JPH08109083A - Conjugate material, its production and slide-sealing member composed of the conjugate material - Google Patents

Abstract

PURPOSE: To obtain a carbon-silicon carbide-metal conjugate material having improved impermeability, mechanical strength, heat resistance and abrasion resistance by subjecting a surface layer of a specified section (sliding section) of a carbon base material to a silication treatment and further impregnating metal to the whole body of the carbon material. CONSTITUTION: This conjugate material is produced by the following processes: (A) a process for forming a carbon base material having an average fine pore semidiameter of >=0.5μm into a product shape; (B) a process for applying a slurry prepared by suspending metallic silicon powder in a solution containing at least one selected from a polyamide imide, a polyvinyl alcohol and a polyamide resin on a specified position of the processed base material; (C) a process for forming a partial silicate coat on the base material by drying and curing the coated base material, and further baking at >=1500 deg.C; and (D) a process for impregnating metal on the whole body of the carbon base material. A metal for the impregnation is preferably antimony, silver, tin, copper or an alloy containing at least one selected from these metals as a main component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel composite material, particularly a composite material suitable as a member for sliding sealing, a method for producing the same, and its use.

More specifically, a novel carbon-silicon carbide-metal composite material obtained by locally silicifying the surface layer portion of a predetermined portion (sliding portion) of a carbon base material and further impregnating the base material with a metal. , And a novel manufacturing method thereof and applications using the material.

Such a composite material is a sliding sealing member which is required to have wear resistance, for example, a bearing, a shaft shaft, a piston cylinder inner wall, a piston ring, a thrust plate, a valve sliding portion component, a vane, a mechanical seal. It is applied to members, etc.

[0004]

2. Description of the Related Art Conventionally, carbon base materials have been widely used for sliding sealing members, but in order to improve the hardness and wear resistance of the carbon base materials, their surface is made harder and more wear resistant. It is necessary to convert and modify it to a silicon carbide having a high quality.

In such a case, it is not always necessary to modify the entire surface of the carbon base material to silicon carbide, and it is possible to selectively and locally modify only a sliding portion with particularly heavy wear, that is, only a predetermined portion. It is often enough.

The method of coating the surface of a carbon substrate with silicon carbide is generally well known, and it is roughly classified into a chemical vapor deposition method and a conversion method.

The chemical vapor deposition method (CVD method) is a method in which silicon carbide is generated by utilizing thermal decomposition and chemical reaction of a silicon compound and is deposited on the surface of a carbon base material. Since this method uses a carbon material as a base material that can be easily cut, it is easy to manufacture a sliding material having a complicated shape, and the obtained silicon carbide coating layer is also highly pure and dense. However, there is a serious drawback in that the coating layer is weakly bonded to the substrate and the coating layer is easily peeled off when subjected to the action of repeated mechanical or thermal stress.

On the other hand, in the conversion method (CVR method), by reacting silicon dioxide with carbon or silicon, the generated silicon monoxide gas is directly reacted with carbon on the surface of the carbon substrate to form a coating made of silicon carbide. This is a method of forming a layer, and for example, there is JP-A-1-264969. The silicon carbide coating layer obtained by this method has a strong bond with the carbon substrate, but is inferior in terms of denseness.

This is because half of the carbon atoms become carbon monoxide gas and scatter due to the reactions of [Chemical Formula 1] and [Chemical Formula 2], and as a result, the coating layer has a porosity almost equal to that of the carbon substrate. growing. Therefore, in order to use it in a portion where airtightness and impermeability are required, it is necessary to impregnate a thermosetting resin or the like to improve the airtightness of the base material.

[0010]

Embedded image

[0011]

Embedded image

However, as described above, both the vapor deposition method and the conversion method require very special equipment, and even unnecessary portions are covered, so that the material becomes high in cost. Therefore, a method of covering a portion of the carbon base material that does not need to be converted to silicon carbide by using a special jig or an inert powder is disclosed in JP-A-56-120584 and JP-A-56-120584. It is proposed in Japanese Patent Publication No. 57-7880. Further, a method of forming a groove on the surface of a carbon base material, applying Si to the portion and heat-treating it to convert it into silicon carbide is also disclosed in JP-A-61-1369.
Although proposed in No. 61, there are drawbacks that the operation is complicated, the workability is poor, and the cost is high.

More specifically, in the above-mentioned two known examples in which the carbon substrate is partially converted into silicon carbide, the coating area is reduced, and the CVD method or the CV method is used.
Since the silicon carbide is formed by the R method, the coating layer is easily peeled off or becomes porous, and the above-mentioned defects remain. Further, in the known example in which Si is placed, it is difficult to say that the operation itself is extremely complicated and extremely practical, and the obtained product has a melt of Si adhered to the surface thereof, and it is difficult to remove it. It's not easy.

Further, the carbon base material as it is generally does not have a perfect sealing property. This is because graphite is generally produced by sintering fine carbon particles and fine pores remain.

As means for the sealing property and mechanical strength of such a porous carbon substrate, a resin is usually provided in the pores of the substrate,
Means for impregnating and filling pitch, tar, inorganic material, metal, etc. are known.

[0016] Such a porous carbon substrate may require mechanical strength and impermeability when it is used as a sliding sealing member. Therefore, when the thermosetting resin described above is used for the purpose of sealing, it is porous,
When impregnated, the resin content becomes high, a large amount of volatile solution contained in the contained resin is generated in the curing step after impregnation, fine pores are formed, and the resin causes heat shrinkage due to curing. , Once again, fine pores are generated, and the desired impermeability cannot be obtained by one treatment of impregnation and curing.
It becomes necessary to repeat curing.

Also, due to the shrinkage of the resin when it is cured, the graphite base material, which is a product, likewise shrinks and its dimensions change greatly.
Further, since the resin is stuck to the outer peripheral portion of the product due to the resin being wiped out, it is necessary to process the outer periphery again.

[0018]

The problem to be solved by the present invention is to eliminate the drawbacks of the above-mentioned conventional sliding sealing materials of this kind.

[0019]

In the present invention, as a result of experiments under various conditions, a carbon substrate, preferably having an average pore radius of 0.
A carbon base material of 5 μm or more is processed into a product shape and suspended and mixed only in a necessary portion with a solution of silicon powder (Si) and a resin, particularly polyamide imide, polyvinyl alcohol, polyamide resin having a low residual carbon rate. Slurry is applied, dried, hardened, and the carbon base material and molten silicon are reacted at a high temperature of 1500 ° C. or higher to locally apply S to a target portion.
By converting to iC and further impregnating with metal,
It was completed by applying a novel carbon silicidation technology that can solve all the problems of conventional sliding sealing materials as a constituent element.

[0020]

The function and structure of the present invention will be described in more detail.

(1) The method for producing the carbon base material used in the present invention may be carried out by using an ordinary carbon material production method. Examples of the carbon base material used here include general graphite materials and isotropic materials. To be It is desirable to use a carbon substrate having an average pore radius of 0.5 μm or more processed into a product shape. If the average pore radius of the carbon substrate is less than 0.5 μm, the slurry in which silicon and resin are mixed or the molten metal silicon tends to be difficult to permeate into the pores. In the present invention, only the sliding portion is locally S
By providing iC, adjusting the ratio of carbon and SiC, and further impregnating a metal, a composite material having good wear resistance, corrosion resistance, heat resistance, and further excellent sealing performance is provided.

(2) As the resin used, a resin having a high film-forming property and a low residual carbon rate, for example, a resin selected from polyamide imide, polyvinyl alcohol and polyamide resin is particularly preferably used. Among them, polyamideimide is more preferable, and it is dissolved in a solvent such as dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl-2pyrrolidone.

(3) This solution has an average particle size of about 30-50.
A silicon powder (Si) of μm is mixed and dispersed to obtain a slurry.

(4) It is possible to convert only the necessary portion to SiC by locally applying the slurry to a desired portion of the carbon base material by a suitable means such as brush coating or hand coating. .

(5) After that, it is dried and cured at about 300 ° C. for 2 hours. The solvent evaporates in this step.

(6) The material obtained as described in (1) to (5) is heat-treated at a high temperature in an inert gas atmosphere or in a vacuum. Temperature rising rate is about 1550-160 at about 800 ° C / hr
Hold at 0 ° C for 20 minutes. The heating means is not particularly limited and may be any suitable means.

(7) In the carbon-SiC composite material thus obtained, since the carbide of the resin adheres to the surface of the carbon base material, it is removed.

(8) A metal impregnation is further applied to the manufacturing method of (1) to (7) to obtain impermeability, mechanical strength, heat resistance,
Improves wear resistance.

(9) Examples of the metal used for impregnation include Sn, Cu, Sb, Ag, Zn and alloys containing these as the main components.

As this metal, a metal or an alloy having a melting point of 200 ° C. or higher and hardly reacting with carbon to form a carbide is used. When the melting point is less than 200 ° C, heat resistance may not be imparted to the produced composite material.

A method of impregnating a carbon-SiC composite with a metal is as follows.
First, put the metal to be impregnated in the impregnating device, and then 1-5 Torr
It is heated under reduced pressure to dissolve the metal. The product prepared in the steps up to (7) is put into this, pressurized to 50 to 100 kg / cm ² and held for 30 minutes or more to impregnate.

In the carbon-silicon carbide-metal composite material obtained by the present invention, a coating layer of silicon carbide is formed on a predetermined portion (sliding surface) of a carbon base material, and the entire surface thereof (the carbon base material and the coating material is coated). Both of the silicon carbide layers are of metal-impregnated structure. Therefore, the sealing property is extremely high and the sliding property is also very excellent. In addition, since the silicon carbide layer, which is the coating layer, is also impregnated with metal, the synergistic effect of these causes the sliding characteristics of the sliding surface to be larger than that of the conventional partial silicon carbide coating. Become.

[0033]

EXAMPLES The present invention will be described in detail below with reference to examples. [I] Test sample

[0034]

Example 1 An isotropic graphite material (SIC-12 manufactured by Toyo Tanso Co., Ltd.) having an average pore radius of 2 μm was processed into a product shape of φ52.2 / φ42.5. On the other hand, polyamide-imide resin (Al
-10, Ohara Kako) to N-methyl-2pyrrolidone 1
It was dissolved in 100 parts by weight to give a 20% solution. Si in this solution
60 parts by weight of C powder (average particle size: 50 μm, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed into a slurry.

This slurry was applied to a required portion of the carbon substrate and then cured at 300 ° C. in a dryer.

Further, the temperature was raised to 1600 ° C. in a vacuum furnace, held for 30 minutes, cooled, and then taken out.

Further, Sb is melted in the impregnating device to obtain SiC.
After dipping the semi-product that is of, by introducing N ₂ gas, 100 kgf
The sample was kept at / cm ^{2 for} 30 minutes and then taken out after cooling. The impregnation rate of Sb was 66% (weight).

[0038]

[Example 2] "ISEM-" having an average pore radius of 1.5 µm
1 "(manufactured by Toyo Tanso Co., Ltd.) was used, and the following manufacturing method was carried out in the same manner as in Example 1 to impregnate SiC with 2.0 mm. The impregnation conditions were the same, and Sn was used as the impregnation metal.

[0039]

[Example 3] "ISO-5 having an average pore radius of 0.5 µm"
0 "(manufactured by Toyo Tanso Co., Ltd.) and a SiC layer of 0.5 mm
Formed. The impregnation method was the same, and Cu was used as the impregnation metal.

[0040]

[Comparative Example 1] "KC-1" having an average pore radius of 1.0 μm
7 "(manufactured by Toyo Tanso Co., Ltd.), φ52.5 / φ42.5 impregnated with phenol resin was prepared.

[0041]

[Comparative Example 2] "KC-1" having an average pore radius of 1.0 μm
7 ”, φ52.5 / φ42.5 were impregnated with Sb in the same manner as in Example 1 to prepare.

[II] Sliding Performance Test These samples of Examples 1 to 4 and Comparative Examples 1 and 2 were molded into the shape shown in FIG. 4 and comparatively evaluated by a sliding performance tester under the same conditions.

(B) The test conditions are shown below. Tester Use mechanical seal tester Fluid pressure 10kgf / cm ² Fluid water Rotation speed 3600rpm Mating material SiC test time 100hr Fluid temperature RT to 30 ℃ Test product size φ52.5 / φ42.5 Balance ratio 1.22

(B) Test results are shown in Table 1.

[0045]

[Table 1]

[III] Physical Property Measurement Test The physical properties of the composite material of Example 1, particularly the fluid sealing ability, were measured. (A) Table 2 shows the results of the physical property test.

[0047]

[Table 2]

(B) Effect of antimony impregnation on sealing property Pore radius before impregnation with antimony is 1.5 μm. Average 1.5μ
m: shown in FIG. Pore radius after antimony impregnation. Hardly measured. : As shown in FIG.

(C) Consideration It has been found that the antimony impregnation improves hardness and strength, almost eliminates pores remaining in the carbon substrate, and improves sealing performance.

[IV] Micrograph of silicified portion and surface composition The component composition of the silicified portion was investigated by the surface analysis method (image integration method by computer).

(1) Pretreatment The silicified portion of the sample of Example 1 was embedded in MMA (methylmethacrylate) and then polished, and then C was vapor-deposited on the polished surface.

(2) Measurement conditions Acceleration voltage 20 KV Sample current 0.6 nA Measurement time 200 sec Equipment used EMAX-2700 (manufactured by Horiba)

(3) Results A surface analysis photograph of Si is shown in FIG. 2 Area ratio

[0054]

[Table 3]

The portion which is not silicified has no SiC component,
Only C and Sb.

[0056]

[Examples 4 to 8] Examples of applications of the composite material of the present invention are shown in Figs.
Shown in The thick line display area (1) shows the silicified part
The other shaded portions (2) indicate the portions not subjected to the silicidation treatment.

However, FIG. 4 is a mechanical seal, FIG. 5 is a bearing, FIG. 6 is a shaft axis, FIG. 7 is a brake disc, and FIG.
Shows a piston cylinder, and FIG. 9 shows a case where it is applied to an annular sealing sliding member for a ball valve.

[0058]

As described above, as a result of comparison with existing materials which are widely used as mechanical sealing materials at present, for example, those in which a carbon substrate is impregnated with resin or those in which a carbon substrate is simply impregnated, the impermeability is good and Very excellent characteristic values were obtained in wear resistance. This is an extremely good material for use as a sliding sealing member such as a mechanical seal and a bearing, and can significantly improve the durability and reliability of the device, and the present invention is very useful industrially. .

[0059]

[Brief description of drawings]

[0060]

[Figure 1]

Pore radius measurement result of the composite material before antimony impregnation.

[0062]

FIG. 2

Measurement result of the pore radius of the composite material after impregnated with antimony.

[0064]

FIG. 3

Surface analysis photograph

[0066]

FIG. 4

Explanatory drawing showing an example in which the composite material of the present invention is applied to a mechanical seal member.

[0068]

[Figure 5]

Explanatory drawing showing an example in which the composite material of the present invention is applied to a bearing member.

[0070]

[Figure 6]

Explanatory drawing showing an example in which the composite material of the present invention is applied to a shaft member.

[0072]

[Figure 7]

Explanatory drawing showing an example in which the composite material of the present invention is applied to a brake disc member.

[0074]

FIG. 8

Explanatory drawing showing an example in which the composite material of the present invention is applied to a piston cylinder member.

[0076]

[Figure 9]

Explanatory drawing showing an example in which the composite material of the present invention is applied to a ball valve member.

[0078]

[Explanation of symbols]

 1-Silicated portion 2-Silicated portion

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 13, 1993

[Procedure Amendment 1]

[Document name to be corrected] Drawing

[Name of item to be corrected] Figure 3

[Correction method] Change

[Correction content]

[Figure 3] ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 25, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0053

[Correction method] Change

[Correction content]

(3) Results A surface analysis photograph of Si is shown in FIG. However, the white part in Figure 3
The SiC quality portion and the shaded portion indicate the carbonaceous portion. 2 Area ratio

[Procedure Amendment 2]

[Document name to be corrected] Drawing

[Name of item to be corrected] Figure 3

[Correction method] Change

[Correction content]

[Figure 3]

[Procedure amendment]

[Submission date] September 20, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel composite material, particularly a composite material suitable as a member for sliding sealing, a method for producing the same, and its use.

More specifically, a novel carbon-silicon carbide-metal composite material obtained by locally silicifying the surface layer portion of a predetermined portion (sliding portion) of a carbon base material and further impregnating the base material with a metal. , And a novel manufacturing method thereof and applications using the material.

Such a composite material is a sliding sealing member which is required to have wear resistance, for example, a bearing, a shaft shaft, a piston cylinder inner wall, a piston ring, a thrust plate, a valve sliding portion component, a vane, a mechanical seal. It is applied to members, etc.

[0004]

2. Description of the Related Art Conventionally, carbon base materials have been widely used for sliding sealing members, but in order to improve the hardness and wear resistance of the carbon base materials, their surface is made harder and more wear resistant. It is necessary to convert and modify it to a silicon carbide having a high quality.

In such a case, it is not always necessary to modify the entire surface of the carbon base material to silicon carbide, and it is possible to selectively and locally modify only a sliding portion with particularly heavy wear, that is, only a predetermined portion. It is often enough.

The method of coating the surface of a carbon substrate with silicon carbide is generally well known, and it is roughly classified into a chemical vapor deposition method and a conversion method.

The chemical vapor deposition method (CVD method) is a method in which silicon carbide is generated by utilizing thermal decomposition and chemical reaction of a silicon compound and is deposited on the surface of a carbon base material. Since this method uses a carbon material as a base material that can be easily cut, it is easy to manufacture a sliding material having a complicated shape, and the obtained silicon carbide coating layer is also highly pure and dense. However, there is a serious drawback in that the coating layer is weakly bonded to the substrate and the coating layer is easily peeled off when subjected to the action of repeated mechanical or thermal stress.

On the other hand, in the conversion method (CVR method), by reacting silicon dioxide with carbon or silicon, the generated silicon monoxide gas is directly reacted with carbon on the surface of the carbon substrate to form a coating made of silicon carbide. This is a method of forming a layer, and for example, there is JP-A-1-264969. The silicon carbide coating layer obtained by this method has a strong bond with the carbon substrate, but is inferior in terms of denseness.

This is because half of the carbon atoms become carbon monoxide gas and scatter due to the reactions of [Chemical Formula 1] and [Chemical Formula 2], and as a result, the coating layer has a porosity almost equal to that of the carbon substrate. growing. Therefore, in order to use it in a portion where airtightness and impermeability are required, it is necessary to impregnate a thermosetting resin or the like to improve the airtightness of the base material.

[0010]

Embedded image

[0011]

Embedded image

However, as described above, both the vapor deposition method and the conversion method require very special equipment, and even unnecessary portions are covered, so that the material becomes high in cost. Therefore, a method of covering a portion of the carbon base material that does not need to be converted to silicon carbide by using a special jig or an inert powder is disclosed in JP-A-56-120584 and JP-A-56-120584. It is proposed in Japanese Patent Publication No. 57-7880. Further, a method of forming a groove on the surface of a carbon base material, applying Si to the portion and heat-treating it to convert it into silicon carbide is also disclosed in JP-A-61-1369.
Although proposed in No. 61, there are drawbacks that the operation is complicated, the workability is poor, and the cost is high.

More specifically, in the above-mentioned two known examples in which the carbon substrate is partially converted into silicon carbide, the coating area is reduced, and the CVD method or the CV method is used.
Since the silicon carbide is formed by the R method, the coating layer is easily peeled off or becomes porous, and the above-mentioned defects remain. Further, in the known example in which Si is placed, it is difficult to say that the operation itself is extremely complicated and extremely practical, and the obtained product has a melt of Si adhered to the surface thereof, and it is difficult to remove it. It's not easy.

Further, the carbon base material as it is generally does not have a perfect sealing property. This is because graphite is generally produced by sintering fine carbon particles and fine pores remain.

As means for the sealing property and mechanical strength of such a porous carbon substrate, a resin is usually provided in the pores of the substrate,
Means for impregnating and filling pitch, tar, inorganic material, metal, etc. are known.

[0016] Such a porous carbon substrate may require mechanical strength and impermeability when it is used as a sliding sealing member. Therefore, when the thermosetting resin described above is used for the purpose of sealing, it is porous,
When impregnated, the resin content becomes high, a large amount of volatile solution contained in the contained resin is generated in the curing step after impregnation, fine pores are formed, and the resin causes heat shrinkage due to curing. , Once again, fine pores are generated, and the desired impermeability cannot be obtained by one treatment of impregnation and curing.
It becomes necessary to repeat curing.

Also, due to the shrinkage of the resin when it is cured, the graphite base material, which is a product, likewise shrinks and its dimensions change greatly.
Further, since the resin is stuck to the outer peripheral portion of the product due to the resin being wiped out, it is necessary to process the outer periphery again.

[0018]

The problem to be solved by the present invention is to eliminate the drawbacks of the above-mentioned conventional sliding sealing materials of this kind.

[0019]

According to the present invention, as a result of experiments under various conditions, a carbon substrate, preferably having an average pore radius of 0.
A carbon base material of 5 μm or more is processed into a product shape and suspended and mixed only in a necessary portion with a solution of silicon powder (Si) and a resin, particularly polyamide imide, polyvinyl alcohol, polyamide resin having a low residual carbon rate. Slurry is applied, dried, hardened, and the carbon base material and molten silicon are reacted at a high temperature of 1500 ° C. or higher to locally apply S to a target portion.
By converting to iC and further impregnating with metal,
It was completed by applying a novel carbon silicidation technology that can solve all the problems of conventional sliding sealing materials as a constituent element.

[0020]

The function and structure of the present invention will be described in more detail.

(1) The method for producing the carbon base material used in the present invention may be carried out by using an ordinary carbon material production method. Examples of the carbon base material used here include general graphite materials and isotropic materials. To be It is desirable to use a carbon base material having an average pore radius of 0.5 μm or more processed into a product shape. If the average pore radius of the carbon substrate is less than 0.5 μm, the slurry in which silicon and resin are mixed or the molten metal silicon tends to be difficult to permeate into the pores. In the present invention, only the sliding portion is locally S
By providing iC, adjusting the ratio of carbon and SiC, and further impregnating a metal, a composite material having good wear resistance, corrosion resistance, heat resistance, and further excellent sealing performance is provided.

(2) As the resin used, a resin having a high film-forming property and a low residual carbon rate, for example, a resin selected from polyamide imide, polyvinyl alcohol and polyamide resin is particularly preferably used. Among them, polyamideimide is more preferable, and it is dissolved in a solvent such as dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl-2pyrrolidone.

(3) This solution has an average particle size of about 30-50.
A silicon powder (Si) of μm is mixed and dispersed to obtain a slurry.

(4) It is possible to convert only the necessary portion to SiC by locally applying the slurry to a desired portion of the carbon base material by a suitable means such as brush coating or hand coating. .

(5) After that, it is dried and cured at about 300 ° C. for 2 hours. The solvent evaporates in this step.

(6) The material obtained as described in (1) to (5) is heat-treated at a high temperature in an inert gas atmosphere or in a vacuum. Temperature rising rate is about 1550-160 at about 800 ° C / hr
Hold at 0 ° C for 20 minutes. The heating means is not particularly limited and may be any suitable means.

(7) In the carbon-SiC composite material thus obtained, since the carbide of the resin adheres to the surface of the carbon base material, it is removed.

(8) A metal impregnation is further applied to the manufacturing method of (1) to (7) to obtain impermeability, mechanical strength, heat resistance,
Improves wear resistance.

(9) Examples of the metal used for impregnation include Sn, Cu, Sb, Ag, Zn and alloys containing these as the main components.

As this metal, a metal or an alloy having a melting point of 200 ° C. or higher and hardly reacting with carbon to form a carbide is used. When the melting point is less than 200 ° C, heat resistance may not be imparted to the produced composite material.

A method of impregnating a carbon-SiC composite with a metal is as follows.
First, put the metal to be impregnated in the impregnating device, and then 1-5 Torr
It is heated under reduced pressure to dissolve the metal. Put the product prepared in the steps up to (7) in this, and 50-100kg / cm
² (The pressure is applied and held for 30 minutes or more to impregnate.

In the carbon-silicon carbide-metal composite material obtained by the present invention, a coating layer of silicon carbide is formed on a predetermined portion (sliding surface) of a carbon base material, and the entire surface thereof (the carbon base material and the coating material is coated). Both of the silicon carbide layers are of metal-impregnated structure. Therefore, the sealing property is extremely high and the sliding property is also very excellent. In addition, since the silicon carbide layer, which is the coating layer, is also impregnated with metal, the synergistic effect of these causes the sliding characteristics of the sliding surface to be larger than that of the conventional partial silicon carbide coating. Become.

[0033]

EXAMPLES The present invention will be described in detail below with reference to examples. [I] Test sample

[0034]

Example 1 An isotropic graphite material having an average pore radius of 2 μm (SIC-12 manufactured by Toyo Tanso Co., Ltd.) was used as φ52.2 / φ42.
It processed into the product shape of 5. On the other hand, 100 parts by weight of polyamide-imide resin (Al-10, manufactured by Ohara Kako) was dissolved in N-methyl-2pyrrolidone to prepare a 20% solution. SiC powder (average particle size of 50 μm manufactured by Wako Pure Chemical Industries) was added to this solution 6 times.
0 parts by weight was mixed to obtain a slurry.

This slurry was applied to a required portion of the carbon substrate and then cured at 300 ° C. in a dryer.

Further, the temperature was raised to 1600 ° C. in a vacuum furnace, held for 30 minutes, cooled, and then taken out.

Further, Sb is melted in the impregnating device to obtain SiC.
After soaking the semi-finished product, N ₂ gas is introduced and 100k
It was kept at gf / cm ^{2 for} 30 minutes, cooled, and then taken out.
The impregnation rate of Sb was 66% (weight).

[0038]

[Example 2] "ISEM-" having an average pore radius of 1.5 µm
1 "(manufactured by Toyo Tanso Co., Ltd.) was used, and the following manufacturing method was performed in the same manner as in Example 1 to impregnate SiC with 2.0 mm. The impregnation conditions were the same, and Sn was used as the impregnation metal.

[0039]

Example 3 “ISO-5 having an average pore radius of 0.5 μm”
0 "(manufactured by Toyo Tanso Co., Ltd.) to form a SiC layer of 0.5.
mm formed. The impregnation method was the same, and Cu was used as the impregnation metal.

[0040]

[Comparative Example 1] "KC-1" having an average pore radius of 1.0 μm
7 "(manufactured by Toyo Tanso Co., Ltd.), φ52.5 / φ42.5
What was impregnated with phenol resin was prepared.

[0041]

[Comparative Example 2] "KC-1" having an average pore radius of 1.0 μm
7 ", φ52.5 / φ42.5 required portion is the first embodiment
In the same manner as above, an Sb-impregnated product was prepared.

[II] Sliding Performance Test These samples of Examples 1 to 4 and Comparative Examples 1 and 2 were molded into the shapes shown in FIG. 4 and comparatively evaluated with a sliding performance tester under the same conditions.

(B) The test conditions are shown below. The tester mechanical seal tester utilizing fluid pressure 10 kgf / cm ² fluid water rpm 3600rpm mating material SiC test time 100hr fluid temperature RT～30 ° C. Specimen dimensions φ52.5 / φ42.5 balance ratio 1.22

(B) Test results are shown in Table 1.

[0045]

[Table 1]

[III] Physical property measurement test The physical properties of the composite material of Example 1, particularly the fluid sealing ability, were measured. (A) Table 2 shows the results of the physical property test.

[0047]

[Table 2]

(B) Effect of antimony impregnation on sealing property Pore radius of 1.5 μm before antimony impregnation. 1.5μ on average
m: shown in FIG. Pore radius after antimony impregnation. Hardly measured. : As shown in FIG.

(C) Consideration It has been found that the antimony impregnation improves hardness and strength, almost eliminates pores remaining in the carbon substrate, and improves sealing performance.

[IV] Micrograph of silicified portion and surface composition The composition of the silicified portion was examined by the surface analysis method (image integration method by computer).

(1) Pretreatment The silicified portion of the sample of Example 1 was embedded in MMA (methylmethacrylate) and then polished, and then C was vapor-deposited on the polished surface.

(2) Measurement conditions Acceleration voltage 20KV Sample current 0.6nA Measurement time 200sec Equipment used EMAX-2700 (manufactured by Horiba)

(3) Results A surface analysis photograph of Si is shown in FIG. However, the white part in Figure 3
The SiC quality portion and the shaded portion indicate the carbonaceous portion. 2 Area ratio

[0054]

[Table 3]

The portion which is not silicified has no SiC component,
Only C and Sb.

[0056]

[Examples 4 to 8] Examples of applications of the composite material of the present invention are shown in Figs.
Shown in The thick line display area (1) shows the silicified part
The other shaded portions (2) indicate the portions not subjected to the silicidation treatment.

However, FIG. 4 is a mechanical seal, FIG. 5 is a bearing, FIG. 6 is a shaft axis, FIG. 7 is a brake disc, and FIG.
Shows a piston cylinder, and FIG. 9 shows a case where it is applied to an annular sealing sliding member for a ball valve.

[0058]

As described above, as a result of comparison with existing materials which are widely used as mechanical sealing materials at present, for example, those in which a carbon substrate is impregnated with resin or those in which a carbon substrate is simply impregnated, the impermeability is good and Very excellent characteristic values were obtained in wear resistance. This is an extremely good material for use as a sliding sealing member such as a mechanical seal and a bearing, and can significantly improve the durability and reliability of the device, and the present invention is very useful industrially. .

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Change

[Correction content]

[Brief description of drawings]

FIG. 1 is a result of measuring a pore radius of a composite material before being impregnated with antimony.

FIG. 2 shows the measurement result of the pore radius of the composite material after the impregnation with antimony.

[Figure 3] Area analysis diagram

FIG. 4 is an explanatory view showing an example in which the composite material of the present invention is applied to a mechanical seal member.

FIG. 5 is an explanatory view showing an example in which the composite material of the present invention is applied to a bearing member.

FIG. 6 is an explanatory view showing an example in which the composite material of the present invention is applied to a shaft member.

FIG. 7 is an explanatory view showing an example in which the composite material of the present invention is applied to a brake disc member.

FIG. 8 is an explanatory view showing an example in which the composite material of the present invention is applied to a piston cylinder member.

FIG. 9 is an explanatory view showing an example in which the composite material of the present invention is applied to a ball valve member.

[Explanation of Codes] 1 ... Siliconized part 2 ... Silicified part

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location F16C 33/04 7123-3J F16D 69/02 B F16J 9/26 C 15/34 Z F16K 5/06 H

Claims (11)

[Claims] 1. A carbon-silicon carbide-metal composite material obtained by subjecting a surface layer portion of a predetermined portion (sliding portion) of a carbon substrate to silicidation, and further impregnating the entire carbon substrate with a metal. 2. The composite material according to claim 1, wherein the metal to be impregnated is at least one of antimony, silver, tin, copper and an alloy containing at least one of these as a main component. 3. A method for producing a carbon-silicon carbide-metal composite material by subjecting a surface layer portion of a predetermined portion (sliding portion) of a carbon base material to a silicidation treatment and further impregnating the carbon base material with a metal. A composite material, characterized in that only a predetermined part to be silicidized is left, and the other part is covered with SiC to prevent contact with Si gas, and then the whole base material is impregnated with a metal component. Manufacturing method. 4. A solution containing (b) at least one of polyimide amide, polyvinyl alcohol, and polyamide resin in a material obtained by processing a carbon substrate having an average pore radius of 0.5 μm or more into a product shape. (C) A slurry in which metallic silicon powder is suspended is applied to a predetermined portion of the carbon substrate, dried, cured, and then calcined at 1500 ° C. or higher to partially silicify the metal. The method for manufacturing a composite material according to claim 3, wherein the composite material is impregnated. 5. A slide using a carbon-silicon carbide-metal composite material obtained by silicifying a surface layer portion of a predetermined portion (sliding portion) of a carbon base material, and further impregnating the whole carbon base material with a metal. Sealing member. 6. A mechanical seal member using a carbon-silicon carbide-metal composite material obtained by silicifying the surface of a predetermined portion (sliding portion) of a carbon base material and further impregnating the entire carbon base material with a metal. . 7. The member according to claim 5, which is a bearing in which only a portion in contact with the mating member is made into SiC and carbon of the base material is impregnated with a metal. 8. The member according to claim 5, which is a shaft shaft in which only a portion in contact with the mating member is made into SiC and carbon of the base material is impregnated with a metal. 9. The member according to claim 5, which is a brake disk in which only a portion in contact with a mating member is made into SiC, and carbon of the base material is impregnated with a metal. 10. The member according to claim 5, which is a piston ring in which only a portion in contact with the mating member is made into SiC, and carbon of the base material is impregnated with a metal. 11. The member according to claim 5, which is a valve sliding member in which only a portion in contact with the mating member is made into SiC, and carbon of the base material is impregnated with a metal.