JPH07169337A - Corrosion resistant insulated wire - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a novel corrosion-resistant insulated wire that is inexpensive and has excellent resistance to molten carbonate. [Structure] A precursor ceramics insulating layer 16 is formed by coating a paint obtained by dissolving or dispersing a precursor ceramics polymer and an inorganic filler in an organic solvent and baking the paint directly on the conductor 10.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulated wire having excellent corrosion resistance, and more particularly to an insulated wire having excellent resistance to molten carbonate.

[0002]

2. Description of the Related Art A fuel cell is expected as a next-generation power generation system in order to maintain high energy conversion efficiency and good environmental protection, and this research and development is being strongly promoted. Especially 6
A molten carbonate fuel cell operated at a high temperature of around 50 ° C. is expected to be put into practical use as a highly efficient combined cycle power generation system.

Since a molten carbonate fuel cell uses an alkali carbonate having a strong corrosive property as an electrolyte medium, the corrosion of metal members constituting the cell is a problem. In particular, the compensating lead wire used for measuring the temperature of the molten carbonate is required to have remarkable corrosion resistance.

Conventionally, as a compensating lead wire for a fuel cell which is corroded by molten carbonate, an insulated electric wire has been proposed in which silver is used as a conductor and alumina fiber is wound directly on it.

[0005]

However, the conventional insulated wire is expensive because it uses a silver conductor. Also,
When general-purpose copper and copper alloys are used, in the wound layer of alumina fibers that serves as an insulator, there is a problem that corrosion of the conductor cannot be suppressed by immersion of molten carbonate.

Therefore, there is a demand for the development of an insulated electric wire, which is an alternative to silver and which is inexpensive and has excellent corrosion resistance and heat resistance, and which is provided with an insulating layer that does not affect the conductor even by immersion of molten carbonate. .

An object of the present invention is to solve the above-mentioned drawbacks of the prior art and to provide a novel corrosion resistant insulated wire which is inexpensive and has excellent resistance to molten carbonate.

[0008]

In order to achieve the above object, the present invention provides a precursor ceramics by coating and baking a coating material prepared by dissolving or dispersing a precursor ceramics polymer and an inorganic filler in an organic solvent and baking the coating material directly on the conductor. An insulating layer is formed. In addition, the paint is a precursor ceramic polymer 100
10 to 300 parts by weight of an inorganic filler is added to parts by weight, and this is dissolved or dispersed in an organic solvent to form a precursor ceramic polymer, and the precursor ceramic polymer is polycarbosilane, polysilazane, polytitanocarbosilane, polysila. 1 from styrene, polyborosiloxane, polysilane, polycarborane siloxane, polyaluminoxane, borazine, polyaluminum nitride, ladder type silicone, mineralized silicone
The inorganic filler is selected from the group consisting of two or more selected from the group consisting of aluminum, chromium metal elements, aluminum oxide, and chromium oxide oxide.
It is composed of a mixed system of at least one kind.

[0009]

The conductor used in the present invention is preferably a flexible SUS clad copper having a Vickers hardness of 200 or less.

The precursor ceramic polymer used in the present invention has a main chain made of a metal element such as Si, Ti, B and Al, and a side chain to which an organic group such as methyl group, hydrogen and phenyl group is bonded. Both are known, for example, polycarbosilane, polysilazane, polytitanocarbosilane, polysilastyrene, polyborosiloxane, polysilane, polycarboranesiloxane, polyaluminoxane, borazine, polyaluminum nitride, ladder type silicone, inorganicized silicone. Is mentioned. These may be used alone or in combination of two or more.

Examples of the inorganic filler used in the present invention include metal elements such as aluminum and chromium, aluminum oxide, and oxides of chromium oxide. You may use these individually or in mixture. The addition amount is preferably 10 to 300 parts by weight with respect to 100 parts by weight of the precursor ceramic polymer.

The precursor ceramics used in the present invention are preferably formed by a thermal decomposition method in which high temperature firing is performed, but chemical vapor deposition (CVD) or sol-gel method may be used.

The coating material used in the present invention can be adjusted in viscosity by adding or diluting an organic solvent such as xylene or toluene, and the coating method is preferably a dipping method.

The conductor used in the present invention has a Vickers hardness of 2
A flexible SUS clad copper of 00 or less is preferable because it is inexpensive and has excellent corrosion resistance and heat resistance. Also, the Vickers hardness is limited to 200 or less is 200
This is because if it is larger, the flexibility as an electric wire is poor.

[0015]

Embodiments of the present invention will be described below with reference to the accompanying drawings.

In FIG. 1, 10 is a flexible SUS clad copper conductor wire as a conductor, the inside is copper 12 and the outside is SUS.
It consists of 304 layers 14. This SUS clad copper conductor 1
A precursor ceramic insulating layer 16 is formed on the outer periphery of 0 to form an insulated wire.

Specific examples of the present invention and comparative examples will be described below with reference to Table 1.

[0018]

[Table 1]

Example 1 As shown in Table 1, 100 parts by weight of polycarbosilane, 100 parts by weight of aluminum and 100 parts by weight of xylene are placed in a predetermined container and dispersed by a pearl mill to obtain a uniform coating. A coating was applied on a flexible SUS clad copper conductor wire (Vickers hardness 100, wire diameter 0.7 mmφ, SUS304 clad thickness 0.05 mmφ) to form a conductor wire. The conductor wire was fired in air at 700 ° C. for 1 hour to produce an insulated electric wire having an insulation thickness of 25 μm.

Example 2 100 parts by weight of aluminum used in Example 1 was changed to 100 parts by weight of aluminum oxide to prepare an insulated electric wire having an insulation thickness of 30 μm.

Example 3 100 parts by weight of polycarbosilane used in Example 1 was changed to 100 parts by weight of polyaluminoxane to prepare an insulated wire having an insulation thickness of 28 μm.

Example 4 As shown in Table 1, 50 parts by weight of polycarbosilane, 50 parts by weight of polyaluminoxane, 50 parts by weight of aluminum, and 100 parts by weight of xylene are dispersed in a pearl mill to prepare a uniform coating composition. Similar to Example 1, the flexible SUS clad copper conductor was coated and fired, and then an insulated electric wire having an insulation thickness of 29 μm was produced.

Comparative Example 1 The aluminum compound of Example 1 was changed from 100 parts by weight to 8 parts by weight to produce an insulated wire having an insulation thickness of 24 μm.

Comparative Example 2 The aluminum compound of Example 1 was added in an amount of 100 parts by weight to 400 parts by weight.
By changing to the weight part, an insulated electric wire having an insulation thickness of 26 μm was produced.

Comparative Example 3 100 parts by weight of aluminum used in Example 1 was changed to 100 parts by weight of silicon oxide to prepare an insulated wire having an insulation thickness of about 30 μm.

Comparative Example 4 An insulated electric wire was produced by changing the flexible SUS clad copper conductor used in Example 1 to an annealed copper conductor (wire diameter 0.7 mmφ).

In order to investigate the resistance to molten carbonate of the conductors based on each example, in a molten carbonate (Li ₂ CO ₃ : K ₂ CO)
₃ = 62: 38, Air: CO ₂ = 70: 30,650
The conductor wire sample was immersed in (heated at 0 ° C), and an immersion test was performed at 60 ° C for 100 hours. The evaluation was performed as follows.

1. Observation of appearance: The presence or absence of cracks or peeling of the insulator was observed using an optical microscope.

2. Corrosion amount: The thickness reduction (half of the difference in conductor diameter before and after the test) was used. In this case, the conductor diameter after the test is the non-corroded part of the corrosion test piece cross section (healthy part).
Refers to the thickness of. In addition, this measurement was performed using a microscope with a micrometer.

3. Volume resistivity: Based on JISC3005, the resistance value was measured by a high insulation resistance meter after applying a direct current voltage of 100 V for 1 minute between the conductors in normal temperature air.

As is clear from Table 1, the insulated wire provided with the precursor ceramics insulating layer of the present invention was 650 ° C./10.
Even in the immersion test in 0 h of molten carbonate, cracks,
No peeling occurs, and the amount of corrosion is 0.7 to 1.2 μm
And the volume resistivity is 10 ¹² to 10
^It can be seen that the corrosion resistance is excellent, being on the order of ¹⁴ Ω · cm. On the other hand, in Comparative Example 1 in which the addition amount of aluminum was as small as 10 parts by weight, cracks were generated, and further, the corrosion amount was as large as 5.0 μm and the corrosion resistance was poor. On the contrary, in Comparative Example 2 in which the addition amount of aluminum is as large as 400 parts by weight, there is no crack or peeling and the corrosion amount is 0.8.
Good as μm, but volume resistivity of 10 ⁷ Ω · cm
And deteriorates. 10 silicon oxide instead of aluminum
In Comparative Example 3 in which 0 part by weight was added, the amount of corrosion was 3.5 μm, which was relatively large, and the value of the volume resistivity was as low as 10 ⁹ Ω · cm. In Comparative Example 4 in which the copper conductor was used, cracks and peeling were generated, the amount of corrosion was 6.0 μm, which was extremely large, and the volume resistivity value was reduced to 10 ⁷ Ω · cm.

[0032]

As described above, the insulated wire of the present invention is found to be extremely excellent in corrosion resistance, and it can be said that its value in this industry is extremely high.

[Brief description of drawings]

FIG. 1 is a diagram showing an embodiment of the present invention.

[Explanation of symbols]

 10 SUS Clad Copper Conductor (Conductor) 16 Precursor Ceramics Insulation Layer

Claims (5)

[Claims] 1. A corrosion-resistant insulated wire comprising a precursor ceramics polymer and an inorganic filler dissolved or dispersed in an organic solvent, which is applied directly on the conductor and baked to form a precursor ceramics insulating layer. 2. The coating material is a precursor ceramics polymer 10.
The corrosion-resistant insulated wire according to claim 1, wherein 10 to 300 parts by weight of an inorganic filler is added to 0 part by weight, and the inorganic filler is dissolved or dispersed in an organic solvent to prepare a coating material. 3. The precursor ceramic polymer is polycarbosilane, polysilazane, polytitanocarbosilane, polysilastyrene, polyborosiloxane, polysilane, polycarboranesiloxane, polyaluminoxane, borazine, polyaluminum nitride, ladder-type silicone, One or more selected from mineralized silicones.
Alternatively, the corrosion-resistant insulated electric wire according to 2. 4. The corrosion resistance according to claim 1, wherein the inorganic filler is one or a mixture of two or more selected from aluminum, chromium metal elements, aluminum oxide, and chromium oxide oxides. Insulated wire. 5. The corrosion-resistant insulated electric wire according to claim 1, 2, 3 or 4, wherein the conductor is a flexible SUS clad copper having a Vickers hardness of 200 or less.