|Publication number||US3650827 A|
|Publication date||Mar 21, 1972|
|Filing date||Nov 17, 1969|
|Priority date||Nov 17, 1969|
|Publication number||US 3650827 A, US 3650827A, US-A-3650827, US3650827 A, US3650827A|
|Inventors||Chester A Brown, Louis F Rossetti|
|Original Assignee||Electronized Chemicals Corp|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (8), Referenced by (24), Classifications (21), Legal Events (8)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent Brown et al.
[451 Mar. 211, 1972 FEP CABLES Inventors:
Chester A. Brown, Andover; Louis F. Rossetti, Arlington, both of Mass.
Electronized Chemicals Corp., Burlington, Mass.
Filed: Nov. 17, 1969 Appl. No.: 877,269
US. Cl .117/218,117/93.3,l17/128.4, 117/161 H, 117/232 int. Cl ..B44d 1/42 Field ofSearch ..l17/128.4,232,2l8, 161 H, 117/93.31
References Cited UNITED STATES PATENTS 5/1959 Greyson ..l17/232 2,929,744 3/1960 Mathes et al. .117/75 2,930,083 3/1960 Vostovich et al. .117/232 2,998,332 8/1961 Osdal ..117/232 2,999,772 9/1961 Burk et al. 1l7/93.31 3,136,680 6/1964 Hochberg 117/218 3,259,688 7/1966 Towne et al. ..117/232 3,269,862 8/1966 Lanza et al. ..1 l7/93.31
Primary Examiner-Murray Katz Assistant Examiner-Raymond M. Speer Artomey-Francis J Thornton I 5 7] ABSTRACT Electric cables of the type known as composite electrical insulated cables are insulated with a first inner layer of insulation material such as polyolefin and second outer layer of an irradiated cross-linked co-polymer of tetrafluoroethylene and hexafluoropropylene known in the trade as FEP to form a superior high temperature cable.
7 Claims, 1 Drawing Figure IRRADIATED POLYOLEFIN CONDUCTOR Patented March 21, 1972 3,650,827
IRRADIATED POLYOLEFIN CONDUCTOR INVENTOR CHESTER A. BROWN JR LOUIS F ROSS "m l ATTORNEY FEP CABLES BACKGROUND OF THE INVENTION It has long been known that polyolefins, such as polyethylene, are excellent insulating materials for electric wires, electrical components and the like. Generally, such wires consist of polyolefins covered with an outer layer of polyvinylidene fluoride (tradename Kynar) inwhich the polymer comprising each one ofthese layers is cross-linked. Cables of this type have been described in U.S. Pat. No. 3,269,862. Difficulties with such prior art cables have arisen since the dielectric properties of polyolefins are offset by their relatively low melting point and their low resistance to flame and oxidation while the polyvinylidenes have been noted for their poor mechanical strength, low operating temperatures and degradation during extrusion under elevated temperatures.
It is important therefore that when cables are to be'used at high temperatures or in mechanically abrasive areas that they be coated with a material which has high mechanical strength, high operating temperature and can be easily fabricated.
SUMMARY OF THE INVENTION l have now discovered that a superior cable of this typewill result from the use of a co-polymer of tetrafluoroethylene and BRIEF DESCRIPTION OF THE DRAWING A more thorough understanding of our invention can be gained from the appended drawing where'the FIGURE shows a cut-away prospective view of the end of a sheet cable made in accordance with our invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The cable indicated in the drawing. has a central copper conductor which may be in stranded or unstranded form, coated with a cross-linked polyolefin extruded thereon with a sheath of cross-linked FEP extruded over this insulating material. As noted above this outer sheath is in accordance with the present invention composed of a co-polymer' of tetrafluoroethylene and hexafluoropropylene'(FEP either in its natural state or radiation cross-linked. Although the draw ing discloses but a single conductor device, the invention is not to be limited to such a single conductor device but may also be applied to multi-conductor cables where one or more conductors are included within a single sheath.
In each of these known general constructions, however, the cable of the present invention is characterized bythe novel; use of a thin sheath of cross-linked FEP over the cross-linked polyolefin material. A suitable F EP material is sold du l Pont de Nemours and Company of Wilmington, Delaware under the designation Teflon I00 FEP Fluorocarbon resin. The method of making the preferred cable consists of coating a central copper conductor with a composition consisting of a mixture of high density, high molecular weight polyethylene composition, plus ingredients such as antioxidants, cross-linking promoters and flame retardants to provide various desired characteristics as is now known to the art. This insulated wire is then subjected to an irradiation dose of approximately 10 megarads using high energy electrons as the irradiation source. Following irradiation of the initial polyolefin coating,
a thin layer of HE? is extruded over the irradiated polyolefin by well-known techniques. The FEP material utilized for the purpose preferably comprises the Teflon I00 FEP fluorocarbon resin noted above. Following the extrusion of the FE? sheath, high energy electron, X-ra'ys or ultraviolet light is used to induce cross-linking in the FE? sheath. It is important to note that it is necessary this irradiation of this jacket occur at temperatures above the glass (internal friction) transition temperature of the FEP where cross-linking predominates over degradation. By proper selection of radiation dose and temperature, modified FEP resins with wide ranges of properties can be made. 7
Large doses of radiation cross-linked the Teflon FEP resin copolym'er such that its resistance to high tempeiature cut-through is significantly improved. Small amounts of radiation alter the resins melt-flow characteristics by changing its molecular weight and molecular weight distribution. This shift in molecular weight and molecular weight distribution also has a significant effect on the dependence of a shear rate on shear stress. Generally, electron irradiations for such operations is carried out using 2 Mev electrons. Such high energy electrons ,ensasi ltz realizes re s a itiqya u sqxsaff me ami- To irradiate cable coated in the described manner, it is preferable that the cable be passed under a 250 microamp 2 Mev beam at a rate such that the beam energy exposure of the completed cable is approximately 11 watts-seconds/cmF/pass. The cable will thus receive a total dose of approximately [.3 megarads. When the described cable is irradiated in this fashion at room temperature, net degradation will occur. However, if the temperature is raised to the glass (internal friction) transition temperature of the FEP resin (approximately 80 C.) the cross-linking of the resin becomes predominant and net degradation does not occur. At this glass (internal friction) transition temperature, under a constant rate dose of irradiation, the melt viscosity of the resin increases with temperature beyond the crystalline melting point. At higher temperatures (greater than 300 C. for FEP resin) thermal degradation again becomes a factor and net increases in viscosity in'the resin are smaller. Thus it is important that duringthe irradiation of the FEP sheath that the temperature of the cable be maintained above 8 0 C. but less than 300 C.
forth in the tables below: A w i i TABLE I Cut MIIrT-5438 throu h Flamma- Abraslon c, biiity Weight inches of lbs. 5 MIL test, AWG pe tape to radius .TC-98, size n 1,000 it failure knife vertical eflon 22 073 5. 4-5. 7 1821 23-41 Pass. MIIr-W-81044 Kynar jacketed cable 22 071 24 55 Do. Vinyl, 0., MIIrW-16878 20 059 4. 5 21 9. 5 Do. FEP, MI-LW1678, tmirradiated. .060 25% v 6 5 D0.
FEP, irradiated At dose rates greater than 2.6 megarads, improved elongation, resistance to deformation under load at elevated temperatures, increased stress resistances with only some slight loss in toughness. When the cable is irradiated at less than 1 megarad, the sheath retains its full characteristics athigh' stresses while at low stresses there is an advantageous decrease in flow rate. Thus, the FEP resin of the sheath increases the cable's mechanical strength at high operating temperatures while simultaneously preventing oxidation of the underlying polyolefin thus preventing degradation of the product.
TABLE II FEP FEP Irradiated Unirrad- 2.6 mr.
iated at 250 C.
Cut Through, time in hours at 250 C., V4" mandrel 40 500 Dielectric Constant after 1000 hours exposure 2.04 2.06
Dissipation Factor after 1000 hours exposure 0.0001 0.0001
Yield Stress p.s.i.
at 23 C. 1,920 2,030 at 225 C. 333 290 Tensile Strength psi.
at 23 C. 3,330 3,010 M225 C. 333 316 Ultimate Elongation k at 23 C. 354 383 21125 C. 160 498 Flexurul Modulus p.s.i.
at 23 C. 102,000 110,000 at 100 C. 15,900 20,900 at 200 C. 6,310 5,290
The method of cable construction thus described permits a significant increase in the operating temperature of cables by creating a wire construction which utilizes one of the best insulations known today, namely irradiated polyolefin. It further provides elevated structural strengths, elevated operating temperatures, reduction in thickness, reduction in weight and prevents combustion of the irradiated polyolefin wire in normally combustible situations. All of this is achieved without I ture ofthe co-polymer.
sacrificing the desirable electrical properties of the irradiated cross-linked polyolefin insulating layer.
Additionally the outer layer of cross-linked FEP provides a highly adherent oxygen barrier preventing oxygen degradation at high temperatures of the inner polyolefin insulating layer. This permits a great increase in the allowable noted temperature of the wire with a reduced thickness which is essentially non-flammable and electrically inert.
It should be noted that the irradiated polyolefin inner layer can be compounded with antioxidants, cross-linking promoters and flame retardants.
1. A structural article of manufacture comprising at least one electric conductor and an insulating material surrounding at least a portion of said conductor, said insulating material comprising an inner layer comprising an irradiated crosslinked polyolefin and an outer layer comprising an irradiated cross-linked co-polymer of tetrafluoroethylene and hexafluoropropylene.
2. A structural article comprising a first layer consisting a polyolefin and a second layer consisting of a co-polymer of tetrafluoroethylene and hexafluoropropylene, each of said layers being irradiated and thereby cross-linked throughout and each of said layers being irradiated and thereby crosslinked at least to an extent that when heated above its respective crystalline melting temperature it has form stability.
3. T e structural article of claim 2 wherein said polyolefin is polyethylene or its copolymers.
4. An electric cable comprising at least one conductor, a plurality of layers of insulation surrounding said conductor, one of said layers comprising an extruded cross-linked polyolefin intimately in contact with said electric conductor and a sheath surrounding said cross-linked polyolefin material and in intimate contact with said cross-linked polyolefin, said sheath comprising an irradiated cross-linked co-polymer of tetrafluoroethylene and hexafluoropropylene.
5. The method of forming an electrically insulated current carrying body comprising selecting electrical current carrying bodies whose lengths are substantially greater than their widths, forming a polyolefin layer over substantially the entire length of one of said electrical current carrying bodies, irradiating and thereby cross-linking said cross-linked polyolefin, coating said polyolefin layer with a co-polymer of tetrafluoroethylene and hexafluoropropylene and, irradiating and thereby cross-linking said co-polymer, said cross-linking being accomplished above the glass transition temperature of the co-polymer.
6. The method of claim 5 wherein said irradiation comprises high energy electrons sufficient to penetrate said co-polymer.
7. The method of claim 6 wherein the irradiation is accomplished at temperatures above the internal friction tempera-
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|U.S. Classification||428/383, 428/421, 427/118, 428/920, 427/379, 427/388.2|
|International Classification||H01B7/28, B05D7/20, H01B3/44, B05D3/06|
|Cooperative Classification||B05D7/20, B05D3/06, Y10S428/92, H01B7/28, H01B3/445, H01B3/441|
|European Classification||B05D7/20, B05D3/06, H01B3/44D2, H01B7/28, H01B3/44B|
|Jun 24, 1996||AS||Assignment|
Owner name: SANWA BUSINESS CREDIT CORPORATION AS COLLATERAL AG
Free format text: COLLATERAL ASSIGNMENT OF COPYRIGHTS, PATENTS, TRADEMARKS AND LICENSES;ASSIGNORS:HIGH VOLTAGE ENGINEERING CORPORATION;DATCON INSTRUMENT COMPANY;HALMAR ROBICON GROUP, INC.;AND OTHERS;REEL/FRAME:008013/0660
Effective date: 19960509
|Jun 25, 1991||AS||Assignment|
Owner name: FLEET NATIONAL BANK
Free format text: SECURITY INTEREST;ASSIGNOR:HIGH VOLTAGE ENGINEERING CORPORATION, A MA CORPORATION;REEL/FRAME:005748/0283
Effective date: 19910607
|Jun 28, 1989||AS||Assignment|
Owner name: FIRST NATIONAL BANK OF BOSTON
Free format text: SECURITY INTEREST;ASSIGNORS:COMFAB TECHNOLOGIES, INC.;HIGH VOLTAGE ENGINEERING CORPORATION;REEL/FRAME:005258/0013;SIGNING DATES FROM
|Dec 2, 1988||AS06||Security interest|
Owner name: HIGH VOLTAGE ENGINEERING CORPORATION
Owner name: MARINE MIDLAND BANK, N.A.
Effective date: 19880801
|Dec 2, 1988||AS||Assignment|
Owner name: MARINE MIDLAND BANK, N.A.
Free format text: SECURITY INTEREST;ASSIGNOR:HIGH VOLTAGE ENGINEERING CORPORATION;REEL/FRAME:005009/0952
Effective date: 19880801
|Aug 29, 1988||AS02||Assignment of assignor's interest|
Owner name: HIGH VOLTAGE ENGINEERING CORPORATION, A CORP. OF M
Effective date: 19880818
Owner name: SEIP, LTD., 551 MADISON AVENUE, NEW YORK, N.Y. 100
|Aug 29, 1988||AS||Assignment|
Owner name: SEIP, LTD., 551 MADISON AVENUE, NEW YORK, N.Y. 100
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:HIGH VOLTAGE ENGINEERING CORPORATION, A CORP. OF MA;REEL/FRAME:004932/0931
Effective date: 19880818
|Nov 12, 1980||AS02||Assignment of assignor's interest|
Owner name: ELECTRONIZED CHEMICALS CORPORATON
Effective date: 19801021
Owner name: HIGH VOLTAGE ENGINEERING CORPORATON, , SOUTH BEDFO