insulectro as Cohrlastic foam, softgrade.
• RubatexTM is a polyvinyl chloride foam insulation with a thickness of 0.75 inch (1.91 cm), available from Rubatex. It contains plasticizers.
• ArmatexTM is a polyvinyl chloride foam insulation with a thickness of 0.75 inch (1.91 cm), available from Armstrong. It contains plasticizers.

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• Resistance Heating (AREA)
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• Compositions Of Macromolecular Compounds (AREA)

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• 1991
  • 1991-05-07 WO PCT/US1991/003123 patent/WO1991017642A1/fr active IP Right Grant
  • 1991-05-07 JP JP50966391A patent/JP3255232B2/ja not_active Expired - Lifetime
  • 1991-05-07 AT AT91910188T patent/ATE125096T1/de active
  • 1991-05-07 KR KR1019920702769A patent/KR100245568B1/ko not_active IP Right Cessation
  • 1991-05-07 CA CA002081029A patent/CA2081029C/fr not_active Expired - Fee Related
  • 1991-05-07 DE DE69111237T patent/DE69111237T2/de not_active Expired - Fee Related
  • 1991-05-07 EP EP91910188A patent/EP0536165B1/fr not_active Expired - Lifetime
• 1992
  • 1992-11-06 FI FI925037A patent/FI100844B/fi active
  • 1992-11-09 NO NO924306A patent/NO302450B1/no unknown

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