U.S. patent number 3,816,643 [Application Number 05/397,719] was granted by the patent office on 1974-06-11 for electrical cable and process.
This patent grant is currently assigned to E. I. du Pont de Nemours and Company. Invention is credited to Engelbert Pechhold.
United States Patent |
3,816,643 |
Pechhold |
June 11, 1974 |
ELECTRICAL CABLE AND PROCESS
Abstract
An electrical cable which can be made by the tandem extrusion
process is provided. The electrical cable comprises (1) a core of
an electrical conductor, (2) an aluminum shield surrounding the
conductor, at least the outer surface treated with a soluble azo
compound cross-linking agent for polyethylene and a complex of
fumarato chromic (III) nitrate, (3) a layer of a polyolefin having
a density within the range of 0.910 to 0.935 surrounding and
adhered to the treated surface of the aluminum shield, and
polyolefin being polyethylene or a copolymer of ethylene with at
least one .alpha.-olefin having three to eight carbon atoms (4) an
outer jacket of polyethylene containing carbon black surrounding
and adhered to the polyolefin layer.
Inventors: |
Pechhold; Engelbert (Chadds
Ford, PA) |
Assignee: |
E. I. du Pont de Nemours and
Company (Wilmington, DE)
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Family
ID: |
26934116 |
Appl.
No.: |
05/397,719 |
Filed: |
September 17, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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241240 |
Apr 5, 1972 |
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Current U.S.
Class: |
174/107; 156/54;
174/36; 174/110PM |
Current CPC
Class: |
H01B
13/14 (20130101); H01B 3/441 (20130101) |
Current International
Class: |
H01B
13/06 (20060101); H01B 13/14 (20060101); H01B
3/44 (20060101); H01b 007/18 () |
Field of
Search: |
;156/51,52,53,54
;174/107,12R,11PM,11R,11SR,36,12R,12C,12SR |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Chem. Abstract of Belgium Patent 765137, Complex Chromium Salt
Metal Surface Primer in AQS Solution..
|
Primary Examiner: Gilheany; Bernard A.
Assistant Examiner: Grimley; A. T.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATION
This is a continuation-in-part of application Ser. No. 241,240,
filed Apr. 5, 1972 now abandoned, and assigned to the assignee of
the present application.
Claims
What is claimed is:
1. An electrical cable comprising (1) a core of an electrical
conductor, (2) an aluminum shield surrounding the conductor, at
least the outer surface treated with an aqueous solution containing
from about 10 to about 30 percent by weight isopropanol, and a
dissolved azo compound cross-linking agent for polyethylene, and a
complex of fumarato chromic (III) nitrate, (3) a layer of a
polyolefin having a density within the range of 0.910 to 0.935
surrounding and adhered to the treated surface of the aluminum
foil, said polyolefin being selected from the group consisting of
polyethylene and a copolymer of ethylene with at least one
.alpha.-olefin having three to eight carbon atoms and (4) an outer
jacket of polyethylene containing carbon black surrounding and
adhered to the polyolefin layer.
2. The electrical cable of claim 1 wherein the azo compound is
selected from the group consisting of 4-t-butylazo-4-cyanovaleric
acid, 2-cyano-2'-carbamoylazobisisopropane, and
4,4'-azobis[4-cyanovaleric acid].
3. The electrical cable of claim 2 wherein the azo compound is
4-t-butylazo-4-cyanovaleric acid.
4. The electrical cable of claim 1 wherein the aluminum strip is
about 5 to 10 mils in thickness.
5. The electrical cable of claim 1 wherein the polyolefin layer is
polyethylene about 1 to 10 mils in thickness.
6. The electrical cable of claim 1 wherein the outer jacket is 40
to 80 mils in thickness and is polyethylene having a density within
the range of 0.910 to 0.935 containing about 2 to 3 percent by
weight of carbon black.
7. An electrical cable comprising (1) a core of an electrical
conductor, (2) an aluminum shield 5 to 10 mils in thickness
surrounding the conductor, at least the outer surface treated with
4-t-butylazo-4-cyanovaleric acid and a complex of fumarato chromic
(III) nitrate, (3) a layer of polyethylene about 1 to 10 mils in
thickness, having a density within the range of 0.910 to 0.935
surrounding and adhered to the treated surface of the aluminum
shield and (4) an outer jacket 40 to 80 mils in thickness of
polyethylene having a density within the range of 0.910 to 0.935
which contains about 2 to 3 percent by weight of carbon black.
8. The electrical cable of claim 1 wherein the treated aluminum
shield has a lap seam extending lengthwise of the cable.
9. The electrical cable of claim 7 wherein the treated aluminum
shield has a lap seam extending lengthwise of the cable.
10. A process for making an electrical cable of claim 1 in which
the azo compound and complex are applied to the aluminum shield by
contacting said shield with an aqueous solution of said complex and
said azo compound.
11. The process of claim 10 in which said azo compound is selected
from the group consisting of 4-t-butylazo-4-cyanovaleric acid,
2-cyano-2'-carbamoylazobisisopropane, and
4,4'-azobis[4-cyanovaleric acid].
12. The process of claim 11 in which said azo compound is
4-t-butylazo-4-cyanovaleric acid.
13. A double extrusion process for making electrical cable in which
a treated aluminum shield is wrapped around a conductor core with a
lap seam, a layer of polyolefin having a density within the range
of 0.910 to 0.935 is extruded onto said treated aluminum foil, said
polyolefin being selected from the group consisting of polyethylene
and a copolymer of ethylene with at least one .alpha.-olefin having
three to eight carbon atoms, and then an outer jacket of
polyethylene containing carbon black is extruded onto said
polyolefin layer, at least the outer surface of said aluminum
shield having been treated by contacting it with a solution in
water and about 10 to 30 percent by weight isopropanol of an azo
compound cross-linking agent for polyethylene and a complex of
fumarato chromic (III) nitrate to provide adhesion between said
aluminum shield and said polyolefin layer.
14. A process of claim 13 in which said azo acid is selected from
the group consisting of 4-t-butylazo-4-cyanovaleric acid,
2-cyano-2'-carbamoylazobisisopropane, and
4,4'-azobis[4-cyanovaleric acid].
15. A process of claim 14 in which said azo acid is
4-t-butylazo-4-cyanovaleric acid.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to electrical cables.
2. Prior Art
The conventional technique for making corrosion resistant
electrical cable employs a laminated shield as described in U.S.
Pat. No. 3,206,541, issued to Ludwik Jachimowicz on Sept. 14, 1965,
and in U.S. Pat. No. 3,233,036, issued to Ludwik Jachimowicz on
Feb. 1, 1966. This shield consists of aluminum or copper foil
coated on one or both sides with a copolymer of ethylene and
acrylic acid or acrylic acid esters of the type described in U.S.
Pat. No. 2,987,501 issued to James K. Rieke et al. on June 6, 1961,
and U.S. Pat. No. 3,027,346 issued to Frank M. Rugg et al. on Mar.
27, 1962. The coating exhibits moderate to good adhesion and fair
durability to moisture. An additional cable structure is described
in U.S. Pat. No. 3,586,756 issued to O. G. Garner et al. on June
22, 1971.
Manufacture of electrical cable of the type above described is
described in U.S. Pat. No. 3,332,138 issued to O. G. Garner on July
25, 1967. Additional manufacturing methods and cable constructions
are described in U.S. Pat. No. 3,272,912, issued Sept. 13, 1966 to
Ludwik Jachimowicz and U.S. Pat. No. 3,504,102 issued Mar. 31, 1970
to F. F. Polizzano.
In electrical cable of the type above described, it would be
desirable to use polyethylene because of its high electrical
resistivity and resistance to chemicals and moisture.
U.S. Pat. No. 3,674,915, issued July 4, 1972 to J. E. Pritchard
recommends the use of certain ethylene-1-olefin copolymers as the
dielectric in electric cables, with lubricants or slip agents
between the various layers of the cable. U.S. Pat. No. 3,681,515 to
R. C. Mildner teaches the use of thick or thin adhesive layers of
ethylene-acrylic acid copolymer to adhere a polyethylene sheath to
an aluminum shield in electrical cable. However, it would be
desirable to have a greater bond strength than is available with
such copolymers.
Belgian Patent 765,137, granted Oct. 1, 1971 discloses the ability
of fumarato chromic nitrates to adhere polyethylene and aluminum,
but even greater strengths are desirable in electric cable.
SUMMARY OF THE INVENTION
According to the present invention there is provided an electrical
cable comprising, (1) a core of an electrical conductor, (2) an
aluminum shield surrounding the conductor, at least the outer
surface treated with a soluble azo compound cross-linking agent for
polyethylene and a complex of fumarato chromic (III) nitrate, (3) a
layer of a polyolefin having a density within the range of 0.910 to
0.935 surrounding and adhered to the treated surface of the
aluminum shield, said polyolefin being polyethylene or a copolymer
of ethylene with at least one .alpha.-olefin having three to eight
carbon atoms and (4) an outer jacket of polyethylene containing
carbon black surrounding and adhered to the polyolefin layer.
BRIEF DESCRIPTION OF THE DRAWING
The accompanying drawing is a cross-sectional view of a cable
constructed in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
In the drawing, there is shown an electrical cable comprising a
plurality of individually insulated conductors 10 making up a cable
core. The core is wrapped longitudinally with an aluminum foil 11
which is treated on one or both surfaces with an aqueous solution
containing an azo acid cross-linking agent for polyethylene and a
complex of fumarato chromic (III) nitrate. The aluminum foil is
folded in such a way that overlap of the edges occurs to form lap
seam 12. While the aluminum foil can be of any convenient
thickness, it will usually be about 5 to 10 mils thick.
The fumarato chromic (III) nitrate complex used to treat the
aluminum surface is described in U.S. application Ser. No. 210,833,
filed Dec. 22, 1971, in the name of Alden J. Deyrup and assigned to
the assignee of the present application, the disclosure of which is
hereby incorporated by reference. A preferred complex is the Type
II complex described therein. This complex has the approximate
formula:
[Cr(H.sub.2 O).sub.4 (C.sub.4 H.sub.2 O.sub.4)].sup.+ NO.sub.3
.sup.-
Cross-linking agents for polyolefins are generally either azo
compounds or peroxide compounds. For commercial applications it is
desirable to have stable treating solutions with long shelf life at
a wide range of temperatures from near freezing to over
40.degree.C. such as might be encountered in transporting the
materials. Available azo compounds are more likely than peroxide
compounds to be stable in the highly acidic (pH about 1.5 to 2.0)
solution of chromium complex.
It is also desirable to have a minimum of organic solvents in the
treating solutions, both to minimize the ecological and economic
need for solvent recovery and also to avoid flammability in the
materials being worked with. Treating solutions may desirably
contain from about 10 to about 30 percent, preferably less than 20
percent, isopropanol and still not present flammability hazards.
Parts and percentages herein are by weight except where indicated
otherwise. Thus, the azo compounds must be soluble and stable in
acidic water containing 10 to 30 percent isopropanol and the
chromium complexes. This potentially includes the so-called water
soluble azo compounds and some that are not soluble in pure
water.
A preferred water soluble compound for use in the invention is
4-t-butylazo-4-cyanovaleric acid which has the following structure:
##SPC1##
This material is sold by the Lucidol Company under the designation
R-A73.
A less effective but still useful water soluble azo compound is
4,4'azobis[4-cyanovaleric acid], having the structure: ##SPC2##
Another effective water soluble azo compound is the monoamide
derivative of azo bisisobutyronitrile, known as
2-cyano-2'-carbamoylazobisisopropane and having the structure:
##SPC3##
Other suitable azo compounds will be readily apparent to those
skilled in the art. Although various levels of azo compounds are
suitable in treating solutions of the invention, 0.1 to 0.4 percent
concentrations are desirable.
Sodium salts and chloride salts are undesirable as the azo
compounds because of reaction with the acid chromium complex
solutions and deleterious effects on adhesion.
Application of an aqueous solution of the azo compound and the
complex to the aluminum surface can be by any convenient technique
such as dipping, spraying, brushing or rolling. After contacting
the aluminum surface with the solution, the surface may be dried by
heating. The effect of the treatment is to cause an invisible,
nonetching surface alteration, probably the adsorption of a
monomolecular layer of the complex which improves the speed and
durability of adhesion of polymers to the substrate.
The treated aluminum foil which is wrapped around the cable core to
form the shield is then surrounded with an adhesive layer 13 of a
polyolefin which is usually 1 to 10 mils in thickness but can be 50
mils or more in thickness. The polyolefin used has a density
between 0.910 to 0.935. Polyolefins useful in the present invention
and which have the specified density are polyethylene and
copolymers of ethylene with at least one .alpha.-olefin having
three to eight carbon atoms. The upper limit of the .alpha.-olefin
in the copolymer is only determined by the specific .alpha.-olefin
used which will give a copolymer having a density within the
specified density range.
In order to protect the coated aluminum shield, a protective outer
jacket 14 of polyethylene filled with carbon black surrounds and
adheres to the polyolefin adhesive layer. The outer jacket is
usually 40 to 80 mils in thickness and is polyethylene having a
density between 0.910 to 0.935. Carbon black is dispersed
throughout the outer jacket at a concentration lower than the
saturation level of carbon black in the polyethylene, but it will
usually be at a concentration between 2 to 3 percent.
The electrical cable of the present invention can be manufactured
by techniques known to those skilled in the art. For instance, the
method of British Patent 1,080,778 can be employed by extruding the
two polyethylene layers by the well-known tandem extrusion
process.
Advantages of the present invention include the ability to use
polyethylene as the adhesive layer and obtain good adhesion to the
aluminum foil. By having the aluminum foil treated with an azo
compound and the complex of fumarato chromic (III) nitrate, the use
of a prelaminated aluminum composite can be avoided. Thus,
manufacture of the electrical cable is simplified because of the
in-line coating of the aluminum shield with polyethylene by tandem
extrusion process.
The invention can be further understood by the following
example:
Wettable, dead soft aluminum foil (3 .times. 0.008 in.) is primed
on both sides with a dilute solution of Type II chromium (III)
fumarate coordination complex as described and prepared in Example
6 of U.S. Ser. No. 210,833 of Deyrup.
In this example, a solution of Type II is prepared. The preparation
is at a total volume of 1 liter, maintained by addition of water to
make up for evaporating losses during boiling.
In a liter of total aqueous solution are placed together 20.0 g.
chromium (III) nitrate, Cr(NO.sub.3).sub.3.sup.. 9H.sub.2 O, and
40.0 g. of fumaric acid. The solution is boiled for 1 hour, then
cooled to 24.degree.C., resulting in a clear blue solution with pH
1.18. To this are added with stirring 34.0 ml. of a 1.000 normal
sodium bicarbonate solution, resulting in a pH of 1.43. The
solution is boiled again 1 hour, then cooled to 24.degree.C.,
resulting in a pH of 1.33. To this are added 33.0 ml. of the 1.000
normal sodium bicarbonate solution, resulting in a pH of 1.63. The
solution is boiled again for 1 hour then cooled to 24.degree.C.,
resulting in a pH of 1.44. To this are added 33.0 ml. of the 1.000
normal sodium bicarbonate solution, resulting in a pH of 1.84. The
solution is boiled 3 hours longer, resulting in a pH of 1.67. It is
then cooled to 4.degree.-5.degree.C. and filtered to remove excess
fumaric acid. The resulting solution had a clear medium green color
with an absorption spectrum characteristic of Type II. This example
illustrates the preparation of a fairly completely converted
solution of II which is essentially pure except for the presence of
by-product sodium nitrate.
The Type II complex solution is diluted with water containing 10-30
percent of isopropanol, such as from 3 to 12 parts per part of
solution, preferably about 7:1. The treating solution of the
invention is made by adding azo compound to this complex solution,
such as about 0.1 to 0.4 percent azo compound, preferably about 0.4
percent based on the weight of the treating solution or 1 to 3
percent based on the chromium complex. Preferably about 0.4 percent
of 4-t-butylazo-4-cyanovaleric acid is dissolved completely in the
solution. This then forms the preferred treating solution which is
ready to use and which has a substantial shelf life stability. It
is applied to aluminum foil in any of a number of manners, and
air-dried in place. A preferred method is the use of gravure roll
application techniques as known in the art.
The treated aluminum foil is used for making cable by a double
extrusion technique. The foil is fed into a cable wrapping guide
where it is folded with the lap seam extending lengthwise of the
cable. No oil is used during the folding process. The resulting
aluminum shield is then pulled into a 2-inch extruder and coated at
230.degree.C. at a speed of 15 feet per minute with approximately
0.05 in. of a commercial grade of unstabilized low density
polyethylene having a density of 0.9201 and a melt index of 1.40.
The polyethylene is made by coordination catalysis at low pressure
with butene-1 comonomer. The coated cable is preheated (ca.
50.degree.C.), fed into an extruder with a different tubing die,
and a jacket of approximately 0.05 inch of black polyethylene
having a density of about 0.93 and containing 2.5 percent carbon
black is coated over it. Excellent adhesion is found between the
treated aluminum and polyethylene.
Comparative tests were made with samples of treated aluminum 0.7
mil thick adhered to 2.5 mil low density polyethylene film having
no antioxidant, "Alathon" 20 film sold by E. I. du Pont de Nemours
and Company. The tests showed much stronger bonds for samples made
with a treating solution of the invention containing azo compound
and Type II chromium complex than for samples made with a treating
solution which contained the Type II chromium complex but not the
azo compound.
The tests were made with a 7:1 dilution in water containing 30
percent isopropanol of the above-described Type II chromium complex
concentrate. The azo compound was 4-t-butylazo-4-cyanovaleric acid
at four concentrations. The treating solution was applied to the
aluminum foil by means of a gravure roll having 180 quadrangular
cells per square inch, and it was then dried at 65.degree.C. The
polyethylene was laminated onto the treated aluminum by passing
rapidly over a roll at 204.degree.C., with less than one second
contact time, and then promptly cooled. Then another sample of each
type was produced by passing over the roll at double the initial
speed. Samples were cut from the coated strip thus produced. The
samples had a width of 1 inch. The aluminum and polyethylene were
separated if possible and then pulled apart for a 180.degree.
separation in an "Instron" tester at a jaw separation rate of 2
inches per minute. Certain tests were also made after soaking in
water and in a 1:1 by volume water-ethanol solution for three
weeks. The force required to separate the aluminum and polyethylene
is reported in Table I below in grams for the one inch specimen
width.
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TABLE
I 180.degree. Peel Strength (g/in) Water- Treating Solution Line
Speed Dry Water Alcohol
__________________________________________________________________________
Complex 1x 24 5 5 do. 2x 22 5 5 Complex+0.15% 1x (insepar- 220 380
azo acid able do. 2x (do.) 50 90 Complex+0.23% 1x (do.) 180 250 azo
acid do. 2x 1230 30 40 Complex+0.32% 1x (insepar- 170 220 azo acid
able do. 2x 307 Complex+0.41% 1x (insepar- 170 290 azo acid able
do. 2x 449 0.15% azo acid 1x 40
__________________________________________________________________________
These data show the superiority of the invention under dry and wet
conditions and after exposure to wateralcohol solutions.
* * * * *