Field of the Invention
[0001] The present invention relates to an insulated wire, and more particularly, it relates
to an insulated wire such as a distribution wire, a wire for winding or the like which
is employed under high-vacuum environment or high-temperature environment such as
a high-vacuum apparatus or a high-temperature service apparatus. Background of the
Invention
[0002] An insulated wire may be applied to equipment such as heating equipment or a fire
alarm, for which safety under a high temperature is required. Further, the insulated
wire is also used under environment in an automobile, which is heated to a high temperature.
An insulated wire formed by a conductor which is coated with heat resistant organic
resin such as polyimide, fluorocarbon resin or the like has generally been used as
such an insulated wire.
[0003] As to application for which high heat resistance is required, or employment under
environment for which a high degree of vacuum is required, organic coating is insufficient
in view of heat resistance, no gas emission property and the like. Thus, an insulated
wire of such a form that a conductor is inserted in an insulator tube of ceramics,
an MI cable (Mineral Insulated cable) of such a form that a conductor is inserted
in a heat resistant alloy tube of a stainless steel alloy etc. which is filled with
metal oxide powder of magnesium oxide etc., or the like has been employed for such
application.
[0004] A fiber-glass braided insulated wire employing textile glass fiber as an insulating
member etc. is listed as an insulated wire for which flexibility is required with
heat resistance.
[0005] In the aforementioned insulated wire coated with organic resin having heat resistance,
the highest temperature at which insulability can be maintained is about 200°C at
the most. Therefore, it has been impossible to employ such an organic insulated coated
wire for application for which guarantee for insulability is required under a high
temperature of at least 200°C.
[0006] Further, the insulated wire which is improved in heat resistance through an insulator
tube of ceramics has disadvantages such as inferior flexibility. The MI cable is formed
by a heat resistant alloy tube and a conductor, and hence the outer diameter of the
cable is increased with respect to the conductor radius. Thus, the MI cable has a
relatively large section with respect to electric energy allowed by the conductor
which is passed through the heat resistant alloy tube. In order to use the MI cable
as a wire for winding which is wound on a bobbin etc. in the form of a coil, however,
it is necessary to bend the heat resistant alloy tube in prescribed curvature. In
this case, bending performed on the heat resistant alloy tube involves difficulty.
When the MI cable is wound in the form of a coil, further, it is difficult to improve
space factor since the tube of its outer layer is thick as compared with the conductor.
[0007] Further, when the fiber-glass braided insulated wire having heat resistance is employed
and worked into a prescribed configuration in response to its application, the network
of the braid is disturbed to cause a breakdown. In addition, dust of glass is generated
from the glass fiber. This glass dust may serve as a gas adsorption source. Therefore,
when the fiber-glass braided insulated wire is used under environment for which a
high degree of vacuum is required, it has been impossible to maintain a high degree
of vacuum due to the gas adsorption source provided by the glass dust.
[0008] On the other hand, there has generally been the so-called alumite wire prepared by
performing anodic oxidation treatment on a wire of aluminum or an aluminum alloy,
as an insulated wire which is excellent in heat resistance, insulability and heat
dissipativity. In this alumite wire, its base material is restricted to aluminum.
Further, an inorganic insulating layer formed on the base material is also restricted
to aluminum oxide. Thus, there has been such a problem that it is impossible to select
combinations of the base material and the inorganic insulating layer which are suitable
for various uses.
Disclosure of the Invention
[0009] Accordingly, the present invention has been proposed in order to solve the aforementioned
problems, and its object is to provide an insulated wire comprising the following
items:
(a) It has high insulability under environment of a high temperature.
(b) It is excellent in flexibility.
(c) It comprises no gas adsorption source.
(d) Combinations of a base material and an inorganic insulating layer suitable for
various uses can be selected.
[0010] An insulated wire according to the present invention comprises a base material, a
chromium oxide containing layer, and an oxide insulating layer. The base material
has an outer surface, and includes a conductor. The chromium oxide containing layer
is formed on the outer surface of the base material. The oxide insulating layer is
formed by applying a precursor solution of a metallic oxide onto the chromium oxide
containing layer by a sol-gel method or an organic acid salt pyrolytic method.
[0011] The chromium oxide containing layer is preferably formed by an electrochemical technique.
The electrochemical technique includes electrolytic plating or electroless plating.
The underlayer to be provided with the oxide insulating layer may be a CrO
3-x (1.5
< X
< 2.5) layer, in order to preferably serve as an adhesion layer. Namely, the layer formed
by the electrochemical technique has a chromium oxide layer as its outermost layer.
The oxide insulating layer preferably contains silicon oxide, aluminum oxide or zirconium
oxide. As to the base material, copper or a copper alloy is preferably employed in
view of high conductivity and the cost. In consideration of a use at a higher temperature
or the like, nickel chromium, silver, iron or a ferroalloy, a stainless steel alloy,
or titanium or a titanium alloy is preferably contained in the surface layer of the
base material.
[0012] It is known that a chrome plated layer is formed on a conductor of copper or a copper
alloy etc. as an excellent adhesion layer. However, insulating oxide ceramics such
as silicon oxide obtained by heat treatment of a precursor solution of a metallic
oxide hardly exhibits adhesion with respect to the chrome plated layer. This is based
on recognition of the inventors.
[0013] In an insulated wire obtained by directly forming a thin film of ceramics on a surface
of a conductor made of copper, further, the ceramics thin film serving as an insulating
layer has insufficient adhesion with respect to a base material.
[0014] According to the present invention, therefore, a layer having a chromium oxide layer
as its outermost layer is formed on an outer surface of a base material. Insulating
oxide ceramics adheres onto the chromium oxide layer as a layer having excellent adhesion.
[0015] The aforementioned chromium oxide layer is formed by an electrochemical technique.
When the chromium oxide layer is formed by electrolytic plating, a substance obtained
by adding a small amount of organic acid to an aqueous solution of chromic anhydride
is used as an electrolyte. Although a sergeant bath mainly composed of chromic anhydride
or sulfuric acid is known as an electrolytic bath employed for chrome plating, it
is different from this bath in the following point: Namely, mineral acid mixed into
the electrolytic bath has a function of dissolving chromic anhydride which is generated
on the surface of a plated layer in electrolytic plating. Therefore, a glossy metallic
chrome layer is plated when a sergeant bath is employed. In the present invention,
it is necessary to preferentially plate chromium oxide. Therefore, a small amount
of organic acid is added to an electrolytic bath employed in the present invention.
In a case of using mineral acid such as sulfuric acid, further, it is necessary to
employ a particularly dilute electrolytic bath. Namely, chromic anhydride concentration
is not more than 50 g/ℓ and sulfuric acid concentration is not more than 1 g/ℓ. Further,
while a thin film of insulating ceramics is formed on the outer surface of a layer
mainly composed of chromium oxide by heat treatment of a precursor solution of a metallic
oxide, the layer mainly composed of chromium oxide preferably has a roughened surface,
in order to further increase adhesion of the thin film.
[0016] The chromium oxide containing layer may be formed by electrolytic plating employing
an electrolyte which is prepared by adding sodium citrate, sodium carbonate or the
like, for example, to an aqueous solution of sodium chromate. In this case, the as-formed
layer is mainly composed of chromium oxide, which is generated by trivalent reduction
of hexavalent chromium contained in the electrolyte. If copper is used as a base material
in this electrolytic plating treatment, the base material surface is oxidized and
the chromium oxide containing layer is formed in the exterior thereof. However, adhesion
of the chromium oxide containing layer with respect to the base material is not reduced
by such oxidation of the base material surface.
[0017] Conditions for electrolytic plating for forming the inventive chromium oxide containing
layer are different from those for general bright plating in treatment current density
etc. Although the current density is set at 10 to 60 A/dm² in the bright plating,
depending on the treatment temperature, the current density is set at 100 to 200 A/dm²
in the present invention. A chromium oxide containing layer having a roughened surface
can be formed by this condition of the current density.
[0018] On the chromium oxide containing layer, an insulating oxide layer is formed by application
of a precursor solution of a metallic oxide. The precursor solution of a metallic
oxide mentioned in this specification is a solution prepared from a metal organic
compound, which is broadly classified in correspondence to a sol-gel method or an
organic acid salt pyrolytic method, and those of the following two types are included:
[0019] The first type of precursor solution is a solution which is generated by making hydrolytic
reaction and dehydration/condensation reaction of a compound containing hydrolyzable
metal-oxygen-organic group bonds such as metal alkoxide or acetate of a metal. This
solution may contain an organic solvent such as alcohol, a raw material compound such
as metal alkoxide, and water and a catalyst required for hydrolytic reaction. Further,
it generally contains an organic residual group such as alkoxide, dissimilarly to
hydroxide sol that is generated from inorganic salt.
[0020] The second type of precursor solution is a solution prepared by dissolving a metal
organic compound such as organic acid salt of a metal in an appropriate organic solvent.
In a method employing this type of precursor solution, a metallic oxide is generated
by pyrolyzation through heating after application. Therefore, a decomposition temperature
of the employed metal organic compound must be lower than its boiling point or sublimation
point.
[0021] The metal organic compound mentioned in this specification is a concept similar to
"metal-organic compounds" described in Journal of Materials Science 12 (1977) pp.
1203 to 1208, for example.
[0022] Further, the applied layer must be left at a temperature higher than the room temperature,
for volatilization of the organic solvent and removal of a residual organic substance.
However, the temperature of the atmosphere for such leaving must not be higher than
the melting point of the metal forming the base material.
[0023] It is possible to form almost all metallic oxide-based ceramics covering by application
of a precursor solution of a metallic oxide. SiO₂, Al₂O₃, ZrO₄, TiO₂, MgO or the like
can be listed as an example of a metallic oxide formed by this method. Further, ethoxide,
propoxide, butoxide or the like can be listed as metal alkoxide employed for the first
type of precursor solution. Metallic salt such as naphtanic acid, caprylic acid, stearic
acid, octylic acid or the like is preferable as organic salt employed for the second
type of precursor solution.
[0024] The oxide insulating layer formed from the precursor solution of the metallic oxide
by the sol-gel method or the organic acid salt pyrolytic method is an oxide which
is completely converted to a metallic oxide. This oxide is preferably formed by heat
treatment under an atmosphere in an oxygen current. In general, decomposition of the
compound contained in the solution which is applied onto the chromium oxide containing
layer is completely terminated at a temperature of about 500°C. If the same is heat
treated at a higher temperature, however, reaction between elements forming the chromium
oxide containing layer and a metal or semimetal contained in the applied solution
is facilitated, whereby adhesion between the chromium oxide containing layer and the
oxide layer is improved.
[0025] Thus, the oxide insulating layer converted to ceramics exhibits excellent heat resistance/insulability
also under a high temperature of at least 500°C. Further, the chromium oxide containing
layer is excellent in adhesion to the conductor forming the base material. Therefore,
adhesion between the oxide insulating layer and the outer surface of the base material
is improved as compared with the case of directly forming the oxide insulating layer
on the outer surface of the conductor by heat treatment of the precursor solution
of the metallic oxide. Thus, the insulated wire provided according to the present
invention has heat resistance/insulability, as well as excellent flexibility.
[0026] Further, the oxide insulating layer formed on the chromium oxide containing layer
has a smooth outer surface. Therefore, a high breakdown voltage proportionate to the
film thickness can be obtained, while it is possible to reduce a gas adsorption source.
[0027] According to the present invention, in addition, the chromium oxide containing layer
is formed between the base material and the oxide insulating layer. Therefore, combinations
with the inorganic insulating layer suitable for various uses can be selected through
the chromium oxide containing layer.
Brief Description of the Drawings
[0029] Fig. 1 is a sectional view showing a cross section of an insulated wire according
to the present invention in correspondence to Example 1.
[0030] Fig. 2 is a sectional view showing a cross section of an insulated wire according
to the present invention in correspondence to Example 2.
[0031] Fig. 3 is a sectional view showing a cross section of an insulated wire according
to the present invention in correspondence to Example 3.
[0032] Fig. 4 is a sectional view showing a cross section of an insulated wire according
to the present invention in correspondence to Example 4.
[0033] Fig. 5 is a graph showing the result of measurement of surface roughness of a chromium
oxide containing layer formed in accordance with Example 3 or Example 4.
[0034] Fig. 6 is a graph showing the result of measurement of surface roughness of a chrome
plated layer formed in accordance with Reference Example. Best Modes of Carrying Out
the Invention
Example 1
[0035] (a) Formation of Chromium Oxide Containing Layer
[0036] Electrolytic plating treatment was performed on an outer surface of a copper wire
of 2 mmφ in wire diameter. At this time, an electrolyte was prepared from that having
concentration of 40 g/ℓ of chromic anhydride and 0.45 g/ℓ of sulfuric acid. As to
plating conditions, the bath temperature was 50°C, the current density was 140 A/dm²,
and the treatment time was two minutes. Thus, a chromium oxide containing layer was
formed on the outer surface of the copper wire with a film thickness of about 1 µm.
[0037] (b) Preparation of Coating Solution used for Sol-Gel Method
[0038] Nitric acid was added to a solution mixed in mole ratios of tetrabutyl orthosilicate:water:isopropyl
alcohol = 8:32:60 in a ratio of 3/100 mole with respect to tetrabutyl orthosilicate.
Thereafter this solution was heated/stirred at a temperature of 80°C for two hours.
Thus, a coating solution used for a sol-gel method was synthesized.
[0040] The wire obtained by (a) was dipped in the coating solution of (b). A step of heating
at a temperature of 400°C for 10 minutes was performed ten times on the wire whose
outer surface was thus coated with the coating solution. Finally, this wire was heated
in an oxygen current of 500°C in temperature for 10 minutes.
[0041] An insulated covered wire obtained in the aforementioned manner is shown in Fig.
1. Fig. 1 is a sectional view showing a cross section of the insulated wire obtained
according to Example 1. Referring to Fig. 1, a chromium oxide containing layer 2 is
formed on an outer surface of a copper wire 1. On this chromium oxide containing layer
2, a silicon oxide layer 3 is formed by the sol-gel method as an oxide insulating
layer. The film thickness of an insulating layer formed by the chromium oxide containing
layer 2 and the silicon oxide layer 3 was about 4.0 µm.
[0042] A breakdown voltage was measured in order to evaluate insulability of the obtained
insulated wire. Its breakdown voltage was 800 V under the room temperature, and was
600 V under a temperature of 800°C. Even if this insulated wire was wound on an outer
peripheral surface of a cylinder having a diameter of 10 cm, no cracking was caused
in the insulating layer.
Example 2
[0043] (a) Formation of Chromium Oxide Containing Layer
[0044] A copper wire of 2 mmφ in wire diameter was vapor-degreased through use of perchloroethylene.
Thereafter the copper wire was dipped in a solution mixed in volume ratios of 85 %
phosphoric acid:70 % nitric acid:water = 15:2:3, thereby roughening its surface.
[0045] Then, the copper wire was used as a cathode and a stainless steel plate was used
as an anode to perform electrolytic plating treatment by feeding a direct current
of 0.05 A/dm². At this time, a solution of about 1ℓ prepared by dissolving 30 g of
sodium chromate, 30 g of sodium citrate and 30 g of sodium carbonate in water respectively
was used as an electrolyte.
[0046] Thus, a copper oxide layer having a film thickness of about 1 µm was formed on the
outer surface of the copper wire, and a chromium oxide containing layer was formed
in its exterior with a film thickness of about 0.1 µm.
[0047] (b) Preparation of Coating Solution used for Sol-Gel Method
[0048] A solution mixed in mole ratios of tetrabutyl orthozirconate [(C₄H₉O)₄Zr]:water:n-butyl
alcohol = 5:15:80 was heated/stirred at a temperature of 120°C for two hours. Thus,
a coating solution used for a sol-gel method was synthesized.
[0050] The wire obtained by (a) was dipped in the coating solution of (b). A step of heating
at a temperature of 400°C for 10 minutes was performed ten times on the wire whose
outer surface was thus coated with the coating solution.
[0051] An insulated covered wire obtained in the aforementioned manner is shown in Fig.
2. Fig. 2 is a sectional view showing a cross section of the insulated wire obtained
according to Example 2. Referring to Fig. 2, a copper oxide layer 12 is formed on
the outer surface of a copper wire 11. Further, a chromium oxide containing layer
13 is formed in the exterior of this copper oxide layer 12. On this chromium oxide
containing layer 13, a zirconium oxide layer 14 is formed by the sol-gel method as
an oxide insulating layer. The film thickness of an insulating layer formed by the
copper oxide layer 12, the chromium oxide containing layer 13 and the zirconium oxide
layer 14 was about 3.0 µm.
[0052] A breakdown voltage was measured in order to evaluate insulability of the obtained
insulated wire. Its breakdown voltage was 700 V under the room temperature, and was
500 V under a temperature of 700°C. Even if this insulated wire was wound on an outer
peripheral surface of a cylinder having a diameter of 10 cm, no cracking was caused
in the insulating layer.
Example 3
[0053] (a) Formation of Chromium Oxide Containing Layer
[0054] Electrolytic plating treatment was performed on an outer surface of a nickel-plated
copper wire of 1.8 mmφ in wire diameter. At this time, an electrolyte was prepared
from that having concentration of 200 g/ℓ of chromic anhydride, 20 g/ℓ of ammonium
methavanadate and 6.5 g/ℓ of acetic acid. As to plating conditions, the base material
was used as a cathode, while the bath temperature was 50°C, the current density was
150 A/dm², and the treatment time was two minutes. Thus, a chromium oxide containing
layer was formed on the outer surface of the nickel-plated copper wire with a film
thickness of about 1 µm.
[0055] As to the surface state of the chromium oxide containing layer, the center line average
roughness Ra was 0.15 µm and the maximum height Ry was 0.87 µm in accordance with
Surface Roughness of ISO468-1982. The surface roughness was measured by using a surface
contour measurer DEKTAK3030 made by Sloan Inc., U.S.A., under conditions of a tracer
diameter of 0.5 µm, a stylus pressure of 10 mg, a reference length of 50 µm, and no
use of a cutoff filter. The result of measurement is shown in Fig. 5.
[0056] (b) Preparation of Coating Solution used for Organic Acid Salt Pyrolytic Method
[0057] A coating solution was prepared by dissolving 20 g of 2-ethyl-hexanoic silicate in
100 mℓ of dibutyl ether.
[0058] (c) The wire obtained by (a) was dipped in the coating solution of (b). A step of
heating at a temperature of 500°C for 10 minutes was performed ten times on the wire
whose outer surface was thus coated with the coating solution.
[0059] An insulated covered wire obtained in the aforementioned manner is shown in Fig.
3. Fig. 3 is a sectional view showing a cross section of the insulated wire obtained
according to Example 3. Referring to Fig. 3, a nickel-plated copper wire comprising
a nickel-plated layer 22 formed on an outer surface of a copper wire 21 is used as
a base material. A chromium oxide containing layer 23 is formed on the outer surface
of this nickel-plated copper wire. On the chromium oxide containing layer 23, a silicon
oxide layer 24 is formed by an organic acid salt pyrolytic method as an oxide insulating
layer. The film thickness of an insulating layer formed by the chromium oxide containing
layer 23 and the silicon oxide layer 24 was about 5 µm.
[0060] A breakdown voltage was measured in order to evaluate insulability of the obtained
insulated wire. The breakdown voltage was 500 V under the room temperature, and was
300 V under a temperature of 800°C. Even if this insulated wire was wound on an outer
peripheral surface of a cylinder having a diameter of 5 cm, no cracking was caused
in the insulating layer.
Example 4
[0061] (a) Formation of Chromium Oxide Containing Layer
[0062] The so-called stainless steel clad copper wire of 1.8 mmφ in wire diameter, in which
a stainless steel alloy (SUS304) was engaged on an outer surface of a copper wire,
was used as a base material. Electrolytic plating treatment was performed on the outer
surface of this stainless steel clad copper wire. At this time, an electrolyte was
prepared from that having concentration of 200 g/ℓ of chromic anhydride, 20 g/ℓ of
ammonium methavanadate and 6.5 g/ℓ of acetic acid. As to plating conditions, the base
material was used as a cathode, while the bath temperature was 50°C, the current density
was 150 A/dm² and the treatment temperature was two minutes. Thus, a chromium oxide
containing layer was formed on the outer surface of the stainless steel clad copper
wire with a film thickness of about 1 µm.
[0063] As to its surface state, the center line average roughness Ra was 0.15 µm, and the
maximum height Ry was 0.87 µm in accordance with Surface Roughness of ISO468-1982.
The measurement was performed by using a surface contour measurer DEXTAK3030 made
by Sloan Inc., U.S.A., under conditions of a tracer diameter of 0.5 µm, a stylus pressure
of 10 mg, a reference length of 50 µm, and no use of a cutoff filter. As the result
of this measurement, that shown in Fig. 5 was obtained similarly to Example 3.
[0064] (b) Preparation of Coating Solution used for Organic Acid Salt Pyrolytic Method
[0065] 25 g of aluminum tetra-i-butoxide was dissolved in 100 mℓ of diethylene glycol monomethyl
ether, and thereafter heated/stirred at 150°C for one hour. This solution was stood
to be cooled to the room temperature, and thereafter mixed with 3 g of alumina particles
of 0.03 µm in nominal particle size, thereby preparing a coating solution.
[0067] The wire obtained by (a) was dipped in the coating solution of (b). A step of heating
at a temperature of 500°C for 10 minutes was performed ten times on the wire whose
outer surface was thus coated with the coating solution.
[0068] An insulated covered wire obtained in the aforementioned manner is shown in Fig.
4. Fig. 4 is a sectional view showing a cross section of the insulated wire obtained
according to Example 4. Referring to Fig. 4, a stainless steel clad copper wire having
a stainless steel alloy layer 32 on an outer surface of a copper wire 31 is used as
a base material. A chromium oxide containing layer 33 is formed on the outer surface
of the stainless steel clad copper wire. On this chromium oxide containing layer 33,
an aluminum oxide layer 34 is formed by an organic acid salt pyrolytic method as an
oxide insulating layer. This aluminum oxide layer 34 consists of an aluminum oxide
mixed layer containing aluminum particulates which have been mixed in the coating
solution from the start. The film thickness of an insulating layer formed by the chromium
oxide containing layer 33 and the aluminum oxide layer 34 was about 12 µm.
[0069] A breakdown voltage was measured in order to evaluate insulability of the obtained
insulated wire. Its breakdown voltage was 900 V under the room temperature, and was
700 V under a temperature of 800°C. Even if this insulated wire was wound on an outer
peripheral surface of a cylinder having a diameter of 15 cm, no cracking was caused
in the insulating layer.
Reference Example
[0070] (a) Formation of Metallic Chrome Plated Layer
[0071] Electrolytic plating treatment was performed on an outer surface of a nickel-plated
copper wire of 1.8 mmφ in wire diameter. At this time, an electrolyte to be used was
prepared from that having concentration of 250 g/ℓ of chromic anhydride and 2.5 g/ℓ
of sulfuric acid. As to plating conditions, the base material was used as a cathode,
while the bath temperature was 50°C, the current density was 40 A/dm², and the treatment
time was two minutes. Thus, a chrome containing layer was formed on the outer surface
of the nickel-plated copper wire with a film thickness of about 1 µm.
[0072] As to its surface state, the center line average roughness Ra was 0.06 µm and the
maximum height Ry was 0.51 µm in accordance with Surface Roughness of ISO468-1982.
The measurement was performed by using a surface contour measurer DEKTAK3030 made
by Sloan Inc., U.S.A., under conditions of a tracer diameter of 0.5 µm, a stylus pressure
of 10 mg, a reference length of 50 µm, and no use of a cutoff filter. The result of
this measurement is shown in Fig. 6. A glossy metallic chrome layer was formed on
the outer surface of the nickel-plated copper wire.
[0073] (b) Preparation of Coating Solution used for Organic Acid Salt Pyrolytic Method
[0074] A coating solution was prepared by dissolving 20 g of 2-ethyl-hexanoic silicate in
100 mℓ of dibutyl ether.
[0076] The wire obtained by (a) was dipped in the coating solution of (b). A step of heating
at a temperature of 500°C for 10 minutes was performed on the wire whose outer surface
was thus coated with the coating solution, whereby the as-formed insulating layer
was separated like a film after heating, and exhibited no adhesion.
Industrial Availability
[0077] As hereinabove described, the insulated wire according to the present invention is
suitable for a distribution wire, a wire for winding or the like, which is employed
under high-vacuum environment or high-temperature environment such as a high vacuum
apparatus or a high temperature service apparatus.