U.S. patent number 3,663,742 [Application Number 05/077,685] was granted by the patent office on 1972-05-16 for method of mitigating sulfide trees in polyolefin insulated conductors.
This patent grant is currently assigned to The Furukawa Electric Co., Ltd.. Invention is credited to Teruo Fukuda, Morikuni Hasebe, Hiroshi Nagai.
United States Patent |
3,663,742 |
Hasebe , et al. |
May 16, 1972 |
METHOD OF MITIGATING SULFIDE TREES IN POLYOLEFIN INSULATED
CONDUCTORS
Abstract
In an electric cable provided with a plastic sheath and an
insulating layer consisting of polyolefin series resin applied
directly or with the aid of other insulating layer on the copper
conductor, polyolefin-series resin insulated electric cable
provided in a desired position with a sulfide-capture layer
consisting of a polyolefin-series resin composition incorporated
with such powder of metals, salts of the metals, or the mixture
thereof as to form water-insoluble metal sulfides by reacting with
water soluble sulfides.
Inventors: |
Hasebe; Morikuni (Yokohama,
JA), Nagai; Hiroshi (Yokohama, JA), Fukuda;
Teruo (Yokohama, JA) |
Assignee: |
The Furukawa Electric Co., Ltd.
(Tokyo, JA)
|
Family
ID: |
13687098 |
Appl.
No.: |
05/077,685 |
Filed: |
October 2, 1970 |
Foreign Application Priority Data
|
|
|
|
|
Oct 6, 1969 [JA] |
|
|
44/79338 |
|
Current U.S.
Class: |
174/120SC;
174/116; 174/110SR |
Current CPC
Class: |
H01B
3/308 (20130101) |
Current International
Class: |
H01B
3/30 (20060101); H01b 007/02 () |
Field of
Search: |
;174/110,12SR,12SC,12SC,15SC,16SC,12C,112,116 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
713,174 |
|
Aug 1954 |
|
GB |
|
836,255 |
|
Jun 1960 |
|
GB |
|
824,861 |
|
Dec 1959 |
|
GB |
|
Primary Examiner: Myers; Lewis H.
Assistant Examiner: Grimley; A. T.
Claims
What we claim is:
1. The method of mitigating formation of sulfide trees in an
insulating layer of an insulated electric cable having at least one
insulated cable core comprising a copper conductor encased within
an insulating layer of polyolefin-series resin and a separate
plastic sheath surrounding said cable core which comprises
providing said electric cable with a sulfide capture layer separate
from said insulating layer and said plastic sheath, said sulfide
capture layer consisting essentially of a layer of
polyolefin-series resin composition containing about 5 to 150 parts
by weight per 100 parts of resin of a substance or mixture of
substances capable of reacting with water-soluble sulfides to form
water-insoluble sulfides selected from the group consisting of
powdered zinc, cadmium, silver, cobalt, strontium, bismuth, gold,
tin, iron, copper, lead, nickel, antimony, manganese, vanadium and
tellurium, and the oxides, hydroxides and salts thereof.
2. A method according to claim 1, wherein the material of said
polyolefin-series resin insulating layer is selected from the group
consisting of high-density polyethylene, medium-density
polyethylene, low-density polyethylene and cross-linked
polyethylene.
3. A method according to claim 1, wherein the number of said
insulated cable cores are at least three.
4. A method according to claim 1, wherein said sulfide-capture
layer surrounds said insulated cable core.
5. A method according to claim 1, wherein said sulfide-capture
layer is contiguous to at least one side of said polyolefin-series
resin insulating layer of said insulated cable core.
6. A method according to claim 1, wherein the material of said
sulfide-capture layer is of a composition consisting of 100 parts
by weight of at least one base resin selected from the group
consisting of high-density polyethylene, medium-density
polyethylene, low-density polyethylene, ethylene-vinylacetate
copolymer, ethylene-ethylacrylate copolymer, ionomer, isotactic
polypropylene and isotactic polybutene-1 and 5 to 60 parts by metal
weight of at least one substance selected from the group consisting
of powdery metals salts of said metals, and the mixture thereof
capable of reaction with the water-soluble sulfide to produce a
water-insoluble sulfide.
7. A method according to claim 1, wherein the material of said
sulfide-capture layer contains at least one substance selected from
the group consisting of oxides, hydroxides, sulfates, chlorides,
nitrates, carbonates and aliphatic and aromatic organic acid salts
of lead, zinc, bismuth, cadmium, copper, iron and tin.
8. A method according to claim 1, wherein the material of said
sulfide-capture layer contains a lead salt selected from the group
consisting of lead oxide, lead hydroxide, lead carbonate, lead
nitrate, lead chloride, lead acetate, lead sulfate, lead chromate,
lead perioxide, red lead, lead sequioxide, white lead, lead
stearate, monobasic lead acetate, basic lead silicate, tribasic
lead sulfate, dibasic lead phosphite, dibasic lead phthalate,
tribasic lead maleate, lead salicylate and dibasic lead
stearate.
9. A method according to claim 1, wherein the material of said
sulfide-capture layer contains a zinc salt selected from the group
consisting of zinc oxide, zinc hydroxide, zinc sulfate, zinc
chloride, zinc carbonate, zinc stearate, zinc laurate and zinc
ricinoleate.
10. A method according to claim 1, wherein the material of said
sulfide-capture layer contains a cadmium salt selected from the
group consisting of cadmium sulfate, cadmium chloride, cadmium
carbonate, cadmium stearate, cadmium laurate and cadmium
ricinoleate.
Description
This invention relates to polyolefin-series resin insulated
electric cables and, more particularly, to polyolefin-series resin
insulated electric cables provided with a means of preventing the
deterioration of the polyolefin-series resin insulation due to
chemical trees (hereinafter referred to as sulfide trees).
Polyolefin-series resins (including polymers of an olefin,
copolymers of two or more olefins and cross-linked polyolefins
prepared by using an organic peroxide as a cross-linking agent)
have inherently excellent electric insulating and anti-chemical
properties. Accordingly, they have been extensively used as the
electric insulating material for electric cables. However, it has
recently been found that the polyolefin series resin insulated
electric cables laid in chemical plants and in water often result
in unexpected dielectric breakdown. Detailed examination of such
troubled cables reveals that copper sulfide and copper oxide grow
in tree-like form within the polyolefin-series resin insulation to
constitute leakage paths (these tree-like leakage paths are
hereinafter referred to as sulfide trees to distinguish them from
the so-called trees, which are electrically created in the
insulation in a high electric field). As result of extensive
investigations conducted by the inventors about the formation of
the sulfide trees, it has been verified that the sulfide trees will
result if the polyolefin-series resin insulated electric cable is
located at places where the water soluble sulfide will be produced.
It frequently occurs in the pits of chemical plants that the cable
is unintentionally exposed to the water-soluble sulfide either in
gase or aqueous solution. Hydrogen sulfide is produced through the
luxuriation of zostera on the sea-bed. It is also produced in the
presence of sulfate-reducing bacteria. In these surroundings,
hydrogen sulfide or sulfur ions will gradually penetrate by the aid
of and together with water through the cable sheath and the
insulator of the cable core to reach the periphery of the copper
conductor, where the hydrogen sulfide or sulfur ions will react
with copper conductor to produce the water insoluble copper
sulfide. The copper sulfide thus produced will sometimes be
oxidized to produce copper oxide. As copper sulfide is
crystallizable, it grows as tree-like crystals within the
polyolefin-series resin insulation at certain temperatures. The
growth rate is usually slow, but will be accelerated according to
the electric field and crystal structure of polymer. The copper
sulfide trees thus grown eventually penetrate the entire thickness
of the insulation and cause the dielectric breakdown of the
cable.
In order to prevent its phenomenon of the sulfide trees, various
measures have been proposed. In one such measure, the cable sheath
may further be covered with a metal, which is strongly resistant
against the water-soluble sulfide, for instance, lead, to prevent
the penetration of said sulfide into the electric cable. In a
second measure, a laminate tape consisting of a polyolefin film and
an aluminum foil may be applied along or wound on the periphery of
the insulated cable core, so that the penetration of the
water-soluble sulfide such as hydrogen sulfide is stopped by the
metal layer interposed between the insulated cable core and the
cable sheath.
These measures are indeed very effective. However, the former
measure is only justified if it is known that there is
water-soluble sulfide in the place where the cable is laid. If the
cable is to be laid in places where the presence of the
water-soluble sulfide is not prediatable, this measure is not
advantageous because the metal sheath increases the cost and weight
of the cable. The latter measure is also not economical because of
the provision of the laminate tape. Besides, it is possible that
during long period of use the water-soluble sulfide will permeate
through the seam between adjacent tape edges to give rise to the
growth of the sulfide trees. Thus, the second measure is not so
effective in spite of the increased steps and cost of manufacture
of the cable.
The invention, accordingly, is intended from the foregoing aspects,
and it has an object of providing a polyolefinseries resin
insulated electric cable, which is simple in construction and
capable of preventing the growth of sulfide trees over a long
period of use.
The present invention is based on the following finding: In
polyolefin-series resin insulated electric cables provided with a
plastic sheath outside the insulated cable core comprising an
insulating layer consisting of polyolefin-series resin applied
directly or with the aid of other insulating layer on the copper
conductor or, if necessary, around a desired number of insulated
cores, stranded together, it was found that hydrogen sulfide,
ammonium sulfide, etc. penetrating into the cable from outside
could be trapped in a sulfide-capture layer in the form of
water-insoluble metal sulfides and that the sulfide tree could be
prevented in the polyolefin-series insulating layer, by providing a
sulfide-capture layer of polyolefin-series resin composition
containing such powder of metals, salts of the metals, or the
mixture thereof as to form water-insoluble metal sulfides by
reaction with water-soluble sulfide, in a desired position that is
on the inside, outside, or both sides of said polyolefin-series
resin insulating layer or around a desired number of insulated
cores stranded together.
The aforesaid sulfide-capture layer made of a polyolefin-series
resin composition containing metals or metal salts capable of
reacting with the water-soluble sulfide such as hydrogen sulfide to
produce a water-insoluble metal sulfide may concurrently serve as a
semiconducting layer usually provided on the outer or inner side or
on both sides of the polyolefin-series resin insulating layer, or
it may be provided separately from the semiconducting layer. When
the sulfide-capture layer is provided on the outer side of the
polyolefin-series resin insulating layer, it may concurrently serve
as the protective sheath layer. In 3-core electric cables, for
example, the jute filler beneath the protective sheath may be
replaced with the polyolefin-series resin composition containing
metals or metal salts according to the invention. Thus, the end of
preventing the growth of the sulfide trees can be achieved by
providing the sulfide-capture layer around the copper conductor of
the polyolefin-series resin insulated electric cable.
To this end, in accordance with the invention it is preferable that
a metals or metal salts to be incorporated into the sulfide-capture
polyolefin-series resin layer are water-insoluble and that the
metal sulfide that will be produced by the reaction of metals or
metal salts with the water-soluble sulfide such as hydrogen sulfide
are also water insoluble. The above metals may be zinc, cadmium,
silver, cobalt, strontium, bismuth, gold, tin, iron, copper, lead,
nickel, antimony, manganese, vanadium, tellurium, and the above
metal salts may be oxides, hydroxides, sulfates, chlorides,
nitrates, carbonates and aliphatic and aromatic organic acid salts
of aforementioned metals. The grain size of these metals or metal
salts should not be too large, and is preferably below 100 meshes.
Among the aforementioned metal salts, such salts of lead as lead
oxide [PbO], lead hydroxide [Pb(OH).sub.2 ], lead carbonate
[PbCO.sub.2 ], lead nitrate [Pb(NO.sub.3).sub.2 ], lead chloride
[PbCl.sub.2 ], lead acetate [Pb(CH.sub.3 CO.sub.2).sub.2 ], lead
sulfate [PbSO.sub.4 ], lead chromate [PbCrO.sub.4 ], lead peroxide
[PbO.sub.2 ], red lead [Pb.sub.3 O.sub.4 ], lead sesquioxide
[Pb.sub.2 O.sub.3 ], white lead [2PbCO.sub.3 -- Pb(OH).sub.2 ],
lead stearate [Pb(C.sub.18 H.sub.35 O.sub.2).sub.2 ], mono-basic
lead acetate [Pb.sub.2 O(C.sub.2 H.sub.3 O.sub.2).sub.2 ], basic
lead silicate [PbO.sup.. H.sub.2 O.sup.. 2PbSiO.sub.3 ], tribasic
lead sulfate [3PbO.sup.. PbSO.sub.4.sup.. H.sub.2 O], dibasic lead
phosphite [2PbO.sup.. PbHPO.sub.3.sup.. 1/2H.sub.2 O], dibasic lead
phthalate [2PbO.sup.. Pb(C.sub.8 H.sub.4 O.sub.4)], tribasic lead
maleate [3PbO.sup.. Pb(C.sub.4 H.sub.2 O.sub.4)H.sub.2 O], lead
salicylate [Pb(C.sub.6 H.sub.4 (OH)CO.sub.2).sub.2 ] and dibasic
lead strearate [2PbO.sup.. Pb(C.sub.17 H.sub.35 COO).sub.2 ], such
salts of zinc as zinc oxide [ZnO], zinc hydroxide [Zn(OH).sub.2 ],
zinc sulfate [ZnSO.sub.4 ], zinc chloride [ZnCl.sub.2 ], zinc
carbonate [ZnCO.sub.3 ], zinc stearate [Zn(C.sub.17 H.sub.35
CO.sub.2).sub.2 ], zinc laurate [Zn(C.sub.11 H.sub.23
CO.sub.2).sub.2 ], and zinc ricinoleate [Zn(C.sub.17 H.sub.32
(OH)CO.sub.2).sub.2 ], and such salts of cadmium as cadmium oxide
[CdO], cadmium hydroxide [Cd(OH).sub.2 ], cadmium sulfate
[CdSO.sub.4 ], cadmium chloride [CdCl.sub.2 ], cadmium carbonate
[CdCO.sub.3 ], cadmium stearate [Cd(C.sub.17 H.sub.35
CO.sub.2).sub.2 ], cadmium laurate [Cd(C.sub.11 H.sub.23
CO.sub.2).sub.2 ] and cadmium ricinoleate [Cd(C.sub.17 H.sub.32
(OH)CO.sub.2).sub.2 ] are particularly preferable as they are
readily miscible with polyolefin-series resin, inexpensive and
readily available.
In accordance with the invention, the polyolefin-series resin, to
which the aforementioned powdery metals or metal salts are to be
incorporated, may include high density polyethylene, medium density
polyethylene, low density polyethylene, ethylene-vinylacetate
copolymer, ethylene-ethylacrylate copolymer, ionomer, isotactic
polypropylene and isotactic polybutene-1. These polyolefin-series
resins are suitable for they are inherently excellent in water
proofness, and less likely to undergo the degradation of physical
properties even when the aforementioned powdery metals or metal
salts are added thereto.
The invention will now be described by having reference to the
accompanying drawings, in which:
FIG. 1 is a sectional view of a polyethylene insulated electric
cable provided with a sulfide-capture layer, which contains a metal
or a metal salt capable of reacting with the water-soluble sulfide
to produce a water-insoluble metal sulfide between a copper
conductor and a polyethylene insulating layer, embodying the
invention;
FIG. 2 is a sectional view of a cross-linked polyethylene insulated
electric cable provided with a sulfide-capture layer, which
contains a metal or metal salt capable of reacting with the
water-soluble sulfide to produce a water-insoluble metal sulfide,
covering a cross-linked polyethylene insulating layer, embodying
the invention;
FIG. 3 is a sectional view of a polyethylene insulated three-core
electric cable provided with a sulfide-capture layer surrounding
three polyethylene insulated cable cores, embodying the invention;
and
FIGS. 4 and 5 illustrate the sulfide-capture effects obtainable in
accordance with the invention.
In the embodiment of FIG. 1, a copper conductor 101 having a
desired diameter is covered with a sulfide-capture coating 102
consisting of a polyolefin-series resin composition containing the
aforementioned metals or metal salts. The sulfide-capture coating
102 is covered with a polyolefin-series resin insulating layer 103
having a desired thickness, which is in turn covered with an
outermost plastic cable sheath 105.
In the embodiment of FIG. 2, the sulfide-capture coating 102 of a
polyolefin-series resin composition containing the aforementioned
metals or metal salts nature is provided on the outer side of the
polyolefin-series resin insulating layer 103.
In the embodiment of FIG. 3, three insulated cable cores, each
having a copper conductor 101 and a polyolefin-series resin
insulating layer 103 thereon, are stranded together with a filler
104. These stranded cable cores are covered with the
sulfide-capture layer 102, which is in turn covered with the
outermost protective plastic cable sheath 105.
In addition to the above embodiments, the aforementioned metals or
metal salts may be incorporated into the outermost protective
plastic cable sheath 105 or the semiconductive layer usually
provided on the outer or inner side of the usual insulating layer
103 so that the sulfide-capture substance-incorporated layer may
also serve as the sulfide-capture coating 102. It is particularly
advantageous in manufacture and from the standpoint of economy to
incorporate metals or metal salts capable of reaction with such
water-soluble sulfide as hydrogen sulfide to produce metal sulfides
in the semiconductive layer on the inner or outer side of the usual
insulating layer of the electric cable. In any case, an excellent
sulfide trapping effect can be expected from the addition of the
aforementioned metals or a metal salts to any other layer
surrounding the copper conductor than the polyolefin-series resin
insulating layer 103.
In this invention, the lower limit of the amount of metals or metal
salts to be added to a polyolefin-series resin composition
constituting the sulfide-capture coating depends upon the
coefficient of water permeability of the polyolefin-series resin
composition. With a polyolefin-series resin composition whose water
permeability coefficient at a temperature of 40.degree. C. is below
20.times.10.sup.12 (gcm/cm..sup.2 sec. cm. Hg), for instance, high,
medium and low-density polyethylene and polypropylene, at least 1
part by weight of the above metals or metal salts should be added
to 100 parts by weight of the resin. With a resin having a
permeability coefficient of above this value, the addition of at
least 10 parts by metal weight of the metals or metal salts to 100
parts by weight of the resin is necessary. The dependence of the
range of the amount of the metals or metal salts to be added to the
polyolefin-series resin composition constituting the
sulfide-capture coating upon the water permeability of the resin
used stems from the fact that the substantial proportion of the
accidents due to the penetration of the water-soluble sulfide have
actually taken place where the cable is laid in water, with water
acting as the carrier of a sulfide. There is no upper limit of the
amount of the above metals or metal salts to be added so long as
the aforementioned end alone is taken into consideration. However,
if more than 100 parts by metal weight of the above metals or metal
salts are added to 100 weight parts of the polyolefin-series resin
used, the degradation of physical and chemical properties of the
resin becomes outstanding depending upon the kind of the resin. For
this reason, the preferable range of the amount of the above metals
or metal salts is practically less than 150 weight parts, and more
practically 5 to 60 parts by metal weight, with respect to 100
parts by weight of the resin.
The effects according to the invention will become more apparent
from the results of experiments given below.
EXPERIMENT 1
Sample rods 10 mm. in diameter and 100 mm. in length were made from
compositions listed in Table 1 below. These sample rods were
immersed either in the aqueous solution of ammonium sulfide or in
the saturated aqueous solution of hydrogen sulfide for a certain
time. After each of the successive time intervals they were drawn
out of the solutions and radially severed to determine the sulfide
penetration speed by measuring the thickness of the portion
blackened due to formation of lead sulfide. The smaller the
thickness of the blackened portion, the greater, it was judged, the
sulfide trapping effect. The results of experiments using the
aqueous solution of ammonium sulfide are shown in FIG. 4, and those
using the saturated aqueous solution of hydrogen sulfide are in
FIG. 5.
---------------------------------------------------------------------------
TABLE
1 Sulfide- Sample rod Base Resin Capture Additive content additive
(in weight parts) 1 Polyethylene White Lead 10 2 Polyethylene White
Lead 20 3 Polyethylene White Lead 40
__________________________________________________________________________
As is apparent from FIGS. 4 and 5, so far as the effect of trapping
the water-soluble sulfide is concerned, it is increased by higher
content of the metal or metal salt additive capable of reacting
with the water-soluble sulfide to produce a metal sulfide.
EXPERIMENT 2
The results of experiments conducted about the effect of adding the
metals or metal salts capable of trapping the sulfide to the base
resin on the processibility and mechnical properties of the
resultant composition are given in Table 2 below. ##SPC1##
EXPERIMENT 3
Sample sheets were made of polyolefin-series resin compositions
shown in Table 3 below. ##SPC2##
Fifty-two sample pieces were prepared, each measuring
1.0-mm.-thick, 40-mm.-wide, and 200-mm.-long and composed of a
copper plate, 0.5-mm.-thick, 20-mm.-wide, and 160-mm.-long,
completely covered by hot-pressing with different kinds of
polyolefin-series resin composition. These sample pieces were then
immersed in the saturated aqueous solution of hydrogen sulfide.
After 35 days of immersion, each copper plate was stripped of its
resin covering and checked for blackening due to formation of
copper sulfide. In Samples Nos. 24, 33, 41, 44, 48 and 52, whose
covering did not contain any powdery metal or metal salt,
remarkable blackening of the copper plate was observed.
As is apparent from the above three kinds of experiments, for
formation of the sulfide-capture layer, it is desirable to
determine the content of sulfide-capture additives, i.e., metals or
metl salts, according to their kinds as well as the kind of the
base resin in which they are used.
Some examples of the fabrication of the polyolefin-series resin
insulated electric cable according to the invention will now be
described.
EXAMPLE 1
On a copper conductor 22 sq. mm in cross section was formed a
5-mm.-thick insulating layer of polyethylene (with density of 0.92
and melt index of 2.0), which was then extrusion-coated to a
thickness of 2.0 mm. with a semiconductive polyethylene composition
consisting of 100 weight parts of ethylene-vinylacetate copolymer
(with a vinylacetate content of 3 percent), 20 weight parts of
carbon black and 20 weight parts of white lead, which was in turn
covered with a polyethylene sheath, 1.5-mm.-thick, to complete a
polyethylene insulated electric cable. As a comparison sample, an
electric cable similar to the above, but free from white lead was
also produced.
These electric cables were then immersed for 245 days in an aqueous
solution of ammonium sulfide held at room temperature. Then, they
were taken out of the solution, and their coverings were removed
off the conductor. In the cable according to the invention, the
copper conductor was found blackened only in a minor degree, and
the formation of lead sulfide was observed in the conductive
polyethylene layer, but no sulfide trees were observed in the
polyethylene insulating layer. On the other hand, in the comparison
cable the copper conductor was observed to be blackened, and
tree-like crystals of copper sulfide about 0.6 mm. long were seen
growing in the polyethylene insulating layer.
EXAMPLE 2
A copper conductor 22 sq. mm. in cross section was extrusion-coated
to a thickness of 1.2 mm. with a semiconductive polyethylene
composition consisting of 100 weight parts of ethylene-vinylacetate
copolymer (with a vinylacetate content of 3 percent), 20 weight
parts of carbon black and 20 weight parts of litharge, on which was
then formed a cross-linked polyethylene insulating layer, 3 mm. in
thickness, which was in turn extrusion coated to a thickness of 1.2
mm. with the semiconductive polyethylene composition consisting of
100 weight parts of ethylene-vinylacetate copolymer (with a
vinylacetate content of 3 percent), 20 weight parts of carbon black
and 20 weight parts of litharge, and the resultant cable core was
finally covered with a polyethylene sheath, 1.5 mm. in thickness to
complete a polyethylene insulated electric cable. A comparison
cable similar to the above, but free from litharge was also
produced.
These electric cables were immersed for 490 days in the saturated
aqueous solution of hydrogen sulfide held at a temperature of
50.degree. C. Then they were taken out of the solution, and their
copper conductor was stripped of the coverings. In the cable
according to the invention, no copper sulfide crystals were
observed in the cross-linked polyethylene insulating layer. On the
other hand, in the comparison cable extreme blacking of the copper
conductor was observed and tree-like copper sulfide crystals, about
1.0 mm. long, were observed in the cross-linked polyethylene
insulating layer.
EXAMPLE 3
Three insulated cable cores, each comprising a conductor consisting
of seven copper wires (0.8 mm. in diameter) stranded together and
polyethylene (with density of 0.92 and melt index of 2.0)
insulating layer, 0.8-mm.-thick, thereon were stranded together
with jute. On the resultant strand was wound a cotton tape, which
was then extrusion coated to a thickness of 2.0 mm. with a
polyethylene composition consisting of 100 weight parts of
polyethylene, 2.5 weight parts of carbon black and 40 weight parts
of white lead to complete a 3-core polyethylene insulated control
cable. A comparison cable similar to the above free from white lead
in the cable sheath was also produced.
These control cables were left immersed for 147 days in an ammonium
sulfide solution while being charged with 200 volts at room
temperature. Thereafter, they were broken for examination. In the
cable according to the invention, no formation of sulfide copper
crystals was recognized in the polyethylene insulating layer. On
the other hand, in the comparison cable tree-like copper sulfide
crystals about 0.4 mm. long, were seen growing in the polyethylene
insulation.
EXAMPLE 4
A conductor consisting of seven copper wires (0.8 mm. in diameter)
stranded together was covered with an insulating layer, 1 mm. in
thickness, of polypropylene (with density of 0.90 and melt index of
1.0), which was then extrusion coated to a thickness of 1.5 mm.
with a polyethylene composition consisting of 100 weight parts of
polyethylene (with density of 0.92 and melt index of 0.3) and 35
weight parts of zinc oxide (ZnO) to form a sulfide-capture layer,
which was in turn extrusion coated to a thickness of 1.5 mm. with a
polyethylene composition (with carbon black content of 2.5 percent,
density of 0.93 and melt index of 0.3) forming the cable sheath,
thus producing a model cable. A comparison cable similar to the
above, but free from zinc oxide in the polyethylene composition
polypropylene insulating layer was produced.
These cables were then immersed for 6 months in the saturated
aqueous solution of hydrogen sulfide held at a temperature of
50.degree. C. while AC voltage of 400 volts was applied to them,
thus causing forced deterioration of them. Before the forced
deterioration, their insulation resistance was 7.17.times.10.sup.5
(m.OMEGA.-km). After the forced deterioration for 6 months, the
insulation resistance of the comparison cable decreased to
3.90.times.10.sup.3 (M.OMEGA.-km), whereas the insulation
resistance of the cable according to the invention decreased merely
to 2.45.times.10.sup.5 (M.OMEGA.-km). Detailed examination of these
deteriorated cables by breaking them revealed that in the cable
according to the invention the copper conductor had undergone only
slight blackening, and the polypropylene insulating layer
contiguous to the conductor had undergone no change. On the other
hand, in the comparison cable a great deal of black copper sulfide
crystals about 10.mu. long were seen growing in the polypropylene
insulating layer.
EXAMPLE 5
Three insulated cable cores, each comprising a conductor consisting
of seven copper wires (0.8 mm. in diameter) stranded together and a
0.8-mm.-thick cross-linked polyethylene (with gel fraction of 78
percent and density of 0.92) insulating layer thereon, were
stranded together with jute. On the resultant strand was wound a
cotton tape, which was then extrusion coated to a thickness of 1.5
mm. with a polyethylene composition consisting of 100 weight parts
of high density polyethylene (with desity of 0.96 and melt index of
0.2) and 45 weight parts of cadmium sulfate (CdSO.sub.4), which was
in turn extrusion coated to a thickness of 1.5 mm. with a
polyethylene composition (with carbon black content of 2.5 percent,
density of 0.93 and melt index of 0.3) forming the cable sheath,
thus producing a model cable. A comparison cable similar to the
above, but free from cadmium sulfate in the high density
polyethylene composition was produced.
These cables were then immersed for 6 months in the saturated
aqueous solution of hydrogen sulfide held at a temperature of
50.degree. C. while AC voltage of 400 volts was applied to them,
thus causing forced deterioration of them. Detailed examination of
these deteriorated cables by breaking them revealed that in the
cable according to the invention the copper conductor had suffered
no corrosion. On the other hand, in the comparison cable a great
deal of black copper sulfide crystals about 70.mu. long were seen
growing uniformly in the cross-linked polyethylene insulating
layer.
As is apparent from the above examples, the sulfide-capture layer
may be provided between the copper conductor and the insulating
layer thereon, or alternatively the sulfide-capture additives,
which are powdery metals or metal salts capable of reaction with
hydrogen sulfide, etc. to produce metal sulfides, may be added to a
covering layer such as an outer semiconductive layer or protective
plastic sheath layer.
It will be appreciated that according to the invention the end of
preventing the dielectric breakdown of the polyolefin-series resin
insulated electric cable (laid at places where they are affected by
chemicals or on the sea-bottom) due to growth of sulfide trees in
the insulation resulting from the reaction of a water-soluble
sulfide with the copper conductor can be achieved by preventing the
growth of the water-insoluble copper sulfide crystals in the
insulation through addition of metals or metal salts, which can
actively react with the water soluble sulfide entering the cable
from outside such as hydrogen sulfide, to produce a water-insoluble
metal sulfide, to at least one of the covering layers surrounding
the copper conductor other than the polyolefin-series resin
insulating layer. Thus, the above examples are by no means
limitative, but various changes and modifications may be made
without departing from the scope of the invention.
As has been described in the foregoing, according to the invention
the sulfide-capture layer surrounding the copper conductor of the
polyolefin-series resin insulated electric cable and containing
metals or metal salts capable of reacting with the water-soluble
sulfide to produce a water-insoluble metal sulfide, completely
captures the water-soluble sulfide entering the cable from the
outside and renders it into a metal sulfide insoluble in water, so
that the complete prevention of the growth of copper sulfide
crystals, the so-called sulfide trees, constituting the leakage
paths in the polyolefin-series resin insulating layer may be
ensured to provide stable insulating characteristic of the cable
insulation over a long period of use.
* * * * *