JPH07310130A - Metallic composite material - Google Patents

Abstract

PURPOSE:To obtain a metallic composite material excellent in resistance to heat and corrosion and mechanical characteristics for plural wiry composite reinforcing materials consisting of many inorg. long fiber filaments and glass present in the clearance between the filaments by filling the clearance with a metallic material. CONSTITUTION:A wiry or tape-shaped composite reinforcing material is formed from many inorg. long fiber filaments (having about 5-200mum average diameter and about 1.9-4.0g/cm<3> density) and the glass (of B2O3.SiO2, etc.) and/or glass ceramics (of MgO.Al2O3.SiO2, etc.) filling the clearance between the filaments. The inorg. long fiber contains, by weight, 30-80% Si and 0.05-8% Ti and/or Zr, 15-69% C and 0.1-20.0% O. The clearance is filled with a metal (Ti-6Al-4V (alpha+beta type), etc.) or an intermetallic compd. (Ti3Al, etc.) to produce a metallic composite material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal-based composite material, and more particularly to a metal-based composite material excellent in heat resistance, corrosion resistance and mechanical properties.

[0002]

2. Description of the Related Art Conventionally, various materials having excellent heat resistance and mechanical properties have been developed as materials used in the fields of space and aeronautics, etc. Metal matrix composites (MMC) and the like have been proposed.

As the MMC, for example, the following composites and the like have been proposed. As a matrix, it has a large specific strength and specific elasticity and is excellent in corrosion resistance as compared with steel, a super heat resistant alloy or a heat resistant eutectic alloy, and has a use limit temperature (for example, 7
23K) is high, α + such as Ti-6Al-4V
β type or β such as Ti-15V-3Cr-3Sn-3Al
Using a titanium alloy such as a mold, as a reinforcing material, the fiber core is carbon fiber, and the SiC / C composite fiber formed by vapor-depositing SiC by the CVD method on the outside thereof (for example, the one made by Textron is most widely used). A complex formed by using

The above-mentioned composite body has the above-mentioned Si which can sufficiently exhibit its performance as a reinforcing material against the above-mentioned titanium alloy.
Since C / C fiber is used, it has been reported to show high performance [Journal of Japan Society for Composite Materials Vol. 17, No. 1 (1
991), page 25 in 24-31]. For example, as the reinforcing material, carbon fiber (PAN-based, pitch-based), A
l ₂ O ₃ fiber (manufactured by Du Pont, 3M, Sumitomo Chemical Co., Ltd., etc.), SiC fiber [“Nicalon” trade name, manufactured by Nippon Carbon Co., Ltd.], Si—Ti—C—O fiber [“ Tyranno fiber "product name, manufactured by Ube Industries, Ltd.], Si-CN fiber [" HPZ fiber "product name, manufactured by Dow Corning Co., Ltd.],
When using all other heat-resistant fibers such as Si ₃ N ₄ fiber (manufactured by Tonen Co., Ltd.), when composited with the above titanium alloy,
Since it reacts remarkably with Ti alloy (depending on the fiber), no reinforcement effect can be obtained at all, or even if the reaction deterioration is small, the reinforcement effect cannot be obtained so much. Does not show sufficient performance.

However, the above composite has the following defects (a) and (b). (A) Since the thermal expansion coefficient is extremely different between the core carbon fiber and the SiC outside the reinforcing material in the reinforcing material, the thermal cycle fatigue (low temperature-high temperature repeating) characteristics are remarkably inferior, and as a reinforcing material for a high temperature structural member. Difficult to use in terms of reliability. (B) High price (1
Since it is more than 1,000,000 yen / kg), it can only be used for special military applications where the price is not a concern at all. Further, the price has recently become a problem in the aircraft industry, and the practical material price is limited to 20 to 300,000 yen / kg, so that the above-mentioned reinforcing material is not practical.

Further, as the MMC, the following composite
The body is also proposed. As a matrix, more
Highly heat resistant Ti ₃Al, TiAl, Nb₃Al, etc.
Using an intermetallic compound of
Taking into consideration the reaction deterioration during compounding, SiC / C fiber
A complex formed by using.

However, even in the above-mentioned composite, there is a problem that the above-mentioned SiC / C fiber is deteriorated by reaction during the production of the composite, and at present the performance as described above is not exhibited.

Further, the followings have been proposed as the MMC. As the matrix, aluminum alloy (A606
1, A2024, A1070, etc.) and SiC / C fiber (made by Textron) as a reinforcing material [Journal of Japan Society for Composite Materials V
ol. 17, No. 1 (1991), pages 25 to 24 to 31], Al ₂
O ₃ fiber (manufactured by Sumitomo Chemical) [Handbook of New Polymer Materials, edited by The Polymer Society of Japan (Maruzen), P.463 (1989)] Carbon fiber [iron steel, V
ol. 75, No. 9 (1989), 41-48] or SiC fiber (Nicalon, manufactured by Nippon Carbon Co., Ltd.) [Handbook of New Polymer Materials, edited by The Polymer Society of Japan (Maruzen), P.472 (1989)]. A complex formed by using.

Further, although the above-mentioned composite material exhibits high performance at a low temperature as described above, there is a problem that the thermal cycle fatigue property is remarkably inferior similarly to the above-mentioned composite material.

However, the above-mentioned composite using SiC / C fibers has a problem in that, although high strength at low temperatures can be obtained as described above, the reinforcing fibers are expensive and the thermal cycle fatigue properties are significantly inferior. There is a complex with carbon fibers, that it does not withstand prolonged oxidation atmosphere above 200 ° C., there is a problem in that poor corrosion resistance and the like for the electrically conductive properties of the carbon fibers, also, Al ₂ The composite using O ₃ fiber and SiC fiber is the most practical A6061 matrix.
Or when using an aluminum alloy such as A2024,
Since the aluminum alloy and the fibers react with each other during MMC molding to deteriorate the fibers, there is a problem that a sufficient reinforcing effect cannot be obtained, and the mechanical properties are far below the theoretical value calculated from the complex rule.

A magnesium alloy (ZE41, AZ91, etc.) is used as a matrix, and SiC is used as a reinforcing material.
/ C composites formed using C fibers [Journal of Japan Society for Composite Materials, Vol. 17, No. 1 (1991), pages 26-31 of 24-31].

[0012] Although MMC in which other inorganic fibers such as Al ₂ O ₃ fibers and SiC fibers are compounded with magnesium alloy has been proposed, in the MMC, the reaction between the fiber and the magnesium alloy during the production of MMC is carried out. At present, the performance is not sufficiently exhibited because the fibers are significantly deteriorated.

That is, the conventionally proposed MMC has the disadvantages that the reinforcing material reacts with the matrix during the production of the composite, that the composite itself is inferior in heat cycle fatigue characteristics, and that it is inferior in heat resistance and oxidation resistance. Therefore, it does not satisfy the heat resistance, corrosion resistance, mechanical properties, etc. required in the space and aviation field, and can exhibit sufficient heat resistance, mechanical properties, etc. without the above-mentioned adverse effects. Development of MMC is desired. Further, in the conventional MMC, when the content (Vf) of the fiber as the reinforcing material is low, it becomes difficult to uniformly disperse the fiber in the matrix, and dispersion unevenness easily occurs, resulting in strength of the obtained composite. Since unevenness occurs, in such a case, there is no choice but to use a reinforcing material in overspecification, which causes a problem of high cost. Further, when the above-mentioned Vf is large, there is a problem that the reinforcing materials may come into contact with each other, and the desired mechanical strength or the like may not be obtained in the obtained composite.

Therefore, an object of the present invention is to provide a metal-based composite material having excellent heat resistance, corrosion resistance and mechanical properties.

As a result of various studies to solve the above problems, the present inventors have found that a metal-based composite material using a specific composite reinforcing material can achieve the above object.

The present invention has been made based on the above findings, and comprises a plurality of composite reinforcing materials and a metal or intermetallic compound present in the gaps between the composite reinforcing materials. It is intended to provide a metal-based composite material comprising a large number of filaments of inorganic long fibers and glass and / or glass ceramics existing in the spaces between the filaments and having a wire shape or a tape shape.

The metal-based composite material of the present invention will be described in more detail below. The composite reinforcing material (hereinafter simply referred to as “reinforcing material”) used in the present invention is composed of a large number of filaments of inorganic long fibers and glass and / or glass ceramics present in the spaces between the filaments, Have a shape.

Examples of the inorganic long fibers used in the present invention include inorganic long fibers composed of silicon (Si) and titanium (Ti) and / or zirconium (Zr), carbon (C) and oxygen (O). Specifically, (a) an amorphous material consisting essentially of Si, Ti and / or Zr, C, and O, (b) the amorphous material and β- of 10000 Å or less.
A crystalline aggregate of SiC and TiC and / or ZrC, or (c) SiOx and TiOx and / or ZrOx (0 <x ≦
Preferred are inorganic long fibers and the like which are an amorphous mixed system composed of 2) and. Here, the “vicinity” in the above (C) is preferably a distance of 10 from the crystalline particles.
This is an area below 00Å. The elemental composition of the above-exemplified inorganic long fibers has a Si content of 30 to 80.
wt%, Ti and / or Zr is 0.05 to 8 wt%, and C is 1
It is preferably 5 to 69 wt% and O is 0.1 to 20.0 wt%.

The inorganic long fibers used in the present invention include inorganic long fibers composed of silicon (Si) and carbon (C), and specifically, (a) substantially S.
i and C amorphous, (b) 10000 Å or less β-SiC crystalline, (c) the amorphous and crystalline, or (d) the amorphous and / or crystalline In addition, inorganic long fibers and the like, which are a mixed system of carbon agglomerates and the like, are also preferable. The elemental composition of the above-exemplified inorganic long fibers is 30 to 80 wt% for Si and 2 for C.
It is preferably 0 to 70 wt% and H is 2 wt% or less.

The inorganic long fibers used in the present invention include silicon (Si), carbon (C) and oxygen (O).
Inorganic long fibers and the like consisting of, and the like, specifically,
(A) an amorphous body substantially consisting of Si, C, and O, or (b) an aggregate consisting of a crystalline aggregate of β-SiC of 10,000 Å or less and amorphous SiO _2. Some inorganic long fibers are also preferred. The elemental composition of the inorganic long fibers specifically exemplified above is such that Si is 30 to 80.
wt%, C is 10 to 65 wt%, O is 0.05 to 25 wt%,
It is preferable that H is 2 wt% or less.

The inorganic long fibers used in the present invention include silicon (Si), nitrogen (N) and oxygen (O).
And carbon (C) and hydrogen (H) and the Periodic Table of Elements Group II-VI
Inorganic long fibers and the like composed of one or more metals (M) selected from the group consisting of Group II metal elements are mentioned, and specifically, Si, N, O, C, H and the periodical element Table 1, which is composed of one or more metals (M) selected from the group consisting of Group II to Group VIII metal elements and has an X-ray small angle scattering intensity ratio of 1
Inorganic long fibers and the like, which are substances that are 1 to 20 times at both 0 ° and 0.5 °, are also preferable. The ratio of each element in the above-exemplified inorganic long fibers is atomic ratio, N / Si is 0.3 to 3, O / Si is 15 or less, C / Si is 7 or less, and H / Si is 1 or less. , M / Si is preferably 5 or less.

The inorganic long fibers used in the present invention include (a) substantially Al, Si, B, and O.
Preference is also given to mullite composed of and / or (b) inorganic long fibers which are aggregates of fine crystals of γ- and η-alumina and amorphous SiO ₂ .

In the above-mentioned inorganic long fibers, the C composition of the outermost surface layer of the fiber is 35 to 100% by weight, the Si composition is 0 to 60% by weight,
Ti composition is 0 to 4 wt%, O composition is 0 to 19 wt%,
It is preferable to have a gradient composition structure in which the C, Si, Ti, and O compositions continuously change within the range of 20 to 20000Å from the surface layer to the inside of the fiber. The gradient ratio in the gradient composition structure may be a change in the linear gradient ratio, a change in the curvilinear gradient ratio, or a change in the gradient ratio in which they are combined as long as the composition changes continuously.

The average diameter of the filaments of the inorganic long fibers is preferably 5 to 200 μm, and the number of the filaments in the reinforcing material of the present invention is 5 to 6000.
The range is preferably. In addition, the shape of the filament may be cylindrical, cylindrical, prismatic, prismatic, or the like. The filament can be easily obtained by molding the inorganic long fiber by a known method. Also,
The density of the filament is usually 1.9 to 4.0 g /
It is cm ³ .

Examples of the above glass include B ₂ O ₃ .SiO ₂
Examples thereof include MgO, CaO, Al ₂ O ₃ and SiO ₂ type glass. Examples of the glass ceramics include Li ₂ O.Al ₂ O ₃ .MgO.SiO ₂ .Nb
₂ O ₅ system, MgO ・ Al ₂ O ₃・ SiO ₂ system, BaO ・
Al ₂ O ₃ · SiO ₂ system, BaO · MgO · Al ₂ O ₃
Preferred examples include SiO ₂ -based and CaO · Al ₂ O ₃ · SiO ₂ -based glass ceramics. In addition, the above-mentioned glass and glass-ceramics have
A group II metal oxide, a group III metal oxide, a group IV metal oxide, and / or a group V metal oxide can be contained. The density of the glass and glass-ceramics is usually 2.0 to 3.8 g / cm ³ .

Further, in the above glass ceramics, the amorphous part and / or the main crystal layer of each composition described above are anorthite,
β-Spodumene, Cordierite, Barium Osumilite, Mulli
It is preferably composed of a crystalline part such as te or Celsian.

The volume fraction of filaments of the inorganic long fibers and the volume fraction of glass and / or glass ceramics in the reinforcing material are 20 to 90 vol% and 8 respectively.
It is preferably 0 to 10 vol%.

The reinforcing material preferably has various impact resistance layers at the interface between the filament and the metal composite oxide, if necessary. The various impact resistance layers are at least one of carbon, carbide, nitride and boride ceramics, specifically carbon, SiC, Si.
₃ N ₄ , TiB ₂ , TiN, TiC, BN, TiC · T
It is preferably made of iN or the like and has a thickness of 5 to 20000Å.

The volume content of each of the various impact-resistant layers is 1
It is preferably 0 vol% or less.

Next, the reinforcing material will be described with reference to FIGS. 1 and 2. Here, FIG. 1 is a partially transparent perspective view showing an example of the reinforcing material, and FIG. 2 is a partially transparent perspective view showing another example of the reinforcing material.

The reinforcing material 10 shown in FIG. 1 comprises a large number of cylindrical filaments 1 of inorganic long fibers and glass and / or glass ceramics 2 present in the spaces between the filaments 1 and has a wire shape.

More specifically, the filaments 1 are formed as an aggregate, and glass and / or glass ceramics 2 are present in the gap between the filaments 1 in the aggregate. Then, the glass and / or glass ceramic 2 forms the outer shape of the reinforcing material 10 itself to form the wire shape.

The reinforcing material 10A shown in FIG. 2 comprises a large number of columnar filaments 1A of inorganic long fibers and glass and / or glass ceramics 2A existing in the gaps between the filaments 1A and has a tape shape. .

More specifically, the filaments 1A are formed into an aggregate, and the glass and / or glass ceramics 2 are provided in the gaps between the filaments 1A in the aggregate.
A exists. The glass and / or glass ceramics 2A form the outer shape of the reinforcing material 10A itself to form the tape shape.

As shown in FIGS. 1 and 2, the reinforcing material itself is composed of a composite material composed of inorganic fibers and a matrix of glass and / or glass ceramics, and the shape thereof is wire-like or It is a tape shape.

The wire diameter in the above wire shape is preferably 20 μm to 5 mm, and the tape width and tape height in the above tape shape are preferably 20 μm to 10 cm and 10 μm to 1 cm, respectively.

Next, a method of manufacturing the above reinforcing material will be described. To prepare the reinforcing material, for example, the following first
~ It can be obtained by sequentially performing the sixth step.

First step: removing organic sizing agent from inorganic long fibers, second step; opening inorganic long fibers from which organic sizing agent obtained in first step has been removed, third step; third step The opened inorganic long fibers obtained in two steps are
A step of passing glass ceramic and / or glass ceramic containing water and / or an organic solvent slurry solution to adhere and support the glass ceramic on the inorganic long fibers; 4th step; adhering the glass ceramic obtained in the 3rd step A step of passing the supported inorganic long fibers through a slit or a roller to form a wire shape or a tape shape, the fifth step; the wire-shaped or tape-shaped glass and / or glass-ceramic adhesion obtained in the fourth step Fifth Step, Sixth Step of Melting and Sintering Glass and / or Glass Ceramics by Continuously Firing Inorganic Long Fibers; Inorganic Long Fibers obtained by Melting and Sintering Glass and / or Glass Ceramics Obtained in Fifth Step / Glass and /
Alternatively, a step of further calcining the glass ceramics to crystallize a part or all of the melted and sintered metal oxide and continuously winding it.

Here, examples of the above-mentioned organic sizing agent removed in the first step include polyethylene oxide and vinyl acetate. In addition, as the method of opening the fibers in the second step, there may be mentioned a method of utilizing an air flow, and the velocity of the air flow at this time is 1 cm / sec to 10 cm / sec.
The pressure is preferably 0 cm / sec and the pressure is 0.1 to 5 kg / cm ² .

In the third step, a fiber sizing binder may be added to the slurry solution in order to enhance the adhesion of glass and / or glass ceramics to the fibers. Examples of the fiber sizing binder used at this time include polyethylene oxide and vinyl acetate. Further, the concentration of glass and / or glass ceramics in the water and / or organic solvent slurry solution is preferably 1 to 80 wt%, and the concentration of the binder for fiber sizing is preferably 0.1 to 50 wt%.

The slit used in the fourth step has a hole diameter of 20 μm to 5 mm and a slit width of 8 μm.
A slit having a length of 1 cm is preferable, and as the roller, a roller made of metal, plastic, rubber or ceramics to which slurry of glass and / or glass ceramics is hard to adhere is preferably used. When the slit is used, a wire-shaped or tape-shaped reinforcing material is obtained, and when the roller is used, a tape-shaped reinforcing material is obtained.

The firing temperature in the fifth step is
The temperature is preferably 500 to 1700 ° C., and the firing time is
It is preferably 30 seconds to 3 hours. Further, the firing temperature in the sixth step is preferably 700 to 1900 ° C., and the firing time is preferably 10 minutes to 500 hours.

In the case of preparing a reinforcing material having the various impact resistance layers described above, the inorganic long fibers previously coated with the various impact resistance layers described above are used as the inorganic long fibers used in the first step. It can be obtained by using.

The above-mentioned metal or intermetallic compound used in the metal-based composite material of the present invention is a component forming a matrix in the metal-based composite material of the present invention, and the metal is Ti-6Al-4V (α + β type). ), Ti-15V-
A titanium alloy such as 3Cr-3Sn-3Al (β type), A6
061, aluminum alloys such as A2024, AZ91,
Examples of the intermetallic compound include magnesium alloys such as ZE41. Ti ₃ AL, TiAl, Nb ₃
An intermetallic compound such as Al may be used. And in the present invention, particularly Ti ₃ AL, TiAl, Ti-6Al-
A titanium alloy such as 4V (α + β type) is preferably used.

The above metal and intermetallic compound are
Any of powder, foil, plate or lump, which is generally commercially available or which is usually produced by a known method, can be used.

The volume content of the reinforcing material in the metal-based composite material of the present invention and the volume content of the matrix metal or the intermetallic compound are each 20 to 80.
It is preferably vol% or 80 to 20 vol%, and can be selected in accordance with the required performance based on the structural design of the product or part to be applied. The density of the reinforcing material is 1.9 to
It is 4.0 g / cm ³ , and the density of the metal or the intermetallic compound is 1.7 to 7.3 g / cm ³ .

Further, the reinforcing form (orientation form) of the reinforcing material in the metal-based composite material of the present invention was unidirectionally strengthened, 0 °, 90 ° and various angles of composite orientation strengthening, and made with a small number of filaments. Various forms such as plain weave, satin weave, woven fabric, triaxial weave, three-dimensional weave, and various woven fabric reinforcements such as blades, which are made of a reinforcing material having a small diameter, are adopted.

In particular, in order to fully exhibit the characteristics of the metal-based composite material of the present invention (when it is used in the fields of space and aviation, etc.), the above-mentioned blending form is adopted according to the performance required by the design. In this case, the volume content of the reinforcing material and the volume content of the metal or the intermetallic compound are preferably 40 to 70 vol% and 60 to 30 vol%, respectively.

The metal-based composite material of the present invention is necessary.
Depending on the reinforcing material and the matrix metal or
Has various shock-resistant layers at the interface with the above intermetallic compounds.
Is preferred. The various impact resistance layers are carbon,
Carbides, oxides, nitrides, borides, ceramics, gold
At least one of the genus, specifically carbon, SiC, ZrO
₂, Si₃N _Four, BN, TiN, TiC, TiB₂, T
It consists of a, Zr, Hf, etc. and has a thickness of 5 to 10000Å
It is preferable to have. Volume of each of the above shock resistant layers
The content is preferably 10 vol% or less.

To prepare the metal-based composite material of the present invention,
Using the reinforcing material and the metal or intermetallic compound, it can be obtained by a generally known method, and is not particularly limited, but specifically, plasma spraying-hot pressing method, plasma spraying-diffusion bonding method, squeeze. Casting method, die casting method, powder coagulation method, infiltration method and the like can be mentioned. In addition, in the case of preparing a metal-based composite material having the above various impact resistance layers, it can be obtained by using a reinforcement material previously coated with the above various impact resistance layers as a reinforcing material to be used.

[0051]

EXAMPLES The metal-based composite material of the present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

[Manufacturing Example 1] Using the filaments of the following inorganic long fibers, the following first to sixth steps were sequentially performed, and amorphous BaO.MgO. Al ₂ O ₃ · SiO ₂ is 1
A composite reinforcing material for an advanced composite material having a wire shape of 0 vol% and inorganic long fibers of 90 vol% was obtained.

Inorganic long fiber: made of Si, Ti, C and O, and the internal elemental composition is Si: 50 wt%, Ti: 2 wt
%, C: 30 wt%, O: 18 wt%, elemental composition of the outermost layer is Si: 0 wt%, Ti: 0 wt%, C: 100 wt%, O: 0
wt%, S from the outermost layer to the inside of 700 Å
It has a graded composition structure in which the composition of i, Ti, C and O continuously changes from the composition of the outermost surface layer to the internal elemental composition, and the fiber diameter is 11
Aggregate of filaments of amorphous inorganic long fibers consisting of 1600 filament / yarn fiber bundles sized with 0.5 to 1 wt% polyethylene oxide

First step; continuous treatment in air at 350 ° C. to remove the sizing agent; second step; after opening by air flow, third step: ultrasonically dispersed BaO.MgO.Al ₂ O ₃
・ SiO ₂ (glass ceramics) fine powder slurry solution (1 polyethylene oxide as fiber cycling agent
The glass-ceramics were adhered to the fibers by passing through the glass ceramics. 4th step; subsequently, the fibers to which the above glass ceramics are adhered are passed through a slit to be formed into a wire shape, and 5th step: Continuous heat treatment is performed in nitrogen at 1000 ° C. to melt and sinter the adhered glass ceramics. After that, the sixth step: 1 of the wire-shaped composite reinforcing material for advanced composite material obtained by continuous heat treatment in 1200 ° C. nitrogen.
As a result of a tensile test in air at 200 ° C., the tensile strength was 2.5 GPa and the breaking elongation was 0.20%.

[Production Example 2] Using the filaments of the following inorganic long fibers, the following 1st to 6th steps were sequentially carried out to obtain β-Sp.
Oddumene A composite reinforcing material for an advanced composite material having a tape shape of 60 vol% of the following glass-ceramic and 40 vol% of the fiber, which is amorphous containing a part of fine crystals, was obtained.

Inorganic long fiber: Amorphous composed of Si, Ti, C, O and ultrafine particles of β-SiC, TiC of 20Å, and internal elemental composition of Si: 54 wt%, Ti: 2 wt
%, C: 32 wt%, O: 12 wt%, elemental composition of the outermost surface layer is Si: 42 wt%, Ti: 3 wt%, C: 47 wt%, O:
8wt%, S from the outermost layer to the inside of 80Å
i, Ti, C, O has a graded composition in which the composition of the outermost surface element changes continuously from the composition of the innermost element, and the thickness applied on the outermost surface layer by a chemical vapor deposition method (CVD method) 8
000Å BN with various impact-resistant layers, fiber diameter is 1
An aggregate of filaments of inorganic long fibers composed of a fiber bundle of 3200 filaments / yarn, which is sized with an epoxy resin of 1 μm and 0.5 to 1 wt%.

First step: continuous treatment in air at 400 ° C. to remove the sizing agent, second step: after opening (performed in the same manner as in Production Example 1), third step: ultrasonically dispersed ZrO Li containing a small amount of _2
2 O ・ Al ₂ O ₃・ MgO ・ SiO ₂・ Nb ₂ O ₅ (glass ceramics) fine powder slurry solution (containing 10% polyethylene oxide as a fiber sizing agent) is passed through to adhere the glass ceramics to the transition. It was 4th step; subsequently, the above-mentioned glass-ceramic-attached fibers are passed through a roller to form a tape having a width of 10 mm, 5th step: after melting and sintering at 950 ° C., 6th step; melting and firing at 1100 ° C. Bonding and continuous heat treatment were performed.

The tensile test results at room temperature of the obtained tape-shaped composite reinforcing material for advanced composite material show that the tensile strength is
It was 1.4 GPa and the elongation at break was 0.35%.

[Production Example 3] The filament of the following inorganic long fibers
The glass cell by sequentially performing the following steps 1 to 5
Amorphous Ca that contains some anorthite microcrystals that are lamic
O ・ MgO ・ Al ₂O₃・ SiO₂Is 10 vol%, inorganic length
A composite reinforcement material with a wire shape of 90 vol% fiber
Obtained.

Inorganic long fiber: Si, C, O and H, the internal elemental composition is Si: 58.3 wt%, C: 3
A fiber diameter of 0.4 wt%, O; 11.1 wt%, H: 0.2 wt%, and an aggregate composed of β-SiC crystalline aggregates of 500 Å or less and amorphous SiO _2. Is 14
μm, 130 nm carbon coating on the surface,
An aggregate of filaments of inorganic long fibers consisting of a fiber bundle of 500 filaments / yarn sized with 0.5 to 1 wt% of polyvinyl alcohol.

First step: continuous treatment in air at 600 ° C. to remove the sizing agent, second step: ultrasonically dispersed CaO.MgO.Al ₂ O ₃
・ SiO ₂ (glass ceramics) fine powder slurry solution (1 polyethylene oxide as a fiber sizing agent)
The glass-ceramics described above were attached to the fibers by passing through the glass fiber. Third step; subsequently, the fiber to which the above glass ceramic is attached is passed through a slit to be formed into a wire shape, and fourth step: 1100 ° C. is continuously treated in nitrogen to melt and sinter the attached glass ceramic. After that, the fifth step; further, continuous heat treatment was performed in nitrogen at 1300 ° C.

1 of the obtained wire-shaped composite reinforcing material
As a result of a tensile test in air at 200 ° C., the tensile strength was 2.2 GPa and the breaking elongation was 0.17%.

[Manufacturing Example 4] Using the filaments of the following inorganic long fibers, glass β
-Spodumene A composite reinforcing material having a tape shape of 60 vol% of the following glass ceramics of amorphous containing a part of microcrystals and 40 vol% of the fiber was obtained.

Inorganic long fiber: Si, C, O and H, and the internal elemental composition is Si: 58.3 wt%, C: 3
A fiber diameter of 0.4 wt%, O; 11.1 wt%, H: 0.2 wt%, and an aggregate composed of β-SiC crystalline aggregates of 1000 Å or less and amorphous SiO _2. Is 1
An aggregate of filaments of inorganic long fibers consisting of a fiber bundle of 500 filaments / yarn having a carbon coating of 2 to 14 μm, a carbon coating of 130 nm on the surface, and sizing with polyvinyl alcohol of 0.5 to 1 wt%.

First step: continuous treatment at 400 ° C. in air to remove the sizing agent, Second step: Li containing a trace amount of ZrO ₂ ultrasonically dispersed
₂ O ・ MgO ・ Al ₂ O ₃・ SiO ₂・ Nb ₂ O ₅ (glass ceramics) Fine powder slurry solution (containing 10 wt% polyethylene oxide as a fiber sizing agent) is passed through to adhere the glass ceramics to the fibers. It was 3rd step: Continuously, the fiber to which the above-mentioned gas ceramics is adhered is passed through a roller to form a tape having a width of 10 mm, and 4th step: after melting and sintering at 950 ° C, 5th step; melting and firing at 1100 ° C. Bonding and continuous heat treatment. The tensile test results at room temperature of the obtained tape-shaped composite reinforcing material were a tensile strength of 1.2 GPa and a breaking elongation of 0.30%.

[Production Example 5] The following filaments of inorganic long fibers
The glass cell by sequentially performing the following steps 1 to 5
Amorphous MgO · A that partially contains the cordierite that is a lamic
l₂O₃・ SiO ₂Is 10 vol%, inorganic long fiber is 90 vol%
A composite reinforcing material having a wire shape was obtained.

Inorganic long fibers: Si, N, C, O, and H, and the internal elemental composition is Si: 59.2 wt%, N: 3
7.5 wt%, C; 1.5 wt%, O; 1.5 wt%, H;
The fiber diameter is 10 to 20 μm, which is 0.3 wt% and mainly consists of a microcrystalline aggregate of Si ₃ N ₄ of 2000 Å or less.
And an aggregate of filaments of inorganic long fibers consisting of a fiber bundle of 200 filaments / yarn, which is sized with 0.5 to 1 wt% of polyvinyl alcohol.

First step: continuous treatment in air at 600 ° C. to remove the sizing agent, second step: ultrasonically dispersed MgO.Al ₂ O ₃ .SiO.
₂ (Glass ceramics) A fine powder slurry solution (containing 10 wt% of polyethylene oxide as a fiber sizing agent) was passed through to adhere the above glass ceramics to the fibers. Third step; subsequently, the fibers to which the above glass ceramics are adhered are passed through a slit to be formed into a wire shape, and fourth step: 1100 ° C. is continuously heat treated in nitrogen to melt and sinter the adhered glass ceramics. After that, the fifth step; further, continuous heat treatment was performed in nitrogen at 1300 ° C. The tensile test result of the obtained wire-shaped composite reinforcing material in air at 1200 ° C. shows a tensile strength of 1.7 GP.
a, the breaking elongation was 0.16%.

[Production Example 6] Using the filaments of the following inorganic long fibers, the following steps 1 to 5 were sequentially carried out to obtain glass β
-Spodumene A composite reinforcing material having a tape shape of 60 vol% of the following glass ceramics of amorphous containing a part of microcrystals and 40 vol% of the fiber was obtained.

Inorganic long fiber: Si, N, C, O, H, and the internal elemental composition is Si: 59.2 wt%, N: 3
7.5 wt%, C; 1.5 wt%, O; 1.5 wt%, H;
The fiber diameter is 10 to 20 μm, which is 0.3 wt% and mainly consists of a microcrystalline aggregate of Si ₃ N ₄ of 2000 Å or less.
And an aggregate of filaments of inorganic long fibers consisting of a fiber bundle of 200 filaments / yarn, which is sized with 0.5 to 1 wt% of polyvinyl alcohol.

First step: continuous treatment in air at 600 ° C. to remove the sizing agent, second step: ultrasonically dispersed Li containing a small amount of ZrO _2.
2 O ・ MgO ・ Al ₂ O ₃・ SiO ₂・ Nb ₂ O ₅ (glass ceramics) Fine powder slurry solution (containing 10 wt% polyethylene oxide as a fiber sizing agent) is passed through to adhere the glass ceramics to the fibers. It was Third step; subsequently, the above-mentioned glass-ceramic-attached fiber is passed through a roller to form a tape having a width of 10 mm, and the fourth step: after melting and sintering at 950 ° C., the fifth step; melting and firing at 1100 ° C. Bonding and continuous heat treatment. The tensile test result at room temperature of the obtained tape-shaped composite reinforcing material was that the tensile strength was 1.0 GPa and the breaking elongation was 0.29%.

[Manufacturing Example 7] Amorphous BaO.MgO.Al ₂ O containing a part of barium osmilite, which is a glass ceramic, is used by sequentially performing the following 1 to 5 steps using the filaments of the following inorganic long fibers. A composite reinforcing material having a wire shape with 10 vol% of ₃ · SiO _{2 and} 90 vol% of inorganic long fibers was obtained.

Inorganic long fiber: made of Al, Si, B and O, the internal elemental composition is Al: 37.1 wt%, Si; 1
8.1 wt%, B: 0.6 wt%, O: 44.2 wt%, and a fiber diameter of 10 to 20 μm, which is composed of an aggregate of mullite microcrystals and an amorphous SiO _2. so,
BN coating of 100 nm is applied on the surface,
An aggregate of filaments of inorganic long fibers consisting of 1800 filament / yarn fiber bundles sized with 1 wt% of polyvinyl alcohol.

First step: continuous treatment in air at 600 ° C. to remove the sizing agent, second step: ultrasonically dispersed BaO.MgO.Al ₂ O ₃
・ SiO ₂ (glass ceramics) fine powder slurry solution (1 polyethylene oxide as a fiber sizing agent)
The glass-ceramics described above were attached to the fibers by passing through the glass fiber. Third step; subsequently, the fibers to which the above glass ceramics are adhered are passed through a slit to be formed into a wire shape, and fourth step: 1100 ° C. is continuously heat treated in nitrogen to melt and sinter the adhered glass ceramics. After that, the fifth step; further, continuous heat treatment was performed in nitrogen at 1300 ° C.
The tensile test result of the obtained wire-shaped composite reinforcing material in air at 1200 ° C. shows a tensile strength of 1.3 GP.
a, the elongation at break was 0.10%.

[Manufacturing Example 8] Using the filaments of the following inorganic long fibers, the following steps 1 to 5 were sequentially carried out to obtain glass β
-Spodumene A composite reinforcing material having a tape shape of 60 vol% of the following glass ceramics of amorphous containing a part of microcrystals and 40 vol% of the fiber was obtained.

Inorganic long fiber: made of Al, Si, B, O, the internal elemental composition is Al: 37.1 wt%, Si; 1
Fiber of 8.1 wt%, B: 0.6 wt%, O: 44.2 wt%, comprising a fine crystalline aggregate of γ- or η-alumina and an aggregate of amorphous SiO _2. Diameter is 1
An aggregate of filaments of inorganic long fibers consisting of a fiber bundle of 1800 filaments / yarn having a BN coating of 0 to 20 μm and a surface of 100 nm and sized with 0.5 to 1 wt% of polyvinyl alcohol.

First step: continuous treatment in air at 600 ° C. to remove the sizing agent, second step: ultrasonically dispersed Li containing a small amount of ZrO _2.
2 O ・ MgO ・ Al ₂ O ₃・ SiO ₂・ Nb ₂ O ₅ (glass ceramics) Fine powder slurry solution (containing 10 wt% polyethylene oxide as a fiber sizing agent) is passed through to adhere the glass ceramics to the fibers. It was Third step; subsequently, the above-mentioned glass-ceramic-attached fiber is passed through a roller to form a tape having a width of 10 mm, and the fourth step: after melting and sintering at 950 ° C., the fifth step; melting and firing at 1100 ° C. Bonding and continuous heat treatment. The tensile test result at room temperature of the obtained tape-shaped composite reinforcing material was that the tensile strength was 0.7 GPa and the breaking elongation was 0.18%.

Example 1 The wire-shaped composite reinforcing material for an advanced composite material produced in Production Example 1 was cut into a length of 90 mm and unidirectionally placed on a carbon plate to which an aluminum foil was attached. It was attached so that the width would be 50 mm. A TiAl (intermetallic compound) atomized powder having a particle size of 90 to 150 μm is vapor-deposited by a vacuum plasma spray method in an argon atmosphere at 20 Torr on the wire-shaped reinforcing material aligned in one direction and on the gap to form a wire shape. A prepreg sheet of a composite reinforcing material for advanced composite material using the composite reinforcing material of 65 vol% of Ti and 35 vol% of TiAl was obtained. A laminate of the obtained prepreg sheets was hot-pressed for 1 minute at 950 ° C. and 10 MPa to give a width of 50 mm, a length of 90 mm and a thickness of 6 mm.
An intermetallic compound (TiAl) composite material using a composite reinforcing material for a wire-shaped advanced composite material of mm was manufactured. The bending strength test results of the obtained intermetallic compound composite material at room temperature to 900 ° C. showed almost no change in strength from room temperature to 900 ° C., and the average value of the three-point bending strength was 1.6 GPa.

For comparison, instead of using the composite reinforcing material for advanced composite materials described above, a prepreg and a composite material were manufactured in exactly the same manner as above using only the filaments of the inorganic long fibers used in Production Example 1. . When the bending strength of this composite material was measured, it was difficult to develop high strength due to the reaction between the fiber and TiAl during prepreg production by vacuum plasma spraying and fiber cutting, and the reaction between the fiber and TiAl during hot pressing. And the three-point bending strength at room temperature is 0.1
It stopped at about 0.2 GPa.

[Example 2] The composite reinforcing material having a wire shape manufactured in Manufacturing Example 1 was cut into a length of 120 mm, aligned in one direction, and mounted on a carbon die (the carbon die is a rectangle). , A split type of upper pig and lower pig was used. Also, there are several holes in each of the upper, lower, and side surfaces so that molten metal can enter. Then, the carbon die equipped with the composite reinforcement is
After preheating at 0 ° C. for 30 minutes, it was placed in a squeeze cast machine and quickly placed in a mold kept at 400 ° C. After that, the mold was closed, and the aluminum alloy A6061 kept at 700 ° C. was melted. Then, it was pressed into a carbon die equipped with a composite reinforcing material at a pressure of 100 MPa with a flanger, and naturally cooled while keeping the pressure for 40 seconds. , Size is width 40mm, length 120mm, thickness 5mm
And the wire-shaped composite reinforcing material is 40 vol%, A6
A metal-based composite material using a wire-shaped composite reinforcing material with 061 being 60 vol% was manufactured (squeeze casting method).

The obtained metal-based composite material was exposed to air at 400 ° C.
As a result of the three-point bending test, the same result as that at room temperature was obtained, and the average value of the three-point bending strength was 1.3 GPa.

[Example 3] The composite reinforcing material having a tape shape produced in Production Example 2 was cut into a length of 60 mm and aligned in one direction on a carbon plate to which an aluminum foil was attached. , So that the width is 60 mm. On the tape-shaped reinforcing material aligned in this one direction and on the gap, a particle size of 60-
90 μm Ti-6Al-4V (titanium alloy, α + β
Type) Atomized powder is vapor-deposited by a vacuum plasma spray method in an argon atmosphere at 20 Torr to form a prepreg sheet of a metal-based composite material using a tape-shaped composite reinforcing material of 50 vol% and a titanium alloy of 50 vol%. Obtained.

The obtained prepreg sheet was placed at 0 ° and 90 °.
The alternately laminated layers were hot pressed at 700 ° and 20 MPa for 1 minute to produce a metal-based composite material using a tape-shaped composite reinforcing material having a width of 60 mm, a length of 90 mm and a thickness of 4 mm. The average value of the tensile strength of the obtained metal-based composite material at 500 ° in air was 0.6 GPa.

Example 4 The composite reinforcing material having a wire shape produced in Production Example 3 was cut into a length of 90 mm,
The aluminum plate was attached on a carbon plate, which was aligned in one direction so that the width was 50 mm. A particle size of 90 is provided on the wire-shaped reinforcing material aligned in this direction and on the gap.
˜150 μm TiAl (intermetallic compound) atomized powder is vapor-deposited by a low pressure plasma spray method in an argon atmosphere at 20 Torr, and is a metal-based composite using a wire-shaped composite reinforcing material of 65 vol% and TiAl 35 vol%. A prepreg sheet of material was obtained.

The prepreg sheets thus obtained were aligned in one direction and laminated to form a sheet under conditions of 950 ° C. and 10 MPa.
By hot pressing for 50 minutes, width 50mm, length 90
mm, a metal composite material using a wire-shaped composite reinforcing material having a thickness of 6 mm was produced. The tensile strength test results of the obtained intermetallic compound composite material at room temperature to 900 ° C. showed almost no change in strength from room temperature to 900 ° C., and the average tensile strength was 1.3 GPa.

For comparison, instead of using the composite reinforcing material for advanced composite material described above, a prepreg and a composite material were manufactured in exactly the same manner as above using only the filaments of the inorganic long fibers used in Production Example 3. Equal volume content of fibers). The flexural strength of this composite material was measured to find that the fibers and T
Due to the reaction with iAl, the fiber cutting, or the reaction between the fiber and TiAl in the hot press, it was difficult to develop high strength, and the tensile strength at room temperature was about 0.1 to 0.2 GPa.

Example 5 The composite reinforcing material having a wire shape produced in Production Example 3 was cut into a length of 120 mm, aligned in one direction, and mounted on a carbon die (the carbon die is a rectangle). , The upper pig, the lower pig split type, and there are several holes on the upper, lower and side,
Molten metal is allowed to penetrate). Then, the carbon die equipped with the composite reinforcing material is heated at 700 ° C. for 30 minutes.
After preheating for 5 minutes, install on a squeeze cast machine and
It was quickly installed in a mold kept at 00 ° C. After that, the mold was closed and aluminum alloy A60 kept at 700 ° C.
After melting 61, pressure 100MP with flanger
In a, press-fit into a carbon die equipped with a composite reinforcing material, let it cool naturally while maintaining the pressure for 40 seconds, and measure 40 mm in width, 120 mm in length, and 5 mm in thickness. Material is 40vol%, A6061 is 60vo
A metal-based composite material using 1% of wire-shaped composite reinforcing material was manufactured (squeeze casting method).

The obtained metal-based composite material was exposed to air at 400 ° C.
As a result of the 3-point bending test, the same result as that at room temperature was obtained, and the average value of the 3-point bending strength was 1.2 GPa.

Example 6 The tape-shaped composite reinforcing material produced in Production Example 4 was cut into a length of 60 mm, and aligned in one direction on a carbon plate to which an aluminum foil was attached. It was attached so that the width would be 60 mm. On the tape-shaped reinforcing material aligned in this one direction and on the gap, a particle diameter of 60 to 9
0 μm Ti-6Al-4V (titanium alloy, α + β type)
Atomized powder was vapor-deposited by a low pressure plasma spraying method in an argon atmosphere at 20 Torr to obtain a prepreg sheet of a metal-based composite material using a tape-shaped composite reinforcing material of 50 vol% and titanium alloy of 50 vol%. .

Obtained prepreg sheet, 0 ° / 90 °
By alternately hot-pressing the alternately laminated layers under conditions of 700 ° and 20 MPa for 1 minute, a metal composite material using a tape-shaped composite reinforcing material having a width of 60 mm, a length of 90 mm and a thickness of 4 mm was manufactured. The average value of the tensile strength of the obtained metal-based composite material at 500 ° C. in the atmosphere was 0.5 GPa.

Example 7 The wire-shaped composite reinforcing material produced in Production Example 5 was cut into a length of 90 mm,
The aluminum plate was attached on a carbon plate, which was aligned in one direction so that the width was 50 mm. A particle size of 90 is provided on the wire-shaped reinforcing material aligned in this direction and on the gap.
˜150 μm TiAl (intermetallic compound) atomized powder is vapor-deposited by a low pressure plasma spray method in an argon atmosphere at 20 Torr, and is a metal-based composite using a wire-shaped composite reinforcing material of 65 vol% and TiAl 35 vol%. A prepreg sheet of material was obtained.

The obtained prepreg sheets were aligned in one direction and laminated, and hot-pressed for 1 minute at 950 ° C. and 10 MPa to form a wire-shaped composite having a width of 50 mm, a length of 90 mm and a thickness of 6 mm. A metal composite material using a reinforcing material was manufactured. The tensile strength test results of the obtained intermetallic compound composite material at room temperature to 900 ° C.
There was almost no change in strength from room temperature to 900 ° C., and the average tensile strength was 1.3 GPa.

For comparison, instead of using the composite reinforcing material for advanced composite materials described above, a prepreg and a composite material were manufactured in exactly the same manner as above, using only the filaments of the inorganic long fibers used in Production Example 5. Equal volume content of fibers). The flexural strength of this composite material was measured to find that the fibers and T
Due to the reaction with iAl, the fiber cutting, or the reaction between the fiber and TiAl in the hot press, it was difficult to develop high strength, and the tensile strength at room temperature was about 0.1 to 0.2 GPa.

[Example 8] The composite reinforcing material having a wire shape produced in Production Example 5 was cut into a length of 120 mm, aligned in one direction, and mounted on a carbon die (the carbon die is a rectangle). , The upper pig, the lower pig split type, and there are several holes on the upper, lower and side,
Molten metal is allowed to penetrate). Then, the carbon die equipped with the composite reinforcing material is heated at 700 ° C. for 30 minutes.
After preheating for 5 minutes, install on a squeeze cast machine and
It was quickly installed in a mold kept at 00 ° C. After that, the mold was closed and aluminum alloy A60 kept at 700 ° C.
After melting 61, pressure 100MP with flanger
In a, press-fit into a carbon die equipped with a composite reinforcing material, let it cool naturally while maintaining the pressure for 40 seconds, and measure 40 mm in width, 120 mm in length, and 5 mm in thickness. Material is 40vol%, A6061 is 60vo
A metal-based composite material using 1% of wire-shaped composite reinforcing material was manufactured (squeeze casting method).

The obtained metal-based composite material was exposed to air at 400 ° C.
As a result of the three-point bending test, a result equivalent to the result at room temperature was obtained, and the average value of the three-point bending strength was 1.0 GPa.

[Example 9] The composite reinforcing material having the tape shape produced in Production Example 6 was cut into a length of 60 mm and aligned in one direction on a carbon plate to which an aluminum foil was attached. It was attached so that the width would be 60 mm. On the tape-shaped reinforcing material aligned in this one direction and on the gap, a particle diameter of 60 to 9
0 μm Ti-6Al-4V (titanium alloy, α + β type)
Atomized powder was vapor-deposited by a low pressure plasma spraying method in an argon atmosphere at 20 Torr to obtain a prepreg sheet of a metal-based composite material using a tape-shaped composite reinforcing material of 50 vol% and titanium alloy of 50 vol%. .

Obtained prepreg sheet, 0 ° / 90 °
By alternately hot-pressing the alternately laminated layers under conditions of 700 ° C. and 20 MPa for 1 minute, a metal-based composite material using a tape-shaped composite reinforcing material having a width of 60 mm, a length of 90 mm and a thickness of 4 mm was manufactured. The average value of the tensile strength of the obtained metal-based composite material at 500 ° in air is 0.3 GPa.
Met.

[Example 10] The composite reinforcing material having a wire shape produced in Production Example 7 was cut into a length of 90 mm and aligned in one direction on a carbon plate to which an aluminum foil was attached. It was attached so that the width would be 50 mm. TiAl (intermetallic compound) atomized powder having a particle size of 90 to 150 μm is vapor-deposited by a low pressure plasma spray method under an argon atmosphere at a pressure of 20 Torr on the wire-shaped reinforcing material aligned in this one direction and in the gap to form a wire-shaped reinforcing material. A prepreg sheet of a metal-based composite material using a composite reinforcement of 65 vol% composite reinforcement and 35 vol% TiAl was obtained.

The prepreg sheets obtained by aligning in one direction and laminated were hot-pressed for 1 minute under the conditions of 950 ° and 10 MPa to obtain a wire-shaped composite having a width of 50 mm, a length of 90 mm and a thickness of 6 mm. A metal-based composite material using a chemical strengthening material was manufactured. In the tensile strength test results of the obtained intermetallic compound composite material at room temperature to 900 ° C, there was almost no change in strength from room temperature to 900 ° C, and the average value of the tensile strength was 0.9 GPa.

For the purpose of comparison, instead of using the composite reinforcing material for advanced composite materials described above, a prepreg and a composite material were manufactured in exactly the same manner as described above using only the filaments of the inorganic long fibers used in Manufacturing Example 7. Equal volume content of fibers). The flexural strength of this composite material was measured to find that the fibers and T
Due to the reaction with iAl, the fiber cutting, or the reaction between the fiber and TiAl in the hot press, it was difficult to develop high strength, and the tensile strength at room temperature was about 0.1 to 0.2 GPa.

[Example 11] The composite reinforcing material having a wire shape manufactured in Manufacturing Example 7 was cut into a length of 120 mm, aligned in one direction, and mounted on a carbon die (the carbon die is a rectangle. , The upper pig, the lower pig split type, and there are several holes on the upper, lower and side,
Molten metal is allowed to penetrate). Then, the carbon die equipped with the composite reinforcing material is heated at 700 ° C. for 30 minutes.
After preheating for 5 minutes, install on a squeeze cast machine and
It was quickly installed in a mold kept at 00 ° C. After that, the mold was closed and aluminum alloy A60 kept at 700 ° C.
After melting 61, pressure 100MP with flanger
In a, press-fit into a carbon die equipped with a composite reinforcing material, let it cool naturally while maintaining the pressure for 40 seconds, and measure 40 mm in width, 120 mm in length, and 5 mm in thickness. Material is 40vol%, A6061 is 60vo
A metal-based composite material using 1% of wire-shaped composite reinforcing material was manufactured (squeeze casting method).

The obtained metal-based composite material was exposed to air at 400 ° C.
As a result of the three-point bending test, the same result as that at room temperature was obtained, and the average value of the three-point bending strength was 0.7 GPa.

Example 12 The composite reinforcing material having a tape shape produced in Production Example 8 was cut into a length of 60 mm,
On a carbon plate to which an aluminum foil was attached, the plates were aligned in one direction and mounted so that the width was 60 mm. On the tape-shaped reinforcing material aligned in this one direction and on the gap, a particle size of 60-
90 μm Ti-6Al-4V (titanium alloy, α + β
(Type) Atomized powder is vapor-deposited by a reduced pressure plasma spray method in an argon atmosphere at 20 Torr to produce a prepreg sheet of a metal-based composite material using a tape-shaped composite reinforcing material of 50 vol% and a titanium alloy of 50 vol%. Obtained.

Obtained prepreg sheet, 0 ° / 90 °
By alternately hot-pressing the alternately laminated layers under conditions of 700 ° C. and 20 MPa for 1 minute, a metal-based composite material using a tape-shaped composite reinforcing material having a width of 60 mm, a length of 90 mm and a thickness of 4 mm was manufactured. The average value of the tensile strength of the obtained metal-based composite material at 500 ° in air is 0.3 GPa.
Met.

[0105]

The metal-based composite material of the present invention is excellent in heat resistance, corrosion resistance and mechanical properties.

More specifically, since the metal-based composite material of the present invention uses the above-mentioned composite reinforcing material as the reinforcing material,
When composited with the above-mentioned metal or intermetallic compound which is a high melting point metal matrix, since the inorganic fibers are protected by glass ceramics or the like having low reactivity with the metal,
As a result of preventing the deterioration of the inorganic fiber due to the reaction between the inorganic fiber and the metal, it has desired mechanical properties.

Furthermore, in the metal-based composite material of the present invention, reaction deterioration during molding can be almost completely suppressed, so that mechanical properties close to theoretical values can be obtained, and
Since the composite reinforcing material is finished to have almost no difference in the coefficient of thermal expansion of the constituent components as compared with the SiC / C composite fiber, the metal-based composite material of the present invention has no problem in the heat cycle, and It can be manufactured at a significantly low cost.

Further, the composite reinforcing material can obtain strength close to the ROM value even when the filament is used at various Vf, and the content ratio of the filament can be freely controlled. Had a low V
Even in the composite of f and high Vf, desired properties can be imparted.

Therefore, the composite material of the present invention is useful as a molding material in the fields of space and aviation.

[Brief description of drawings]

FIG. 1 is a view of a composite reinforcing material 1 used in the present invention.
It is a 1st part perspective view which shows an example.

FIG. 2 is a partial perspective view showing another example of the composite reinforcing material used in the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C22F 1/18 H (72) Inventor Mitsuhiko Sato 5 Ube Industries Ltd., 5 1978, Kogushi, Ube City, Yamaguchi Prefecture Company Inorganic Material Research Institute Advanced Material Utilizing Gas Generator Research Institute Ube Room (72) Inventor Makoto Tamura 5 1978, Kozugushi, Ube City, Yamaguchi Prefecture Ube Industrial Co., Ltd. Advanced Material Utilizing Gas Co., Ltd. Generator Research Laboratory Ube Room (72) Inventor Shinji Kajii 5 1978, Ogushi, Ube City, Yamaguchi Prefecture 5 1978, Ube Industries, Ltd. Yasuo 5 1978 Kogushi, Ube City, Yamaguchi Prefecture 5 Ube Kosan Co., Ltd. Advanced Materials Utilized Gas Generator Research Institute, Ube Division, Materials Research Laboratory (72) Inventor Yoshikatsu Harada 5 1978, Kogushi, Obe, Ube City, Yamaguchi Prefecture Ube Industries Ltd. Advanced Materials Utilization Gas Generator Research, Inc. Tokou part indoor

Claims (8)

[Claims] 1. A composite reinforcing material comprising a plurality of composite reinforcing materials and a metal or an intermetallic compound existing in a gap between the composite reinforcing materials, wherein the composite reinforcing material comprises a large number of filaments of inorganic long fibers and filaments of each filament. A metal-based composite material comprising glass and / or glass ceramics present in a gap and having a wire shape or a tape shape. 2. The inorganic long fibers are (a) substantially Si.
And (b) the above amorphous and β-S of 10000 Å or less, and Ti and / or Zr, C, and O.
a crystalline aggregate of iC and TiC and / or ZrC,
Or (c) the above crystalline material and S existing in the vicinity thereof
iOx and TiOx and / or ZrOx (0 <x ≦ 2)
And an elemental composition of Si is 30 to 80 wt% and Ti and / or Zr is 0.
05-8 wt%, C 15-69 wt%, O 0.1-2
The metal-based composite material according to claim 1, wherein the content is 0.0 wt%. 3. The inorganic long fibers are (a) substantially Si.
And C, amorphous, (b) β less than 10,000 Å
-SiC crystalline, (c) the amorphous and crystalline,
Or (d) a mixed system of the amorphous and / or crystalline material and an aggregate of carbon, the elemental composition of which is S
i is 30-80 wt%, C is 20-70 wt%, H is 2 wt%
The metal-based composite material according to claim 1, wherein: 4. The inorganic long fibers are (a) substantially Si.
And an amorphous material composed of C and O, or (b) 10000
Å β-SiC crystalline aggregates below and amorphous Si
It is an aggregate composed of O ₂ and its elemental composition is S
i is 30 to 80 wt%, C is 10 to 65 wt%, and O is 0.0
The metal-based composite material according to claim 1, wherein the content is 5 to 25 wt% and H is 2 wt% or less. 5. The inorganic long fiber comprises Si, N, O,
C, H, and one or more metals (M) selected from the group consisting of Group II to Group VIII metal elements of the Periodic Table of Elements, and having an X-ray small angle scattering intensity ratio of 1 ° and 0.5. It is a substance that is 1 to 20 times in any of °, and the ratio of each element is atomic ratio, N / Si is 0.3 to 3,
Is 15 or less, C / Si is 7 or less, H / Si is 1 or less, M
/ Si is 5 or less, The metal type composite material of Claim 1 characterized by the above-mentioned. 6. The inorganic long fibers are (a) substantially Al.
And / or (b) γ- and η-alumina microcrystals, and amorphous Si.
The metal-based composite material according to claim 1, which is an aggregate with O ₂ . 7. The metal-based composite material according to claim 1, wherein the metal is a titanium alloy, an aluminum alloy or a magnesium alloy. 8. The metal-based composite material according to claim 1, wherein the intermetallic compound is a titanium-aluminide-based or niobium-aluminide-based intermetallic compound.