U.S. patent number 3,909,507 [Application Number 05/422,326] was granted by the patent office on 1975-09-30 for electrical conductors with strippable polymeric materials.
This patent grant is currently assigned to General Electric Company. Invention is credited to Joseph E. Betts, Joseph E. Vostovich.
United States Patent |
3,909,507 |
Betts , et al. |
September 30, 1975 |
Electrical conductors with strippable polymeric materials
Abstract
A composite of polymeric materials which are adheringly joined
to each other and which can be easily and cleanly separated by
stripping apart with a low pulling force whereupon the contacting
surfaces of their interface each separate cleanly without retention
of any residue from the other, and which comprises the combination
of a body of peroxide curable ethylene-containing polymer adjoined
to a body of a sulfur curable elastomer comprising chlorosulfonated
polyethylene. The combination of materials is especially
advantageous when used in wire and cable constructions comprising a
composite of an electrical insulation and an overlying strippable
semiconductive layer.
Inventors: |
Betts; Joseph E. (Westport,
CT), Vostovich; Joseph E. (Bridgeport, CT) |
Assignee: |
General Electric Company (New
York, NY)
|
Family
ID: |
23674390 |
Appl.
No.: |
05/422,326 |
Filed: |
December 6, 1973 |
Current U.S.
Class: |
174/102SC;
174/120SR; 174/120SC; 427/118 |
Current CPC
Class: |
B05D
7/20 (20130101); B05D 7/54 (20130101) |
Current International
Class: |
B05D
7/20 (20060101); B05D 5/12 (20060101); H01b
007/34 () |
Field of
Search: |
;174/12SC,12SR,12R,12SC
;117/232 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Goldberg; E. A.
Attorney, Agent or Firm: Simkins; R. G. Schlamp; P. L.
Neuhauser; F. L.
Claims
We claim:
1. An insulated metallic electrical conductor having a covering
thereon comprising, a combination of polymeric compositions
including a composite of an electrically-insulating body of a
peroxide-cured product of an ethylene-containing polymer with a
surface adheringly joined to a contacting surface of an easily and
cleanly strippable overlying semi-conductive body of a sulfur-cured
product of an elastomer of chlorosulfonated polyethylene, with said
contacting surfaces of the insulating body and overlying
semiconductive body being adheringly joined to each other as a
result of at least one of said polymeric materials having been
cured while the said surfaces of each of the bodies are in
adjoining physical contact with each other.
2. The insulated metallic electrical conductor of claim 1, wherein
the said contacting surfaces of the insulating body and overlying
semiconductive body are adheringly joined to each other as a result
of both the ethylene-containing polymer and the elastomer of
chlorosulfonated polyethylene having been cured simultaneously
while the surfaces of their bodies are in adjoining physical
contact with each other.
3. The insulated metallic electrical conductor of claim 1, wherein
the body of the sulfur-cured product of an elastomer of
chlorosulfonated polyethylene contains an electrically conductive
filler dispersed therethroughout.
4. The insulated metallic electrical conductor of claim 3, wherein
the electrically conductive filler is present in an amount of about
15 to about 75% by weight of the chlorosulfonated polyethylene
elastomer.
5. The insulated metallic electrical conductor of claim 3, wherein
the electrical conductive filler comprises carbon black.
6. The insulated metallic electrical conductor of claim 1, wherein
the semiconductive body of a sulfur-cured product of an elastomer
of chlorosulfonated polyethylene includes up to about 30% by weight
of an ethylenepropylene terpolymer.
7. The insulated metallic electrical conductor of claim 1, wherein
the semiconductive body of a sulfur-cured product of an elastomer
of chlorosulfonated polyethylene includes up to about 20% by weight
of an ethylene-propylene copolymer.
8. The insulated metallic electrical conductor of claim 1, wherein
the electrically insulating body of a peroxide-cured product of an
ethylene-containing polymer is polyethylene cured with an organic
tertiary peroxide curing agent.
9. An insulated metallic electrical conductor having a covering
thereon comprising, a combination of polymeric compositions
including a composite of an electrically insulating body of a
peroxide-cured product of polyethylene and an organic tertiary
peroxide curing agent, with a surface thereof adheringly joined to
a contacting surface of an easily and cleanly strippable overlying
semiconductive body of a sulfur-cured product of an elastomer of
chlorosulfonated polyethylene and a sulfur-containing curing agent
having an electrically conductive filler dispersed therethroughout
in an amount of about 15 to about 75% by weight of the elastomer,
said contacting surfaces of the insulating body and overlying
semiconductive body being adheringly joined to each other as a
result of both the polyethylene and the elastomer of
chlorosulfonated polyethylene having been cured simultaneously
while the surfaces of their bodies are in adjoining physical
contact with each other.
10. The insulated metallic electrical conductor of claim 9, wherein
the semiconductive body of a sulfur-cured product of an elastomer
of chlorosulfonated polyethylene includes up to about 20% by weight
of at least one ethylene-propylene rubber selected from the group
consisting of copolymers and terpolymers of ethylene and propylene.
Description
CROSS REFERENCE TO RELATED APPLICATION
This application is related to U.S. application Ser. No. 336,146,
filed Feb. 26, 1973, for Insulated Conductor With Strippable Layer,
by Thaddeus D. Misiura and Joseph E. Vostovich, now U.S. Pat. No.
3,793,476, and assigned to the same assignee as this
application.
BACKGROUND OF THE INVENTION
A common type of construction for electrical wires or cables
designed for medium to high voltage applications, for example about
15 to 35 KV, as well as other classes of electrical service,
comprises combinations of one or more insulating layers and
semiconductive layers. In a typical cable structure, for instance,
the metallic conductor may be provided with an organic polymeric
insulation such as cross-linked polyethylene, and an overlying body
of semiconducting material comprising an organic polymeric
composition which has been rendered electroconductive by the
inclusion therein of electrical conductivity imparting agents or
fillers such as carbon black. Although these cable constructions
may vary in certain elements, and often include an intermediate
component disposed between the metallic conductor and the primary
body of dielectric insulation such as a layer of separating tape or
inner layer of semiconductive material, or are enclosed within
protective covering sheaths, all such cable constructions
conventionally include therein at least a body of primary
insulation surrounding the conductor with an overlying body of
semiconducting material in physical contact with the insulation.
However, this arrangement of a layer of insulation with a
superimposed layer of semiconductive material thereover incurs
certain handicaps.
For example, to prevent the occurrence of ionization or corona
formation resulting from internal voids or pockets within the cable
construction and consequent ultimate breakdown of the insulation,
it is necessary to eliminate the presence or possible occurrence of
any free space or voids within or resulting from the interface
between the adjoining surfaces of the body of the insulation and
the body of semiconducting material. U.S. Pat. No. 3,677,849 deals
with this problem of intermediate void spaces at the interface of
the insulation and semiconductive material by applying a heat
treatment to the assembled product to induce a shrinkage of the
semiconductive material tightly about the insulation. U.S. Pat. No.
3,259,688 proposes a different solution to this problem comprising
a distinctive construction and an irradiation treatment. Further,
U.S. Pat. No. 3,646,248 discloses that this problem is resolved by
the use of an olefinic terpolymer insulation with a first curing
system and an olefinic terpolymer semiconductive material with a
second curing system comprising a different curing agent.
Further, the insulation layer and overlying semiconductive layer
for electrical cable can be formed concurrently about the wire or
metal conductor by means of a continuous simultaneous extrusion
process with one extruder apparatus, or these layers are formed in
sequence employing tandem extruders, and both layers are thereafter
cured at the same time in a single operation and unit to minimize
manufacturing steps and apparatus. However, the simultaneous curing
of both layers together, or even the curing of only one layer alone
while it is in a contiguous arrangement with the other, can result
in the apparent formation of cross-linking bonds bridging the
interface between the adjoining surfaces of each phase. The
occurrence of such cross-linking bonds bridging the interface
between the surfaces of said phases renders very difficult their
subsequent separation, such as in the removal of a portion of the
body of semiconductive material from about the insulation by
stripping for the purpose of making cable splices or terminal
connections. Such separation requires the application of great
force, and, upon being peeled off, the semiconductive material is
prone to leaving a substantial residue of its mass firmly adhering
to the other surface or insulation. As is known in the art, it is
necessary when splicing and treating cable ends that the
semiconductive material be cleanly stripped or completely removed
from the terminal section of the cable end without any damage or
material loss to the underlying surfaces of the insulation, and
thus the separation can require an appreciable amount of added
labor time and costs when the semiconductive material is difficult
to remove by stripping and/or a residue thereof is retained
tanaciously adhering to the surface of the insulation. The
difficulties of this aspect of such cable constructions are the
subject of U.S. Pat. Nos. 3,684,821 and 3,643,004.
SUMMARY OF THE INVENTION
This invention comprises a combination of specific organic
polymeric materials, which are cured with dissimilar curing
systems, and a composite construction formed therewith wherein the
two phases or bodies of the curable materials are adheringly united
with each other at their abutting surfaces to provide a
substantially continuous and secure union of their contacting
surfaces extending over their common interface. The combination and
cure systems of the invention effectively obviate the occurrence of
intermediate void spaces between the interface of the two phases or
bodies, while at the same time providing an interface union between
the phases which is easily separated with a relatively small
pulling force whereupon the components part with clean surfaces
each free of any residue from the other. The invention also
comprises a method of producing electrically insulated and shielded
cables.
The invention includes the combination of a first body of peroxide
curable ethylene-containing polymer with a second body composed of
a sulfur curable chlorosulfonated polyethylene rubber (Hypalon).
The sulfur curable chlorosulfonated polyethylene can contain minor
amounts of an ethylene-propylene rubber dispersed therethrough to
enhance the plastic properties of the chlorosulfonated polyethylene
rubber.
The compositions and the attributes of this combination are
uniquely suitable and advantageous for use in the construction of
insulated electrical wires and cables in the formation of a
composite insulation of an ethylene-containing polymer with an
easily and cleanly strippable semiconductive material superimposed
over the insulation. The polymeric material comprising the said
chlorosulfonated polyethylene elastomer can be rendered suitably
electroconductive so as to perform as a semiconductive material by
appropriately filling it with a typical electrical conductivity
imparting agent or filler such as carbon black, dispersed
therethrough, or some other electrically conductive particulate
material such as silicon carbide, iron, aluminum, etc., in such
amounts so as to impart the desired degree of conductivity.
OBJECTS OF THE INVENTION
It is a primary object of this invention to provide curable
polymeric materials that can be joined in a contiguous relationship
with their interfacial surfaces adheringly united together so as to
eliminate the presence or any occurrence of intermediate void
spaces therebetween, and which thereafter can be separated by the
application of a very low pulling force with the interfacial
surfaces of the bodies cleaving cleanly and free of any adhering
residual material.
It is also a primary object of this invention to provide insulative
electrical conductors or wire with coverings including a
combination of bodies of cured organic polymeric materials
comprising a first layer of insulation with a surface thereof
adheringly joined to a surface of a second layer which may be of
any suitable thickness down to less than about 1 millimeter, and
wherein the second layer of the polymeric material is easily and
cleanly strippable from the first layer of insulation with a very
low peeling effort of only a few pounds pulling force per 1/2 inch
wide strip of material, leaving the separated surface of each layer
intact, and clean and free of any residue, and a method of making
the same.
It is an additional and specific object of this invention to
provide an insulated electrical wire or cable having a multilayered
covering about a metallic conductor comprising a combination of
cured polymeric materials consisting of an insulation and an
overlying semiconductive shield which is free of intermediate voids
or spaces at the interface of said materials, and wherein the
material consisting of the semiconductive shield comprising a
polymeric carrier or matrix for particulate conductive filler
material dispersed therethrough can be peeled or stripped off the
underlying insulation with little effort or pull and it separates
or parts cleanly from the surface of the insulation leaving it
intact and without adhering material, and a method of making the
same.
It is a further object of this invention to provide a curable
composite polymer system of two layers or bodies which can be
substantially simultaneously formed and joined together such as in
a dual-head extruder and simultaneously cured joined in intimate
physical contact with each other, and the thus formed layers or
bodies can thereafter be cleanly separated or stripped apart with a
very small effort or force.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 comprises a perspective view of a portion of an insulated
conductor having a semiconductive shield thereon; and
FIG. 2 comprises a cross-sectional view of the insulation and
overlying semiconductive layer about a portion of metallic
conductor.
DESCRIPTION OF A PREFERRED EMBODIMENT
This invention is hereinafter described in relation to its
principal field of application and utility, namely, the
construction and method of producing electrical wire and cable,
although other areas of application are contemplated.
The invention specifically comprises a novel combination of given
curable polymeric materials, or combined bodies composed thereof,
which provide unique interfacial characteristics when their
contiguous surfaces are adheringly joined together by curing the
polymeric material of at least one of the combined bodies. Curable
polymeric materials of the invention comprise for the one phase, a
body or unit of peroxide curable ethylene-containing polymer, and
for the other phase of the composite, a body or unit of a sulfur
curable chlorosulfonated polyethylene elastomer.
The peroxide curable ethylene-containing polymer of one phase of
the combined polymeric bodies includes polyethylene, a common and
extensively used electrical insulation material for wire and cable,
which is cross-link curable with peroxide curing agents to a
thermoset state in keeping with the requirements of the invention.
Also included are similar copolymers of ethylene and other
polymerizable materials, and blends of such polymers and copolymers
which are at least predominantly composed of ethylene and are known
in the art to provide effective cross-link curable electrical
insulations. For example, copolymers of ethylene and vinyl acetate
and similar copolymers wherein the ethylene content is a majority
of more than 50% by weight, and preferably at least about 75% by
weight of ethylene content. The latter class of copolymers of
ethylene and blends for electrical insulating materials for wire
and cable are disclosed in the above mentioned U.S. Pat. Nos.
3,259,688 and 3,684,821, and other prior art publications.
The sulfur curable chlorosulfonated polyethylene (Hypalon)
elastomer phase, which when joined with the peroxide curable
ethylene-containing polymer phase together produce the distinctive
interfacial characteristics and functions of this invention, may
include minor amounts of an ehtylene-propylene copolymer or
terpolymer rubber as a softening agent or plasticizer to render the
chlorosulfonated polyethylene more tractable in compounding with
the electroconductive filler and other ingredients and in
processing and forming. Being curable with the same sulfur curing
systems as the chlorosulfonated polyethylene, the terpolymers of
ethylene, propylene and a diene can be included in amounts of up to
about 30 % by weight of the blend with the chlorodulfonated
polyethylene. The copolymers of ethylene and propylene which are
not curable with sulfur systems, cannot be tolerated in proportions
of more than about 20% by weight of the blend with the
chlorosulfonated polyethylene elastomer. Terpolymers of
ethylene-propylene include commercially available rubbers produced
by the copolymerization of ethylene and propylene together with
minor proportions of dienes such as ethylidiene norbornene, or
dicyclopentadiene or 1,4-hexadiene. The terpolymers of
ethylene-propylene with dienes, as is well known in the art, give
greater latitude in the available curing systems in relation to the
copolymers of only ethylene and propylene. Specifically, the
copolymers require a free radical curing mechanism as provided by a
peroxide compound, whereas the terpolymers with this additional
unsaturated radicals can also be cured with a conventional
sulfur-accelerator curing system, as well as with a peroxide free
radical system.
Sulfur-bearing curing systems for the chlorosulfonated polyethylene
(Hypalon), and ethylene-propylene terpolymers, are conventional and
well known in the art, for example, tetramethylthiuram disulfide
(METHYL TUADS), tetraethylthiuram disulfide (ETHYL TUADS),
dipentamethylene thiuram tetrasulfide (SULFADS), and the like
commercial sulfur bearing curing agents.
For service in electrical applications such as a semiconductive
component in cable for medium to high voltage service, the sulfur
curable chlorosulfonated polyethylene elastomer can be easily
rendered electroconductive to any appropriate degree desired by the
filling or inclusion therethroughout of a suitable amount of an
electrical conductivity imparting agent, such as about 15 to 75
parts of carbon black or metal particles by weight of the polymeric
ingredients according to conventional practices. When aptly
rendered electroconductive with a suitable amount of a conductive
material, dispersed therethroughout, the chlorosulfonated
polyethylene can fulfill the required electrical functions of a
semiconducting material in electrical cable, and when combined with
an ethylene-containing polymer insulation and cured in accordance
with requirements of this invention, it provides the unique
interfacial properties which effectively eliminate the occurrence
of intermediate void spaces between the interfaces of insulation
and semiconductive materials and also enables an easy and clean
separation of the semiconductive material from the insulation.
The ethylene-containing polymeric material or phase of the
combination of this invention is curable to a substantially
thermoset condition by cross-linking with a free radical forming
peroxide according to conventional practices such as described in
U.S. Pat. Nos. 2,888,424 and 3,079,370, and subsequent relevant
prior art. A preferred cross-linking curing system for the
ethylene-containing polymeric material comprises the use of a
tertiary peroxide curing agent such as a dicumyl peroxide.
In the practice of this invention it is required that at least one
of the polymeric bodies or phases, either the peroxide curable
ethylene-containing polymer or the sulfur curable chlorosulfonated
polyethylene, undergoes curing while the surface thereof is in
intimate physical contact with the surface of the other polymeric
body or phase whereby the curing mechanism of one phase can effect
the apparent bonds bridging the surfaces to adheringly unite the
contacting surfaces of the interface. However, as a practical
matter the most expedient manufacturing systems such as the
sequential or tandem extrusion of the dual layers of
ethylene-containing polymer and overlying chlorosulfonated
polyethylene upon the wire core followed by simultaneous curing of
both phase together, would incur the preferred curing of each
polymeric phase or material of the combination at the same time to
achieve the optimum effects thereof.
Referring to the drawing, a typical cable of medium-to-high voltage
capacity of the type to which this invention is especially
applicable and advantageous, is shown in perspective in FIG. 1, and
a short portion of such a cable is also shown with the insulation
and semiconductive layer in longitudinal cross section about the
conductor in FIG. 2. The overall cable product 10, primarily
comprises a metallic conductor 12, a relatively thick first body of
a peroxide cured ethylene-containing polymeric insulation 14
surrounding the conductor; and overlying the insulation is a second
body or layer of a sulfur cured chlorosulfonated polyethylene
semiconductive material 16. Other components can be included in the
cable structure following known designs, for example separating
paper or tape, or a semiconductive layer located between the
metallic conductor 12 and the primary insulation 14, such as are
shown in the aforementioned U.S. Pat. Nos. 3,259,688 and 3,684,821,
and the means of this invention apply thereto with its attendant
advantages whenever the insulation abuts the semiconductive
component, as is conventional in medium-to-high voltage capacity
cables. Upon curing at least one component of the superimposed
combination, either the body of the peroxide curable
ethylene-containing polymer insulation 14 or the body of the sulfur
curable chlorosulfonated polyethylene, filled semiconductive
material 16, and preferably both together, the insulation and
semiconductive material covering the insulation become adheringly
joined to each other producing a united interface 18 of unique
attributes which eliminate intermediate voids. Moreover, the thus
formed adhering bond between these components can be separated upon
the application of a small pulling force of only a few pounds and
the surfaces at the interface separate cleanly leaving each surface
free of adherents from the other.
The following comprise specific examples of suitable and preferred
polymeric materials for the application of this invention in the
construction of high-voltage cable comprising a body of peroxide
curable polyethylene insulation combined with an overlying body of
semiconductive material of a polymeric carrier or matrix comprising
sulfur curable chlorosulfonated polyethylene elastomer filled with
particulate conductive material.
The ethylene-containing polymer composition comprising the
insulation, or one phase or polymeric body of the combination of
this invention, consisted of the following typical commercial
insulating formula:
EXAMPLE A Percent Parts by By Weight Weight
______________________________________ Polyethylene, low density -
R-4 62.70 100.00 Sinclair Koppers Company Calcined Clay - Whitetex
Clay 31.04 50.00 Titanium Dioxide Pigment 3.10 5.00 Titanox RA-NC
Antioxidant - Monsanto Flectol-H, 1.09 1.75
polytrimethyldihydroquinoline Vinyl Silane 0.93 1.50 Curing Agent -
Hercules Di-Cup T, 1.77 2.85 di .alpha.- cumyl peroxide
______________________________________
These ingredients were compounded in a suitable mixer comprising a
roll mill, until substantially homogeneously dispersed. However,
pursuant to conventional practices, all ingredients, except for the
peroxide, were first admixed at elevated temperatures of about
250.degree.F, or within a range of about 200.degree.F to
300.degree.F, to flux the polymer and expedite the mixing.
Thereafter the mix was cooled to below the decomposition
temperature of the particular peroxide curing agent, in this case
down to below about 220.degree.F, whereupon the peroxide curing
agent was added and dispersed through the mix. The compound was
then ready for forming to a given shape and curing by the
application of heat.
The following comprises examples of the sulfur-cured
chlorosulfonated polyethylene elastomer, which as a body or layer
in combination with a body or layer of peroxide-cured
ethylene-containing polymer, produces the unique interface
characteristics of this invention. In these examples the sulfur
curable chlorosulfonated polyethylene component is filled with an
electrically conductive carbon black for the purpose of performing
as a semiconductive material in an electrical cable in combination
with a polyethylene insulation of the above formulation.
EXAMPLES I - IV
In the following examples, samples composed of the peroxide curable
polyethylene composition given in Example A, and a sample of sulfur
curable chlorosulfonated polyethylene elastomer and a blend thereof
with an ethylenepropylene terpolymer formulation given in Examples
I and II were individually sheeted on a hot mill, and a warm strip,
measuring about 0.060 to 0.075 inch thickness, of the polyethylene
composition was combined with a similar warm strip of each one of
the formulations of Examples I and II of about the same thickness.
The thus formed combined strip specimens comprising composite
Examples A-I and A-II were each individually molded as composite
slabs in a press and cured at 310.degree.F for about 45 minutes to
simulate a sequential extrusion molding of one warm layer upon the
other followed by a simultaneous curing.
Upon cooling each specimen to room temperature and conditioning
each at ambient conditions for approximately 16 hours, a 4 inch
long and 1/2 inch wide section of each composite cured specimen was
tested in a Scott tester for strippability, and the pulling force
in pounds required to separate the adhering layers of each specimen
is given in the following table for Examples I and II.
The formulations given in Examples III and IV, were respectively
extruded in a thickness of about 0.045 inch over an uncured
polyethylene insulation of the composition of Example A which had
been formed with an extruder around a core of a number 20 AWG wire
conductor in a thickness of about 0.175 inch. Each of said wire
specimens of the composite of peroxide curable polyethylene and
sulfur curable chlorosulfonated polyethylene blends were then cured
with steam at a temperature of about 210 psig (392.degree.F) for a
dwell period of about 3 minutes. After cooling and conditioning at
room temperature the pull required for stripping or separating the
layer of each sample of polymer composite and its parting
characteristics were determined. The pulling force to strip a one
half inch wide section of the chlorosulfonated polyethylene
formulation given in Examples III and IV from the adhesively joined
polyethylene composition of Example A is also given in the
following Table for Examples I- IV. Also each of the specimens were
found to separate clean and free of any residue.
__________________________________________________________________________
INGREDIENTS EXAMPLES I II III IV
__________________________________________________________________________
Chlorosulfonated polyethylene-duPont, Hypalon 40S 100.0 70.0 80.0
90.0 Ethylene-propylene terpolymer-duPont, Nordel 1320 -- 30.0 20.0
10.0 Conducting carbon black-Cabot, Vulcan XC-72 45.0 45.0 45.0
45.0 Hydrocarbon processing oil-Sun Oil, Circosol 4240 17.0 17.0
17.0 17.0 Litharge (90%) in ethylene-propylene binder-TLD-90 20.0
20.0 20.0 20.0 Microcrystalline wax - Sunoco Anti-Chek 2.0 2.0 2.0
2.0 Antioxidant-dihydro-trimethylquinoline-Vanderbilt, 0.5 0.5 1.0
1.0 Agerite Resin D N,N'-m-phenylenedimaleimide - duPont HVA-2 0.5
0.6 0.5 0.5 Curing agent-dipentamethylene thiuram hexasulfide- 0.6
0.6 0.6 0.6 Vanderbilt, Sulfads Approximate force in pounds needed
to strip cured Hypalon composition from cured polyethylene com-
position of Example A. 0.78 1.58 2.4 2.1
__________________________________________________________________________
* * * * *