JPH11322476A - Composite material having thermally sprayed layer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite material having thermally sprayed layers which are excellent in reaction resistance (powder-product-chemical-medicinal liquid-atmosphere), has impact resistance, creep resistance, spalling, respectively, wear resistance and low friction coefft. as well and have lightweightness, high strength and high reliability and a process for producing the same. SOLUTION: This composite material is constituted by forming the thermally sprayed layers on the surfaces of the fiber composite material 7 having the matrix consisting of yarn assemblies 6 which are three-dimensionally combined with yarns 2A, 2B contg. at least bundles 3 of carbon fibers and carbon component exclusive of the carbon fibers and are integrated so as not to separate the same from each other and Si-SiC-base materials 4A, 4B, 5A, 5B which are packed between the yarns 2A, 2B adjacent to each other in these yarn assemblies 6.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention mainly relates to a setter for sintering ferrite, a capacitor, etc., a sintering crucible for ceramic powders and compacts and a crucible for hot sulfuric acid, or a roll member strongly required to have high wear resistance. The present invention relates to a composite material having a sprayed layer to be used and a method for producing the same.

[0002]

2. Description of the Related Art SiC, S is used as a constituent member or a heat treatment member for semiconductors, ceramics, electronic components, vehicles, aircrafts, etc.
i ₃ N ₄ , Si—SiC, Al ₂ O ₃ —SiO ₂ , CaO,
Ceramics such as ZrO ₂ are widely and widely used. This is high temperature strength, corrosion resistance, far superior to metal materials,
This is because of its advantages such as abrasion resistance and low specific gravity and abundance of raw material resources.

However, ceramics are generally known to have low toughness and brittleness, and have a fracture energy of at most about 50 J / m ^2. Therefore, once cracks are formed, cracks easily occur. Even if ceramics having spalling resistance are selected to solve this problem, it has been difficult to sufficiently extend the life due to generation of microcracks. From the above, there is a problem that ceramics have low mechanical and thermal shock resistance and low reliability against destruction. In order to maintain the resistance of the ceramic (powder-product-chemical-chemical-atmosphere), ceramic coating is performed by a thermal spraying method. T. E. FIG. (Coefficient of thermal expansion), there was a problem that the coating formed on the substrate was easily peeled off.

As a means of overcoming the drawbacks of ceramics, a ceramic-based composite material (CMC) in which continuous ceramic fibers are composited has been used. This material has high strength and high toughness even at high temperatures, has excellent impact resistance and environmental resistance, can be lighter than ceramics, and has excellent workability. R & D is actively conducted mainly in Europe and the United States.

The above ceramic matrix composite material (CMC)
As a specific example, a C / C composite in which a matrix made of carbon is formed at intervals between carbon fibers arranged in two-dimensional or three-dimensional directions, and a formed body containing SiC fibers and SiC particles impregnated with Si. There are known SiC fiber reinforced Si-SiC composite materials and the like. Further, British Patent No. 1457775 discloses a treatment method in which a C / C composite is immersed in molten Si.
According to this method, it is presumed that a composite material in which C / C composite is impregnated with Si is produced.

[0006]

However, currently used C / C composites are used in a wide range of fields because of their high toughness, excellent impact resistance, and light weight and high strength. Since it is composed of carbon, it cannot be used at high temperatures in the presence of oxygen, and its use as a super heat-resistant structural material is limited. On the other hand, SiC
The fiber-reinforced Si-SiC composite is excellent in oxidation resistance, creep resistance, spalling resistance, etc., but the fiber surface is easily damaged, and the SiC fiber has lubricity with Si-SiC, etc. Poor in toughness compared to C / C composite, because the effect of drawing out between matrix and fiber is small.
For this reason, there is a problem that the impact resistance is low and it is not suitable for a structural material having a complicated shape or a thin portion.

Further, in a composite material in which Si is impregnated into a C / C composite disclosed in British Patent No. 1457775, a conventional C
/ C composite is used and has a structure in which many fine pores are present throughout. That is, as described in Example 1 of British Patent No. 1457775, carbon fibers are coated with a phenolic resin, and then placed in a mold so as to have a desired fiber direction and shape. After curing, the obtained molded body is released from the mold and heated to 800 to 900 ° C. under a nitrogen atmosphere to carbonize the phenol resin. In this way, a C / C composite having a structure in which fibers are oriented in a certain direction and are laminated is obtained.

In such a C / C composite, the phenol resin is carbonized to become a part of the carbon matrix. However, since the residual carbon ratio is about 50%, the C / C composite has a structure in which many fine pores are present throughout. When this C / C composite is immersed in molten Si and impregnated with Si,
Although Si penetrates in the vicinity of the surface, Si cannot penetrate all over the C / C composite, particularly the center thereof. Therefore, the disadvantages of the C / C composite as the material properties have not been solved yet. In addition, the molten S / C composite
When impregnated with i, the structure of the carbon fiber near the surface is broken by direct contact with the molten high-temperature Si,
As a result, there is a problem that impact resistance, strength, high lubricity, and wear resistance are lost.

The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to have excellent reactivity (powder-product-chemical-chemical-atmosphere), impact resistance, and impact resistance. An object of the present invention is to provide a composite material having a lightweight, high-strength, and high-reliability thermal spray layer, which has both creep properties, spalling resistance, wear resistance, and a low coefficient of friction, and a method for producing the same.

[0010]

That is, according to the present invention, yarns containing at least a bundle of carbon fibers and a carbon component other than carbon fibers are three-dimensionally combined and integrated so as not to be separated from each other. Yarn assembly,
A composite having a thermal spray layer, wherein a thermal spray layer is formed on a surface of a fiber composite material having a matrix made of a Si-SiC-based material filled between adjacent yarns in the yarn aggregate. Materials are provided.

In the present invention, the matrix preferably has a silicon carbide phase generated along the surface of the yarn, and the matrix has a silicon phase composed of silicon. More preferably, a silicon carbide phase is formed between the phase and the yarn. Further, the matrix may have a gradient composition in which the content ratio of silicon increases as the distance from the surface of the yarn increases. Furthermore, the yarn aggregate includes a plurality of yarn arrays, and each yarn array is formed by two-dimensionally arranging the plurality of yarns substantially in parallel, and each yarn array is stacked. It is preferable that a yarn aggregate is formed by this. In this case, it is preferable that the longitudinal directions of the yarns in the adjacent yarn arrays cross each other.

In the present invention, the matrix forms a three-dimensional network structure by being continuous with each other in the fiber composite material. More specifically, the matrices are two-dimensionally arranged substantially parallel in each yarn array, and the matrices generated in each adjacent yarn array are continuous with each other, whereby the matrix is formed. It is preferable to form a three-dimensional lattice. Also,
The thickness of the sprayed layer is preferably from 10 to 2000 μm, and the main components of the sprayed layer are Al ₂ O ₃ , ZrO ₂ , M
g0, CaO, and is preferably any one of TiO _2.

Further, according to the present invention, a carbon fiber bundle is produced by including a powdery carbon component and an organic binder component that finally become a matrix in the carbon fiber bundle, and then the carbon fiber bundle is Forming an intermediate material by forming a plastic coating around it, then forming the intermediate material into a yarn, and optionally into a sheet,
After laminating a predetermined amount and molding to obtain a molded body, or after sintering this molded body to obtain a sintered body, this molded body or sintered body and Si, in an inert gas atmosphere, 1100-1
By maintaining the temperature at 400 ° C. and then raising the temperature of the compact or sintered body and Si to a temperature of 1450 to 2500 ° C., Si- is introduced into the open pores of the compact or sintered body.
A method for producing a composite material having a thermal spray layer, characterized in that a fiber composite material is produced by impregnating with a SiC-based material, and then a thermal spray material is sprayed on the surface of the fiber composite material to form a thermal spray layer. Is done.

[0014] In the above-described manufacturing method, the molded body or the sintered body and Si are heated at a temperature of 1100 to 1400 ° C.
It is preferable that the pressure is maintained at 10 hPa for 1 hour or more, and at that time, the inert gas is controlled to flow at 0.1 normal liter (NL) or more per 1 kg of the total weight of the compact or sintered body and Si. , Compact or sintered body and Si
Is 1450-2500 under a pressure of 0.1-10 hPa.
Preferably, the temperature is raised to a temperature of ° C. Further, after calcining the fiber composite material at 200 to 800 ° C. in an air atmosphere, it is preferable to spray a thermal spray material on the surface of the fiber composite material to form a thermal spray layer.
Preferably, it contains any of ₂ O ₃ , ZrO ₂ , MgO, CaO, and TiO ₂ . Further, at the time of thermal spraying, thermal spraying may be performed after plating of Ni or the like.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The composite material of the present invention is a yarn in which yarns containing at least a bundle of carbon fibers and a carbon component other than carbon fibers are three-dimensionally combined and integrated so as not to be separated from each other. Aggregate and Si-S filled between adjacent yarns in this yarn aggregate
A sprayed layer is formed on the surface of a fiber composite material having an iC-based matrix.

The composite material of the present invention can impart toughness to a fiber composite material by using a C / C composite as a base material, so that the composite material has excellent impact resistance, light weight, high strength, high lubricity, It can be a wear-resistant material. Therefore, the disadvantage of low impact resistance of the SiC fiber reinforced Si—SiC composite can be overcome, and the composite can be used for a structural material having a complicated shape or a thin portion. Further, since the C / C composite is manufactured so as to have continuous open pores in the C / C composite, the Si—SiC-based material impregnated and formed into the pores is
Take a continuous structure and a three-dimensional network structure. Therefore, no matter which part is cut out, it has higher wear resistance than the C / C composite used as the base material, and also maintains the lubricity of the original C / C composite. Further, by arranging a layer made of a Si-SiC material on the surface of the base material made of the C / C composite, the fiber composite material is given oxidation resistance, creep resistance and spalling resistance.

The composite material of the present invention, by forming a thermal spray layer on the surface of the fiber composite material, inherits the excellent properties of the fiber composite material, and further has a resistance (powder-product-drug-) by the thermal spray layer. (Chemical liquid-atmosphere) reactivity is imparted, and the low oxidation resistance of the C / C composite used as a base material can be overcome. Further, since the low hardness, which is a problem of the fiber composite material, can be improved, the abrasion resistance can be further improved. Further, since the sprayed layer can be firmly fixed to the surface of the fiber composite material, for example, the surface can be roughened or
Even if the film is heated at 200 to 800 ° C. in an oxidizing atmosphere for forming an O ₂ film, it can be processed into a stable state. From the above, it is possible to use at high temperature even in the presence of oxygen, and to prevent the reaction with the partner material,
It can be suitably used as a super heat resistant structural material.

Hereinafter, a fiber composite material which is a basic material used for the composite material of the present invention will be described. This is a material of a new concept based on a so-called C / C composite, with an improved basic configuration.

Usually, hundreds to tens of thousands of carbon fibers having a diameter of about 10 μm are bundled to form a fiber bundle (yarn),
These fiber bundles are arranged in a two-dimensional direction to form a unidirectional sheet (UD
Sheets) and various cloths, or by laminating the sheets and cloths in a three-dimensional direction to form a preform (fiber preform) having a predetermined shape, and the inside of the preform is formed by a CVI method. (Chemical Vapor Infiltrat
ion: chemical vapor impregnation method) or inorganic polymer impregnation sintering method, etc.
C composites are known.

This fiber composite material has a C / C
Since the composite is used and is manufactured by the specific manufacturing method described below, the structure of the carbon fiber is
It has a great feature that it is held without being destroyed. As described in the above-mentioned British Patent No. 1,457,575, a fiber composite material in which a C / C composite is impregnated with silicon is known. However, in this material, the structure of carbon fibers is destroyed. The impact resistance, strength, high lubricity, and abrasion resistance of the / C composite were lost. On the other hand, in the fiber composite material used in the present invention, a flexible coating made of a plastic such as a thermoplastic resin is formed at least around the carbon fiber bundle to obtain a flexible intermediate material, which is formed into a yarn. Then, in some cases, since it is subjected to a specific treatment of laminating and heating and molding in a sheet shape, carbon particles other than high-temperature molten Si and carbon fibers, organic binders, plastic coatings are thermally decomposed. It is presumed that the highly active carbon produced first reacts in contact and does not directly contact the carbon fiber bundle,
The carbon fiber structure is not destroyed. Moreover, the fiber composite material used in the present invention has a microstructure in which a matrix made of a Si-SiC-based material is filled between adjacent yarns in the yarn aggregate.

In the present invention, the term “Si—SiC-based material” is a general term for a material containing silicon and silicon carbide as main components. In the present invention, the C / C composite or its molded product is impregnated with silicon. At this time, the silicon reacts mainly with carbon components other than carbon fibers or residual carbon in the composite, and is partially carbonized. Therefore, partially carbonized silicon is generated between the yarn aggregates. This matrix may contain several intermediate phases, from a silicon phase with almost pure silicon remaining to a substantially pure silicon carbide phase. In other words, this matrix is typically composed of a silicon phase and a silicon carbide phase, but between the silicon phase and the silicon carbide phase, the Si-based material in which the carbon content is graded varying based on silicon. It may include a SiC coexisting phase. The Si-SiC-based material refers to such S
In the i-SiC series, it is a general term for materials in which the concentration of carbon changes from 0 mol% to 50 mol%.

[0022] The fiber composite preferably comprises a matrix in which the matrix is formed along the surface of the yarn. In this case, the strength of each yarn itself is further improved, and it is difficult to break.

Further, the fiber composite material preferably includes a silicon phase in which the matrix is made of silicon,
A silicon carbide phase is generated between the silicon phase and the yarn. In this case, the surface of the yarn is strengthened by the silicon carbide phase, and the central portion of the matrix is made of a silicon phase having a relatively low hardness, so that microscopic stress dispersion is further promoted.

Further, the fiber composite material preferably has a gradient composition in which the content ratio of silicon increases as the matrix moves away from the surface of the yarn. Further, in this fiber composite material, preferably, the yarn aggregate includes a plurality of yarn arrays, and each yarn array is formed by two-dimensionally arranging the plurality of yarns substantially in parallel. Each yarn array is laminated to form a yarn aggregate. As a result, the fiber composite material has a laminated structure in which a plurality of yarn arrays are laminated in one direction.

In this case, it is particularly preferable that the longitudinal directions of the yarns in adjacent yarn arrays cross each other. Thereby, the dispersion of the stress is further promoted. The longitudinal directions of the yarns in adjacent yarn arrangements are particularly preferably orthogonal.

Preferably, the matrix is continuous with each other in the fiber composite material to form a three-dimensional network structure. In this case, it is particularly preferable that the matrices are two-dimensionally arranged substantially in parallel in each yarn array, and the matrices generated in each adjacent yarn array are continuous with each other, whereby the matrix is formed. It forms a three-dimensional lattice.

The gap between adjacent yarns is 10
Although 0% matrix may be filled, the case where the matrix is partially filled in the yarn gap is also included.

The carbon component other than the carbon fiber in the yarn is
Preferred is carbon powder, and particularly preferred is graphitized carbon powder.

FIG. 1 is a schematic perspective view for explaining the concept of a yarn aggregate, and FIG. 2A is IIa-II in FIG.
FIG. 2B is a sectional view taken along the line a, and FIG. 2B is a sectional view taken along the line IIb-IIb in FIG. FIG. 3 is a partially enlarged view of FIG.

The skeleton of the fiber composite material 7 is constituted by the yarn aggregate 6. The yarn aggregate 6 is formed by vertically stacking the yarn arrays 1A, 1B, 1C, 1D, 1E, and 1F. In each yarn array, the yarns 3 are two-dimensionally arranged, and the longitudinal directions of the yarns are substantially parallel. The longitudinal direction of each yarn in each vertically arranged yarn array is orthogonal. That is, the longitudinal direction of each yarn 2A of each yarn array 1A, 1C, 1E is parallel to each other, and each yarn array 1B, 1E.
D and 1F are orthogonal to the longitudinal direction of each yarn 2B.

Each yarn is composed of a fiber bundle 3 made of carbon fiber and a carbon component other than carbon fiber. The yarn assembly 6 having a three-dimensional lattice shape is formed by stacking the yarn arrays. Each yarn is crushed during a pressure forming process as described below, and has a substantially elliptical shape.

In each yarn array 1A, 1C, 1E, a matrix 8A is provided between adjacent yarns.
And each matrix 8A extends along and parallel to the surface of the yarn 2A. In each of the yarn arrays 1B, 1D, and 1F, the gap between adjacent yarns is filled with a matrix 8B, and each matrix 8B extends along the surface of the yarn 2B and parallel thereto.

In the present example, the matrices 8A, 8B
Respectively, a silicon carbide phase 4A covering the surface of each yarn,
4B and Si-SiC-based material phases 5A and 5B having a lower carbon content than silicon carbide phases 4A and 4B. Silicon may be partially contained in the silicon carbide phase. In this example, silicon carbide phases 4A and 4B are also generated between yarns 2A and 2B that are vertically adjacent to each other.

Each of the matrices 8A and 8B is elongated, preferably linear, along the surface of the yarn, respectively, and each of the matrices 8A and 8B is orthogonal to one another. Then, the matrix 8A in the yarn arrays 1A, 1C, and 1E and the yarn array 1 orthogonal to the matrix 8A
The matrix 8B in B, 1D, and 1F is continuous at the gap between the yarns 2A and 2B, respectively. As a result, the matrices 8A and 8B form a three-dimensional lattice as a whole.

FIG. 4 is a partial sectional perspective view schematically showing a main part of a fiber composite material according to another embodiment. In this example, a silicon carbide phase does not substantially exist between each of the yarns 2A and 2B that are vertically adjacent to each other. In each yarn arrangement, a matrix 8 is provided between adjacent yarns 2A and 2A or between yarns 2B and 2B, respectively.
A and 8B are formed. The form of the matrices 8A and 8B is the same as in the examples of FIGS. 1 to 3 except that there is no silicon carbide phase between the vertically adjacent yarns. Each of the matrices 8A and 8B includes a silicon carbide phase 5C generated in contact with the surface of the yarns 2A and 2B, and a Si-SiC-based material phase 4C generated separately from the yarn inside the silicon carbide phase 5C. ing.

The Si—SiC-based material phase preferably has a gradient composition in which the carbon concentration decreases as the distance from the yarn surface increases, or
It is preferable that it is composed of a silicon phase.

As shown in FIG. 5A, the fiber composite material 11 of the present invention comprises a C / C composite 15 and a fiber composite material layer formed by impregnating the surface of the C / C composite 15 with silicon. 13 is preferably provided, and a silicon layer 14 may be formed on the fiber composite material layer 13. In addition, 12 is C / before impregnation with silicon.
Shows the range of the C composite body. Further, as shown in FIG. 5B, it is preferable that the entire member 16 is formed of the fiber composite material of the present invention.

When the fiber composite material layer 13 is provided,
The thickness is preferably from 0.01 to 1 mm.
Further, it is preferable that the Si concentration in the fiber composite material layer increases from the carbon fiber surface toward the outside.

If the fiber composite material used in the present invention contains 10 to 70% by weight of carbon fibers, for example, other than carbon such as boron nitride, boron, copper, bismuth, titanium, chromium, tungsten, molybdenum, etc. It may contain an element.

Here, the thickness of the fiber composite material layer 13 obtained by impregnating the base material with the Si—SiC-based material will be described in further detail. In FIG. 2A, for example, in the relationship between the carbon fiber bundle 3, the silicon carbide phase 4B, and the silicon phase 5B, the C / C composite 15 is formed on the carbon fiber bundle 3 in FIG.
Corresponds to silicon carbide phase 4B, and silicon layer 14 corresponds to silicon phase 5B. Here, the layer 13 preferably has a thickness of 0.01 mm or more, more preferably 0.05 mm or more. The maximum thickness is about 1 mm. At this time, the Si concentration in the layer 13 is 0 from the portion of the carbon fiber bundle 3 to the portion of the silicon phase 5B through the silicon carbide phase 4B.
It is preferable to form them so as to be inclined in the range of / 100 to 90/100. Further, for example, the slope of the Si concentration from a macroscopic viewpoint when a block having a thickness of 200 mm is assumed will be described in detail. The present invention provides a method for manufacturing a laminate of carbon fiber bundles using Si.
Impregnated with Si, the center of the block having a thickness of 200 mm of Si has a low concentration, and the surface layer can have a high concentration. The most preferable form for this purpose is to form a plurality of preformed sheets comprising preformed yarns having different binder pitches so that the open porosity of the C / C composite molded body or sintered body decreases from the surface toward the inside. This is realized by arranging and molding such that the binder pitch increases from the inside toward the surface layer side. By doing so, in the case of FIG. 2A, the silicon carbide phase 4A of the yarn array 1A layer> the yarn array 1B
Silicon carbide phase 4A> yarn arrangement 1C layer silicon carbide phase 4A> yarn arrangement 1D layer silicon carbide phase 4A, so that the SiC concentration (= Si concentration) decreases, and the Si concentration decreases. To go. Therefore, if you look at the material macroscopically, up to 1
The Si concentration is inclined within a thickness of about 00 mm. The Si concentration is 90 / 100-0 / 0 from the surface to the inside.
It is preferable to form it so as to be inclined in the range of 100.

As described above, the fiber composite material used in the present invention contains one or more substances selected from the group consisting of boron nitride, boron, copper, bismuth, titanium, chromium, tungsten, and molybdenum. You may.

Since these substances have lubricity, C
By containing the base material made of the / C composite, the lubricating properties of the fibers can be maintained even in the part of the base material impregnated with the Si-SiC-based material, and a decrease in physical properties can be prevented.

For example, the content of boron nitride is C
For 100% by weight of base material composed of / C composite,
Preferably it is 0.1 to 40% by weight. If the content is less than 0.1% by weight, the effect of imparting lubricity by boron nitride cannot be sufficiently obtained, and if it exceeds 40% by weight, the brittleness of boron nitride appears in the composite material.

The fiber composite material used in the present invention can be preferably produced by the following method. That is, a carbon fiber bundle is produced by incorporating a powdery binder pitch and coke, which eventually become a matrix, into the carbon fiber bundle, and further including a phenol resin powder or the like as necessary. A flexible coating made of a plastic such as a thermoplastic resin is formed around the carbon fiber bundle to obtain a flexible intermediate material. This flexible intermediate material is formed into a yarn (Japanese Patent Application No. 63-231791), laminated in a required amount, and then hot-pressed at 300 to 2000 ° C.
By molding under the condition of 500 kg / cm ² ,
Obtain a molded body. Alternatively, this molded body is optionally
Carbonized at 00 to 1200 ° C and graphitized at 1500 to 3000 ° C to obtain a sintered body.

[0045] The carbon fiber is made from petroleum pitch or coal tar pitch as a raw material, and pitch-based carbon fiber and acrylonitrile (co) polymer fiber obtained by adjusting spinning pitch, melt-spinning, infusibilizing and carbonizing, and flame-retarding acrylonitrile (co) polymer fiber. Any of PAN-based carbon fibers obtained by carbonization may be used.

As the organic binder necessary for forming the matrix, a thermosetting resin such as a phenol resin or an epoxy resin, tar, pitch, and the like are used. These include cokes, metals, metal compounds, inorganic and organic compounds, and the like. May be included. Some of the organic binder may serve as a carbon source.

Next, the compact or sintered compact produced as described above and Si are held for 1 hour or more in a temperature range of 1100 to 1400 ° C. and a furnace pressure of 0.1 to 10 hPa.
Preferably, at this time, 0.1 NL (normal liter: 1200) per kg of the total weight of the molded body or the sintered body and Si.
(In the case of 0 ° C. and a pressure of 0.1 hPa, which corresponds to 5065 liters) or more, an Si—SiC layer is formed on the surface of the compact or sintered body while flowing an inert gas of not less than 5065 liters. Then the temperature 1450
To 2500 ° C., preferably 1700 to 1800 ° C., and Si-SiC is introduced into the open pores of the compact or sintered body.
The system material is melted and impregnated. In this process, when a molded body is used, the molded body is also baked to produce a fiber composite material.

A molded body or a sintered body and Si are mixed with 1100
The temperature is maintained at 1400 ° C. and the pressure of 0.1 to 10 hPa for 1 hour or more, and at that time, the inert gas is 0.1 NL or more, preferably 1 NL or more per 1 kg of the total weight of the compact or sintered body and Si, More preferably, it is desirable to control so as to flow at 10 NL or more.

As described above, by setting the inert gas atmosphere at the time of firing (that is, the stage before melting and impregnation of Si), the generated gas such as CO due to the change of the inorganic polymer or the inorganic substance into ceramic is converted into the firing atmosphere. By further removing and preventing contamination of the firing atmosphere from the outside due to O ₂ or the like in the air, the porosity of the fiber composite material obtained by subsequently melting and impregnating Si can be kept low.

In addition, the molded body or the sintered body is contacted with Si,
When impregnating, the ambient temperature is 1450-2500 ° C,
Preferably, the temperature is raised to 1700 to 1800 ° C. In this case, the firing furnace internal pressure is preferably in the range of 0.1 to 10 hPa. Further, the atmosphere in the furnace is preferably an inert gas or Ar gas.

As described above, when a flexible intermediate material is used and combined with silicon impregnation and melting, elongated voids remain in the gaps between the yarns in the molded body or sintered body, and the elongated voids remain along the elongated voids. Silicon penetrates deep into the sintered body or molded body. During this infiltration process, the silicon reacts with the carbon of the yarn and gradually carbonizes from the yarn surface side to produce a fiber composite material.

[0052] Si-Si in the entire fiber composite material
The concentration gradient of the C-based material is adjusted based on the open porosity and the pore diameter of the compact or sintered body. For example, when the concentration of the Si-SiC-based material is 0.01 to 10 mm from the surface layer of the fiber composite material, and the concentration of the Si-SiC-based material is higher than that of other places, the open porosity in the desired high-concentration portion of the compact or sintered body is 5 to 5. 50%,
The average pore diameter is set to 1 μm or more, and the open porosity and the average pore diameter of the portion other than the desired high concentration are set to the high concentration portion or less.
Preferably, the open porosity in the desired high-concentration portion of the compact or sintered body is 10 to 50%, and the average pore diameter is 1
It is set to 0 μm or more, and the open porosity and the average pore diameter of the portion other than the desired high concentration are set to the high concentration portion or less. If the open porosity is less than 5%, the binder in the compact or sintered body is difficult to remove. This is because the process proceeds beyond the control range of other manufacturing method parameters such as time.

Further, in order to form the fiber composite material layer on the surface of the C / C composite, a molded body adjusted so that the open porosity at least in the vicinity of the surface becomes 0.1 to 30% during sintering is used. Is preferred.

In order to reduce the open porosity of the molded body or the sintered body from the surface toward the inside, a plurality of reformed sheets made of the reformed yarns having different binder pitches are formed from the inside to the surface layer side. This is carried out by arranging and molding such that the binder pitch increases toward.

When a gradient is provided in the silicon concentration in the fiber composite material layer, the sintered body is adjusted so that the open porosity near the surface decreases from the surface toward the inside, or at least the open pore near the surface. Using a compact adjusted so that the rate decreases from the surface toward the inside during sintering,
Manufacture of fiber composite materials.

The composite material of the present invention can be manufactured by forming a thermal spray layer on the surface of the fiber composite material produced as described above. FIG. 6 is a cross-sectional view showing an example of the composite material of the present invention.
A C / C composite 15; a fiber composite material layer 13 formed by impregnating the surface of the C / C composite 15 with silicon;
A silicon layer 14 is formed thereon and configured. And
The thermal spray layer 17 is formed on the silicon layer 14, which is the surface layer of the fiber composite material 11, to form the composite material of the present invention.

Next, the C / C composite used for the composite material of the present invention is a C / C composite having a C.C.
T. E. FIG. (Coefficient of thermal expansion) and C.I. T. E. FIG. Is in the range of 1: 1 to 1: 5, and the C.I. T. E. FIG. Is preferably 1 × 10 ⁻⁶ / ° C. to 5 × 10 ⁻⁶ / ° C. This is because simply spray coating the surface of a fiber composite material manufactured using a C / C composite as a base material, the C.I.
T. E. FIG. Is large, and C.I. T. E. FIG. This is because the difference causes the thermal sprayed layer to be easily peeled around the corners of the side surface of the base material in the XY direction and the YZ direction. Accordingly, C.I. T. It is preferable to have an E (thermal expansion coefficient) ratio and range.

The thickness of the sprayed layer in the composite material of the present invention is preferably 10 to 2000 μm. This is because the thickness of the sprayed layer is 10 μm or more,
It has excellent adhesion to the surface of the fiber composite material, can be used in a constant high-temperature oxygen-containing atmosphere, and has a C.I. T. This is because peeling due to the E difference can be suppressed.

The main component of the sprayed layer is Al
It is preferable to use any one of ₂ O ₃ , ZrO ₂ , MgO, CaO, and TiO _2.
More preferably, it is rO ₂ . When ZrO ₂ is used, it may be stabilized with Y, Ca, Mg or the like.

As described above, the composite material of the present invention has the impact resistance, high hardness and light weight of the C / C composite as the base material, the low coefficient of friction of the Si—SiC-based material as the impregnating material,
In addition to oxidation resistance, spalling resistance, self-lubrication, abrasion resistance, etc., it also has reactivity (powder-product-chemicals-chemical liquid-atmosphere) reactivity due to the sprayed layer. Because it also has, it can withstand long-term use under high-temperature oxidation conditions, specifically, a composite material that can be used in the fields of automobiles, aircraft, space, oceans, semiconductors, electronics, etc., such as ferrite, It can be suitably used for firing jigs such as condensers, containers for heat treating ceramic powder, crucibles for hot sulfuric acid, and the like.

Further, in order to surely perform the thermal spray coating, a polishing process or a Ni plating for smoothing the surface of the fiber composite material may be performed.

In the method for producing a composite material according to the present invention, the sprayed layer can be firmly fixed to the surface of the fiber composite material.
Oxidation treatment (calcination) is performed at about 00 to 800 ° C. for about 1 to 24 hours to form uniform unevenness on the surface of the fiber composite material. The oxidation temperature (calcination temperature) is 2
When the temperature is lower than 00 ° C., the oxidation time is 24 hours or more, which is not economical. On the other hand, when the oxidation temperature (calcination temperature) exceeds 800 ° C., the oxidation time is too short. It is difficult to form uniform irregularities on the surface of the composite material.

Next, a thermal spray material is thermally sprayed on the surface of the fiber composite material produced as described above to form a thermal spray layer. Thereby, the (spray-product-drug-chemical-solution-atmosphere) reactivity is imparted to the surface of the fiber composite material by the sprayed layer, and the low oxidation resistance of the C / C composite used as the base material can be overcome. Not only that, it is also possible to improve low hardness, which is a problem of the fiber composite material, so that wear resistance can be further improved.

Here, the thermal spraying method is to melt a thermal spray material such as a metal or ceramics, and compress the molten material with compressed air or
This is a technique in which a ceramic film is formed by spraying the substrate with the driving force of a compressed inert gas.

The thermal spraying method used in the present invention is not particularly limited, but is preferably performed by plasma thermal spraying. For example, using Ar as a primary gas and H ₂ as a secondary gas,
When performing plasma spraying on the impregnated and fired body (base material) with a current of Amp, the spraying distance is preferably 50 to 300 mm, more preferably 100 to 200 mm, and still more preferably 100 to 150 mm. .

At this time, the thermal spray material used in the present invention is:
It preferably contains any of Al ₂ O ₃ , ZrO ₂ , MgO, CaO, and TiO ₂ , and more preferably ZrO ₂ from the viewpoint of fixing the thermal sprayed layer. In addition, ZrO ₂
In the case where is used, a material stabilized with Y, Ca, Mg or the like may be used.

[0067]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The properties of the composite materials obtained in the respective examples were evaluated by the following methods.

(Method of Measuring Surface Roughness (Ra) and Flatness of Substrate) Surface roughness (Ra) and flatness were measured at three points of 5 mm length using Surfcom 550A (manufactured by Tokyo Seimitsu). It was measured as an average over time. Here, the surface roughness (Ra) means that a reference length 1 is extracted from the roughness curve in the direction of the average line, the X-axis is in the direction of the average line of the extracted portion, and the Y-axis is in the direction of the vertical magnification. And take the roughness curve as y = f
When expressed by (x), the value obtained by the following equation is expressed in micrometers (μm).

[0069]

(Equation 1)

(Evaluation Method of Adhesion State of Thermal Sprayed Layer) After a gum tape was attached to the surface of the sprayed layer of the composite material, the gum tape was peeled off, and it was evaluated whether or not the sprayed layer was separated from the composite material. The gum tape is a cloth adhesive tape No. 3310 (JIS Z1524 type 1 manufactured by Sliontec Co., Ltd.).
No. Permission No. 387030) was used.

(Method of Evaluating Peeling and Chipping of Thermal Sprayed Layer After Thermal History) The composite material was placed in a furnace maintained at 500 ° C.
After holding for 15 minutes, pull it out of the furnace and place it in the atmosphere for 15 minutes.
The operation of standing for 20 minutes was repeated 20 times, and the presence or absence of peeling and chipping of the sprayed layer was evaluated.

(Method of measuring open porosity) Open porosity (%) = [(W3−W1) / (W3−W2)] ×
100 (according to the Archimedes method) Dry weight (W1): dried for 1 hour in an oven at 100 ° C., then weighed Weight in water (W2): boil the sample, completely penetrate water into open pores, and weigh in water Drinking water weight (W3): A sample in which water has completely penetrated into the open pores is weighed in the atmosphere

(Oxidation resistance evaluation method)
Leave in a furnace at 150 ° C. (1% O ₂ , 99% N ₂ )
The oxidation resistance was evaluated by measuring the weight loss rate after 0 hour.

(Method of Evaluating Compressive Strength) A compressive load was applied to a test piece, and calculated by the following equation. Compressive strength = P / A (where P is the load at the maximum load, and A represents the minimum cross-sectional area of the test piece.)

(Evaluation Method of Interlaminar Shear Strength) Three-point bending was performed using a distance four times the thickness h of the test piece as a distance between fulcrums, and calculated by the following equation. Interlaminar shear strength = 3P / 4bH (where P is the maximum bending load at break, and b represents the width of the test piece)

(Evaluation Method of Flexural Modulus) Three-point bending is performed with the distance between supports as 40 times the thickness h of the test piece, and the initial gradient P / σ of the linear portion of the load-deflection curve is used. Then, it was calculated by the following equation. Flexural modulus = １ ／ · L ³ / bh ³ · P / σ (where b represents the width of the test piece)

(Method of Evaluating Self-Healing Property) Max: 20M
Pa-Min: After applying a repetitive stress of 5 MPa 100,000 times to generate micro cracks inside, 900 ° C.
For 2 hours, and the compression strength was measured.

(Evaluation Method of Dynamic Friction Coefficient) A test piece was set on a jig and rotated, and a mating material (SUJ, 10 mm
The ball was pressed against the test piece with a constant load Fp (N), and the frictional force Fs (N) at that time was measured. The value of the dynamic friction coefficient was calculated by the following equation. Coefficient of friction μ = Fs / Fp

(Method of Evaluating Specific Abrasion Amount) A test piece was set on a jig and rotated, and a mating material (SUJ, 10 mm
The ball (ball) was pressed against the test piece with a constant load P, and the weight Wa (mg) before the test and the weight Wb (mg) after the test were measured. From the density ρ (g / cm ³ ) of the test piece, the wear amount V (mm ³ ) was calculated by the following equation. V = (Wa−Wb) / ρ The specific wear amount Vs (mm ³ / (N · km)) is the wear amount V
(Mm ³ ), test load P (N) and sliding distance L (km)
From the following equation, it was calculated. Vs = V / (P · L)

Example 1 C having a thickness of 10 mm
An impregnated fired body (base material) in which a layer made of a Si-SiC material was arranged on a / C composite base material was manufactured, and a composite material was manufactured using the fired body. The thickness from the surface of the layer to be impregnated and formed in the arranged Si-SiC material base material was 50 μm. Note that S
The i impregnation rate was 40%.

The C / C composite was manufactured by the following method. By impregnating a carbon fiber in one direction with a phenol resin, about 10,000 long carbon fibers having a diameter of 10 μm are bundled to obtain a fiber bundle (yarn), and the yarns are arranged as shown in FIG. Thus, a prepreg sheet was obtained. Next, this prepreg sheet was laminated in 50 stages, and treated by a hot press at 180 ° C. and 10 kg / cm ² to cure the phenol resin. Then, it was fired at 2000 ° C. in nitrogen to obtain a C / C composite. The resulting C / C composite had a density of 1.0 g / cm ³ and an open porosity of 50%.

Next, the obtained C / C composite was
It was set up in a carbon crucible filled with Si powder having a purity of 99.8% and an average particle diameter of 1 mm. Next, the carbon crucible was moved into the firing furnace. The temperature inside the firing furnace was 1300
° C, the flow rate of argon gas as an inert gas is 20 NL /
Minutes, the internal pressure of the firing furnace is 1 hPa, and the holding time is 4 hours. After the treatment, while maintaining the pressure in the firing furnace as it is,
By raising the furnace temperature to 1600 ° C., the C / C composite was impregnated with Si to produce a fiber composite material. Table 1 shows the measurement results such as the density, open porosity, interlaminar shear strength, compressive strength, and flexural modulus of the obtained fiber composite material. In addition, each data is about the test piece cut out from the surface vicinity of the fiber composite material in which Si-SiC type material and C / C composite are fully composited.

Next, a test piece cut out from the vicinity of the surface layer of the fiber composite material was 60 mm long by a surface grinder.
After cutting to the size of 60mm in width and 60mm in thickness,
Surface grinding was performed with an 800 # grinding wheel. The plane roughness (Ra) and flatness of the fiber composite material (test piece) before thermal spraying are as shown in Table 2.

Next, a composite material was manufactured by spraying 150 μm of Y-stabilized ZrO ₂ on the surface of the fiber composite material. Here, the thermal spraying on the fiber composite material was performed in the YZ direction on the side surface of the C / C composite. Table 3 shows the adhesion state of the thermal spray layer of the obtained composite material, and the results of peeling and chipping of the thermal spray layer after thermal history.

Example 2 The same fiber composite material as in Example 1 was heated at 400 ° C. × 2 hours in an air atmosphere, and then Y-stabilized ZrO ₂ was applied to the surface of the fiber composite material.
A composite material was manufactured by spraying 00 μm. still,
The surface roughness (Ra) and flatness of the fiber composite material before thermal spraying are as shown in Table 2. Table 3 shows the adhesion state of the thermal spray layer of the obtained composite material, and the results of peeling and chipping of the thermal spray layer after thermal history. Where fiber composite material (test piece)
Is sprayed in a direction X- parallel to the fiber lamination direction.
Y performed.

Example 3 The same fiber composite material as in Example 1 was subjected to a heat treatment at 500 ° C. × 2 hours in an air atmosphere, and then a 20 μm Ni plating was electrolessly applied to the surface of the fiber composite material. , Y-stabilized ZrO ₂ was sprayed at 300 μm to produce a composite material. The plane roughness (Ra) and flatness of the fiber composite material before thermal spraying are as shown in Table 2. Table 3 shows the adhesion state of the thermal spray layer of the obtained composite material, and the results of peeling and chipping of the thermal spray layer after thermal history. Here, the thermal spraying on the fiber composite material was performed in a direction XY parallel to the lamination direction of the fibers.

Example 4 The same fiber composite material as in Example 1 was subjected to a heat treatment at 500 ° C. × 3 hours in an air atmosphere, and then Y-stabilized ZrO ₂ was applied to the surface of the fiber composite material.
A composite material was manufactured by spraying 00 μm. still,
The surface roughness (Ra) and flatness of the fiber composite material before thermal spraying are as shown in Table 2. Table 3 shows the adhesion state of the thermal spray layer of the obtained composite material, and the results of peeling and chipping of the thermal spray layer after thermal history. Here, the thermal spraying on the fiber composite material was performed in a direction XY parallel to the lamination direction of the fibers and in a direction YZ perpendicular to the lamination direction of some of the fibers.

Example 5 C having a thickness of 10 mm
A fiber composite material in which a layer made of a Si—SiC material was disposed on a / C composite base material was manufactured, and a composite material was manufactured using the composite material. The thickness from the surface of the layer in which the Si / SiC-based material disposed is impregnated into the C / C composite base material is 100
μm. The fiber composite material was manufactured by the same manufacturing method as in Example 1, and the Si impregnation rate was 40%.
And In addition, the plane roughness (Ra) of the fiber composite material before thermal spraying
And the flatness are as shown in Table 2.

Next, Al ₂ was added to the surface of the fiber composite material.
A composite material was manufactured by spraying O ₃ at 10 μm. Table 3 shows the adhesion state of the thermal spray layer of the obtained composite material, and the results of peeling and chipping of the thermal spray layer after thermal history. here,
Thermal spraying on the fiber composite material was performed in a direction XY parallel to the lamination direction of the fibers.

Example 6 The same fiber composite material as in Example 5 was subjected to a heat treatment at 200 ° C. × 5 hours in an air atmosphere, and then the surface of the fiber composite material was sprayed with 100 μm of MgO to obtain a composite material. Was manufactured. The plane roughness (Ra) and flatness of the fiber composite material before thermal spraying are as shown in Table 2. Adhesion state of the sprayed layer of the obtained composite material,
Table 3 shows the results of peeling and chipping of the sprayed layer after the heat history. Here, the thermal spraying on the fiber composite material was performed in a direction XY parallel to the lamination direction of the fibers.

[0091] The same fiber composite material (Example 7) Example 5, was heated at 500 ° C. × 2 Hr in an air atmosphere, the TiO ₂ on the surface of the fiber composite material 1000μ
The composite material was manufactured by spraying m. The plane roughness (Ra) and flatness of the fiber composite material before thermal spraying are as shown in Table 2. Table 3 shows the adhesion state of the thermal spray layer of the obtained composite material, and the results of peeling and chipping of the thermal spray layer after thermal history.
Shown in Here, the thermal spraying on the fiber composite material was performed in a direction XY parallel to the lamination direction of the fibers and in a direction YZ perpendicular to the lamination direction of some of the fibers.

Example 8 The same fiber composite material as in Example 5 was subjected to a heat treatment at 800 ° C. × 1 Hr in an air atmosphere, and then the surface of the fiber composite material was coated with 2000 μm of CaO.
The composite material was manufactured by spraying. Table 2 shows the surface roughness (Ra) and flatness of the fiber composite material before thermal spraying.
As shown in FIG. Table 3 shows the adhesion state of the thermal spray layer of the obtained composite material, and the results of peeling and chipping of the thermal spray layer after thermal history.
Shown in Here, the thermal spraying on the fiber composite material was performed in a direction XY parallel to the lamination direction of the fibers and in a direction YZ perpendicular to the lamination direction of some of the fibers.

Comparative Example 1 As a base material of a composite material, Si was used.
-SiC material is 60 mm long and 60 m wide using a surface grinder
m, after cutting to the size of thickness 60mm, 800 #
A composite material was manufactured by using a surface-finished grinding wheel and performing heat treatment at 500 ° C. for 3 hours in an air atmosphere, and then spraying 500 μm of Y-stabilized ZrO ₂ on the surface of the base material. The surface roughness (Ra) of the substrate before thermal spraying
And the flatness are as shown in Table 2. Table 3 shows the adhesion state of the thermal spray layer of the obtained composite material, and the results of peeling and chipping of the thermal spray layer after thermal history. Here, thermal spraying on the substrate
The test was performed in a direction XY parallel to the lamination direction of the fibers and in a direction YZ perpendicular to the lamination direction of some of the fibers.

[0094]

[Table 1]

[0095]

[Table 2]

[0096]

[Table 3]

(Consideration: Examples 1 to 8, Comparative Example 1) From the results shown in Table 1, in Comparative Example 1, the adhesion state of the sprayed layer formed on the base material was poor (1.5 cm ² peeling), It was found that peeling of the sprayed layer (1.5 cm ² or less) and chipping (0.5 cm ² or less) occurred upon impact.
This is not a fiber composite material as the substrate, but Si-Si
Since the C material is used, the C.I. T.
E. FIG. It is considered that (coefficient of thermal expansion) is large.

On the other hand, in Examples 1 to 8, the thermal sprayed layer did not suffer chipping due to thermal shock, and in Examples 1 to 7, the adhered state of the thermal sprayed layer formed on the substrate was good (no peeling). It was found that there was no peeling of the sprayed layer due to thermal shock. In Example 8, the adhesion state of the thermal sprayed layer formed on the base material (peeling of 0.5 cm ² or less) had some problems, and the thermal spraying caused the peeling of the thermal spray layer (peeling of 0.5 cm ² or less). Although there are some, it seems to be safe in practical use.

From the above, as in Examples 1 to 8, a thermal spray layer is formed on the surface of a fiber composite material in which a matrix made of a Si—SiC-based material is arranged on a base material made of a C / C composite. The thickness of the sprayed layer is 10 to 2
When the thickness is controlled to 000 μm, the adhesiveness to the surface of the fiber composite material is excellent, and it can be used under a constant high-temperature oxygen-containing atmosphere. T. It has been found that peeling due to the E difference can be suppressed.

[0100]

As described above, according to the composite material of the present invention, the impact resistance of the C / C composite as the base material,
In addition to high hardness and light weight, low friction coefficient, oxidation resistance, spalling resistance, self-lubricating property, abrasion resistance, etc. of the Si-SiC-based material that forms the matrix with the impregnating material, resistance to the sprayed layer (Powder-Product-Chemical-Chemical-Atmosphere) In addition to having reactivity, the base material also has self-healing properties, so that it can withstand long-term use under high-temperature oxidation conditions.

Further, since the C / C composite is used as a base material, it is light in weight and has a small specific heat, so that energy loss is small and the requirement for energy saving is met. Further, since the base material is a C / C composite, the base material is rich in toughness, and has excellent impact resistance and high hardness.
Therefore, the disadvantage of low impact resistance of conventional ceramics can be overcome, and it can be used for composite materials having complicated shapes and thin portions.

[Brief description of the drawings]

FIG. 1 is a perspective view schematically showing a form of a yarn aggregate of a fiber composite material used in the present invention.

FIGS. 2A and 2B are cross-sectional views schematically showing a microstructure of a main part of the fiber composite material used in the present invention, wherein FIG. 2A is a cross-sectional view taken along the line IIa-IIa of FIG. 1, and FIG. It is sectional drawing.

FIG. 3 is a partially enlarged view of FIG.

FIG. 4 is a partial cross-sectional perspective view schematically illustrating a microstructure of a fiber composite material according to another embodiment.

FIG. 5A is a cross-sectional view showing a fiber composite material 11,
(B) is a sectional view showing the fiber composite material 16.

FIG. 6 is a sectional view showing an example of the composite material of the present invention.

[Explanation of symbols]

1A, 1B, 1C, 1D, 1E, 1F...
2A, 2B ... yarn, 3 ... carbon fiber bundle, 4A, 4B ... silicon carbide phase, 5A, 5B ... silicon phase, 6 ... yarn assembly, 7
... fiber composite material, 11, 16 ... fiber composite material, 13 ... fiber composite material layer, 15 ... C / C composite, 17 ... thermal sprayed layer.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takao Nakagawa 2-16-27 Nishikicho, Warabi-shi, Saitama Prefecture Inside Across Co., Ltd. (72) Mihoko Yamashita 2-16-27 Nishikicho Warabi-shi, Saitama Prefecture Across Inc. Inside

Claims (15)

[Claims] 1. A yarn aggregate in which yarns containing at least a bundle of carbon fibers and a carbon component other than carbon fibers are three-dimensionally combined and integrated so as not to be separated from each other. A composite material having a thermal spray layer, wherein a thermal spray layer is formed on a surface of a fiber composite material comprising: a matrix made of a Si-SiC-based material filled between the adjacent yarns. 2. The matrix according to claim 1, wherein said matrix has a silicon carbide phase formed along the surface of said yarn.
A composite material having the sprayed layer according to the above. 3. The composite material according to claim 2, wherein the matrix has a silicon phase made of silicon, and the silicon carbide phase is generated between the silicon phase and the yarn. 4. The composite material having a sprayed layer according to claim 1, wherein the matrix has a gradient composition in which the content of silicon increases as the distance from the surface of the yarn increases. 5. The yarn assembly includes a plurality of yarn arrays, each yarn array being formed by two-dimensionally arranging a plurality of the yarns in a substantially parallel manner. The composite material having a sprayed layer according to any one of claims 1 to 4, wherein the yarn aggregate is configured by stacking an array. 6. The composite material having a sprayed layer according to claim 5, wherein the longitudinal directions of the respective yarns in the adjacent yarn array cross each other. 7. The composite material having a thermal spray layer according to claim 1, wherein the matrix is continuous with each other in the fiber composite material to form a three-dimensional network structure. 8. The matrix is arranged two-dimensionally in a substantially parallel manner in each of the yarn arrays, and the matrices generated in each of the adjacent yarn arrays are continuous with each other. The composite having a sprayed layer according to claim 7, wherein the matrix forms a three-dimensional lattice. 9. The composite material having a sprayed layer according to claim 1, wherein the thickness of the sprayed layer is 10 to 2000 μm. 10. The main component of the sprayed layer is Al ₂ O ₃ , ZrO.
_2, Mg0, CaO, and a composite material having a sprayed layer as claimed in any one of claims 1 to 9 is any one of TiO _2. 11. A carbon fiber bundle is produced by incorporating a powdery carbon component finally serving as a matrix into a bundle of carbon fibers, and then a plastic film is formed around the carbon fiber bundle to form an intermediate layer. The intermediate material is then made into a yarn and then laminated in a predetermined amount and molded to obtain a molded body, or the molded body is sintered to obtain a sintered body, and then the molded body or sintered body is formed. The body and Si are kept at a temperature of 1100 to 1400 ° C. under an inert gas atmosphere,
The molded body or the sintered body and Si are heated at 1450 to 2500 ° C.
By raising the temperature to the above temperature, the interior of the open pores of the compact or sintered body is impregnated with a Si-SiC-based material to produce a fiber composite material, and then a thermal spray material is sprayed on the surface of the fiber composite material. A method for producing a composite material having a sprayed layer, wherein the sprayed layer is formed. 12. The molded body or sintered body and Si are
The temperature is maintained at a temperature of 00 to 1400 ° C. and a pressure of 0.1 to 10 hPa for 1 hour or more, and at that time, 0.1 normal liter (NL) of inert gas is added per 1 kg of the total weight of the compact or sintered compact and Si. 2) controlling the flow so as to flow at least.
A method for producing a composite material having the thermal spray layer according to claim 1. 13. The method according to claim 13, wherein the compact or the sintered compact and Si are mixed in an amount of 0.1.
The method for producing a composite material having a sprayed layer according to claim 11 or 12, wherein the temperature is raised to a temperature of 1450 to 2500 ° C under a pressure of 1 to 10 hPa. 14. The method according to claim 12, wherein the fiber composite material is
After calcining at 200 to 800 ° C., a thermal spray material is thermally sprayed on the surface of the fiber composite material to form a thermal spray layer, and the thermal spray layer according to any one of claims 11 to 13 is provided. Manufacturing method of composite material. 15. A thermal spraying material comprising Al ₂ O ₃ , ZrO ₂ , Mg
O, CaO, and method for producing a composite material having a sprayed layer as claimed in any one of claims 11 to 14 containing either TiO _2.