JPS61284541A - Inorganic fiber reinforced metallic composite material - Google Patents

Abstract

PURPOSE:To develop an inorg. fiber reinforced metallic composite material having excellent mechanical strength by incorporating fibers consisting of inorg. materials such as SiC, TiC, ZrC or SiO2, TiO2, ZrO2, etc., as a reinforcing material into Al, Mg and Ti light metals. CONSTITUTION:The inorg. fiber reinforced metallic composite material having the excellent mechanical strength is developed by incorporating the inorg. fibers at 10-70vol% as the reinforcing material into the light alloys such as Al, Mg and Ti and the alloy thereof as the matrix metal. The inorg. fibers for which beta-SiC, TiC, ZrC consisting of Si, Ti, Zr, C and O or the solid soln. thereof as well as ultrafine crystalline particles of Ti1-x, Zr1-x(0<x<1) having <=500Angstrom grain size, amorphous aggregate of SiO2, TiO2 and ZrO2 and the mixtures of the above-mentioned ultrafine amorphous and crystalline particle aggregates are used for the inorg. fibers to be used as the reinforcing material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a material with excellent mechanical properties that uses inorganic fibers mainly made of silicon, titanium, zirconium, carbon, and oxygen as a reinforcing material and a metal or alloy (hereinafter abbreviated as metals) as a matrix. This invention relates to inorganic fiber-reinforced metal composite materials (hereinafter abbreviated as composite materials).

Until now, silicon carbide fibers obtained by spinning, infusible, and firing an organosilicon polymer called polycarbosilane have been used as fibers to strengthen metals such as aluminum, magnesium, and titanium. JP-A-52-7811, JP-A-52-2
No. 4111, Tokukai Sho 5! No. l-30407, Japanese Patent Application Publication No. 1983
It is disclosed in various publications such as No.-26305. However, as described in the reference example below, the strength of silicon carbide fibers decreases significantly when immersed in molten metal such as aluminum, so the strength of composite materials with aluminum as a matrix is The theoretical strength calculated from the fiber volume ratio is also lower.

An object of the present invention is to solve the above problems and provide a composite material with excellent mechanical properties.

Another object of the present invention is to provide a composite material with excellent bonding strength between a metal matrix and inorganic fibers.

Another object of the present invention is to provide a composite material with excellent compatibility between a matrix and inorganic fibers and with excellent reinforcement efficiency by the inorganic fibers.

Still another object of the present invention is to provide a composite material in which the strength of inorganic fibers is less reduced during formation of the composite material.

Another object of the invention is to provide a composite material suitable for mass production.

The composite material of the present invention has an inorganic fiber as a reinforcing material, a metal or an alloy as a matrix, α, the inorganic fiber is an amorphous material consisting essentially of (i) , 5 i , M , C, and O; or (ii) substantially consisting of a solid solution of β-5sC, MC, β-8iC and MC, each crystalline ultrafine particle having a particle size of 500A or less, and amorphous Sin and MO. aggregate, or (iii) the amorphous substance of (i) above and the above (
ii) A mixed system of crystalline ultrafine particle aggregates, (wherein M in the above formula represents Ti or Zr, and 0〈z〉
1) is an inorganic fiber containing silicon, titanium or zorconium, carbon and oxygen; and the fiber strength reduction rate is about 30X or less, and the interlaminar shear strength of the C6 composite material is about 8 kg/l112 or more, and d, the tensile strength in the direction perpendicular to the fibers of the composite material is about 6 k.
g/w2 or more, and e, the ratio of fatigue limit to tensile strength of the composite material is about 0.
It is an inorganic fiber reinforced metal composite material consisting of 4 or more.

The inorganic fiber used in the present invention is European Patent No. 30
It is described in No. 145 and No. 37249,
It can be manufactured as follows.

+11 It has a number average molecular weight of about 500 to 1000o and has a main chain skeleton mainly consisting of structural units of the formula +5i-CH, +, and the silicon atoms in the formula essentially consist of hydrogen atoms, lower alkyl groups, and phenyl groups. Polycarbosilane having two side chain groups selected from the group and (2) a metalloxane bonding unit + M-0-j- (where M represents Tj or Zr) having a number average molecular weight of about 500 to 10 cioo and has a main chain skeleton consisting of siloxane bonding units + 5i - 0 ÷, and the ratio of the total number of metalloxane bonding units to the total number of siloxane bonding units is 30:1 to 1.
: within the range of 30, most of the silicon atoms of the siloxane bonding unit have one or two side chain groups selected from the group consisting of lower alkyl groups and phenyl groups, and the metalloxane bonding unit A polymetallosiloxane in which most of the metal atoms have one or two lower alkoxy groups as side chain groups, +5t-CH of the polycarbosilane, total number of 10 structural units to +M-0+( of the polymetallosiloxane) However, MFiT
i or Zr) bond units and +5i-0 part bond units in a quantitative ratio within the range of 100:1 to 1:100, and the resulting mixture is reacted in an organic solvent. At least a portion of the silicon atoms of the polycarbosilane are exchanged with at least one portion of the silicon atoms and/or metal atoms of the polymetallosiloxane via oxygen atoms by heating in an atmosphere inert to By combining, the number average molecular weight of the crosslinked polycarbosilane portion and polymetallosiloxane portion is approximately 1000 to 500.
00 organometallic polymer, a second step of spinning a spinning dope of the polymer, a third step of making the spun fiber infusible under tension or no tension, and infusibility. From the fourth step of firing the spun fibers in a vacuum or in an inert gas atmosphere at a temperature range of 800 to 1800°C, inorganic fibers consisting essentially of Si, Ti, C, 0, or essentially Si, Zr, Inorganic fibers made of C and O can be produced respectively.

As another method, the main chain skeleton mainly represented by the general formula % (wherein R represents a hydrogen atom, a lower alkyl group, or a phenyl group) and a number average molecular weight of 200 to
IQ, 000 polycarbosilane, and general formula (where M in the formula represents Ti or Zr, and X has 1 carbon number
an organometallic compound represented by an alkoxy group, phenoxy group or acetylacetoxy group having ~20 units, +5i-CH of the polycarbosilane, the total number of 1,000 structural units vs. +M-0+ (of the organometallic compound). However, "f"
indicates Ti or Zr), the ratio of the total number of structural units is 2:
In addition to the quantitative ratio within the range of 1 to 200:1, at least a portion of the silicon atoms of the above-mentioned supporting carbosilane are converted to the metal atoms of the organometallic compound by a heating reaction in an atmosphere inert to the reaction. A first step of bonding via oxygen atoms to produce an organometallic polymer having a number average molecular weight of about 700 to 100,000, a second step of preparing and spinning a spinning dope of the organometallic polymer; A third step is to infusible the spun fibers under tension or no tension, and the infusible spun fibers are infusible in a vacuum or in an inert gas atmosphere.
Producing inorganic fibers consisting essentially of Si, Ti, C and O, or inorganic fibers consisting essentially of Si, Zr, C and 0, each comprising a fourth step of firing at a temperature range of 00 to 1800°C. I can do it.

The proportion of each element in the inorganic fibers is as follows: St: 5α~60% by weight, Ti'il: Zr: 0.5~
35% by weight, particularly preferably 1-10% by weight, C: 25-
40% by weight, 0:0.01-30% by weight.

Inorganic fibers can be produced by blending the fibers themselves in uniaxial or multiaxial directions, or in plain weave, satin weave, mock-satin weave, twill weave,
There are methods of using it in various fabrics such as leno weave and three-dimensional fabric, and methods of using it as chopped fiber.

Next, examples of metals that can be used in the present invention include aluminum, aluminum alloys, magnesium, magnesium alloys, titanium, and titanium alloys.

The mixing ratio of the inorganic fibers in the matrix according to the present invention is preferably 10 to 70% by volume.

These metal composite materials can be manufactured by the following conventional method for manufacturing fiber-reinforced metal composite materials.

Namely, (i) diffusion bonding method, (2) melt infiltration method, (3)
(4) electrodeposition method, (5) extrusion and hot roll method, (6) chemical vapor deposition method, and (7) sintering method.

(i) According to the diffusion bonding method, inorganic fibers and matrix metal wires are arranged alternately in one direction, and the upper and lower sides thereof are covered with a thin film of matrix metal, or only the lower part is covered with the thin film and the upper A composite layer is formed by covering with matrix metal powder mixed with an organic binder, and after laminating several layers of this layer, it is heated and pressurized to produce a composite material with inorganic fibers. can. The organic binder is preferably one that volatilizes and dissipates before the temperature is raised to a temperature that produces matrix metal and carbide; for example, CMC, Nora Fine, Reson, mineral oil, etc. can be used.

Alternatively, a composite material can be obtained by arranging and laminating inorganic fibers coated with matrix metal powder mixed with an organic binder and pressurizing them under heat.

(2) According to the melt infiltration method, a composite material can be obtained by filling the gaps between arranged inorganic fibers with molten aluminum, aluminum alloy, magnesium, magnesium alloy, titanium, or titanium alloy. In this case, since the wetting property between the metal-coated fibers and the matrix metal is particularly good, the gaps between the arranged fibers can be evenly filled with the matrix metal.

(3) According to the thermal spraying method, a tape-shaped composite material can be manufactured by applying a matrix metal to the surface of arranged inorganic fibers by plasma spraying or gas spraying. The tape-shaped composite material can be used as it is, or the tape-shaped composite material can be further laminated to produce a composite material by the diffusion bonding method described in (i) above.

(4) According to the electrolytic deposition method, a matrix metal is electrolytically deposited on the surface of the fiber to form a composite, which is further layered and arranged, and a composite material can be obtained by the diffusion bonding method described in (i) above.

(5) According to the extrusion and hot roll method, fibers are arranged in one direction, sandwiched between (Ma) IJ Lux metal foils to form a sandwich, and then passed between rolls heated as necessary. Composite materials can be produced by joining fibers and matrix metals.

(6) According to the chemical vapor deposition method, the fibers are placed in a heating furnace,
For example, a mixed gas of aluminum chloride and hydrogen gas is introduced and thermally decomposed to precipitate aluminum metal on the surface of the fibers to form a composite. Further, the metal-deposited fibers can be layered and arranged to form a composite material by the diffusion bonding method described in (i) above.

()) According to the sintering method, the gaps between the arranged fibers are filled with matrix metal powder, and then heated and sintered with or without pressure to form a composite material.

The tensile strength (σ, ) of a composite material manufactured from inorganic fibers and a metal matrix is expressed by the following formula.

σ, == a t Vt + 6 br Fyσ,:
Tensile strength of composite material σf: Tensile strength of inorganic fiber σM: Tensile strength of metal matrix Vf: Volume percentage of inorganic fiber VM: Metal matrix) IJ lux volume percentage As shown in the above formula, the strength of the composite material is The volume ratio of inorganic fibers in the material increases as the volume ratio increases. Therefore,
In order to manufacture a composite material with high strength, it is necessary to increase the volume ratio of inorganic fibers to be composited. However, if the volume ratio of inorganic fiber exceeds 70%, metal matrix (IJ)
Since the amount of lux is small, the gaps between the inorganic fibers cannot be sufficiently filled with the metal matrix, so even if a composite material is produced, it will not exhibit the strength shown in the above formula. Furthermore, as the number of fibers is reduced, the hardness of the composite material decreases as shown in the previous equation, so in order to make a practical composite material, it is necessary to combine 10% or more of inorganic fibers. It is. Therefore, in producing the inorganic fiber-reinforced metal composite material of the present invention, the best effect can be obtained when the volume ratio of the inorganic fibers to be composited is 10 to 70%.

When manufacturing composite materials, as mentioned above, it is necessary to heat metals near or above their melting temperature to combine them with inorganic fibers. Therefore, the inorganic fibers and metals react with each other, resulting in a decrease in the strength of the inorganic fibers, making it impossible to fully satisfy the tensile strength (σ, ) of the composite material.

However, when the inorganic fibers used in the present invention were immersed in molten metals, no rapid deterioration of the inorganic fibers as observed in ordinary silicon carbide fibers was observed.

Preferred composite materials of the invention have an interlaminar shear strength of about 8
kg/m” or more, the tensile strength perpendicular to the fiber is approximately 6
kg/vx” or more and the ratio of fatigue limit to tensile strength is about α4 or more, and the inorganic fibers in the composite material at the time of composite material formation have an initial reaction deterioration rate of about 0.3
kg/va"·8eC-' or less and a fiber strength reduction rate of about 50% or less.

More preferable mechanical properties vary depending on the type of metal forming the matrix, and examples thereof are as follows.

The methods for measuring various mechanical properties used in the present invention will be described below.

(α) Initial reaction deterioration rate (a) For metals and alloys with a melting point of 1,200°C or less Inorganic fibers are immersed in molten metal heated to a temperature 50°C higher than the melting point of the metal for 1 minute, 5 minutes, or 10 minutes. After soaking for 30 minutes, the fibers are extracted and the fiber tensile strength is measured. From this result, the relationship between the immersion time and the fiber tensile strength, that is, the reaction deterioration curve, was determined, and the initial reaction deterioration rate (kg/m''·5ec-') was calculated from the tangent at the immersion time of 0 minutes.

(b) In the case of metals and alloys with a melting point of 1200°C or higher, inorganic fibers and metal foil are laminated, and this is heated in a vacuum to a temperature of the melting point X (0.6 to α7) of the metal foil.
The fibers are held for 5 minutes, 10 minutes, 20 minutes, and 30 minutes under pressure of 2/2, and then the fibers are extracted and the fiber tensile strength is measured. From this result, determine the initial reaction deterioration rate using the same procedure as in (a).

(b) Fiber strength reduction rate The fiber strength reduction rate is determined by determining the fiber strength at immersion time and holding time of 30 minutes each in (α), and calculating the initial strength -
The fiber strength was determined by dividing the above fiber strength by the initial strength.

The initial reaction deterioration rate indicates the degree of reaction between the fibers and the matrix when producing fiber-reinforced metals in a short period of time, and the smaller this value is, the better the compatibility between the fibers and the matrix, and the greater the reinforcing effect of the fibers. .

The fiber strength reduction rate indicates the degree of reaction between the fiber and matrix when manufacturing fiber-reinforced metal over a long period of time; the smaller this value is, the better the compatibility between the fiber and matrix, and the greater the reinforcing effect of the fiber. shows.

(C) Interlaminar shear strength test A test method for determining interlaminar shear stress with a radius of curvature of 611
110X1 on top of two 111φ bottles (length 20B)
Place a composite material made of 2x2 inorganic fibers uniaxially oriented, and set the radius of curvature at the tip! It is compressed with an indenter of 1.5M1Lφ and tested by a so-called 6-point bending method to measure the interlaminar shear stress. It is expressed in shear stress (kg/m").

(Method) A uniaxial fiber-reinforced composite material with a tensile strength thickness of 2R in the direction perpendicular to the fibers is produced, and a test piece is taken from this so that the axial direction of the test piece is perpendicular to the fiber arrangement direction.Thickness of the test piece The thickness is 2n, and a curvature of 12511IR is applied in the thickness direction of the central part to a thickness of approximately 1fi.The tensile speed was 1 pul/min.Tensile strength (kg/
m”).

The interlaminar shear strength and tensile strength in the direction perpendicular to the fibers are
This is an index that indicates the strength of bonding with IJ lux fibers.

(6) F-labor test A round bar of 10φ x 1005m was manufactured so that the axial direction of the composite material in which inorganic fibers were oriented in a uniaxial direction was the long axis direction, and this was processed into a specified rotary bending fatigue test piece. Is the capacity 1.5 kg? ? + rotational bending fatigue test was carried out at 107
The fatigue strength of each cycle was determined and used as the fatigue limit.

The ratio of fatigue limit to tensile strength is an indicator of the strength of the bond between the matrix and the fibers.

The inorganic fiber-reinforced metal composite material obtained by the present invention has excellent mechanical properties such as tensile strength, high modulus of elasticity, and excellent heat resistance and abrasion resistance. It is used as a variety of materials such as industrial materials, construction machinery materials, marine development (including Udo) materials, automobile materials, and food materials.

Production method of inorganic fiber (I) 6 parts by weight of polyborosiloxane was added to 100 parts by weight of polydimethylsilane synthesized by dechlorination condensation of somethylsochlorosilane with metallic sodium, and 350 parts by weight of polyborosiloxane was added to
Ti A polytitanium carbosilane consisting of 100 parts of carbosilane units and 10 parts of titanoxane of the formula +Ti-0+ was obtained by adding an alkoxide and carrying out crosslinking polymerization at 340° C. in nitrogen. This polymer was melt-spun, treated to make it infusible at 190°C in air, and subsequently calcined at 1300°C in nitrogen.
Fiber diameter 13 μ and tensile strength 310 kg used in the present invention
An inorganic fiber (I) containing 6% by weight of a titanium element mainly composed of silicon, titanium, carbon and oxygen and having an elastic modulus of 16 t/m" and an elastic modulus of 16 t/m" was obtained. The obtained inorganic fiber is 5iXT
i.

Amorphous consisting of C and O, and β-SiC, Tic.

A solid solution of β-Etc and Tic and a mixture of each crystalline ultrafine particle with a grain size of Z(i) of about 50.4 and an aggregate of amorphous Sin and Tic2 It is an inorganic fiber consisting of the system.The elemental composition of the inorganic fiber is 5
i45% by weight, Ti3. Q weight%, C25.4 weight%,
It was 024.7% by weight.

Production method of inorganic fiber (2) Tetrakis acetylacetonate turconium was added to the precarbosilane obtained as described above, and the mixture was heated at 65% in nitrogen.
A polyturconocarbosilane consisting of 100 parts of cycarfosilane and 60 parts of zirconoxane of the formula +Zr-0+ was obtained by crosslinking polymerization at 0°C. This polymer was dissolved in benzene and dry spun, treated to be infusible at 170°C in air, and then calcined at 1200°C in nitrogen.
Mainly silicon, zirconium, fiber diameter 10 μ, tensile strength 350 kll/m", elastic modulus 1 Bt/1 m"
Work and rj Eka 1,5, 7=tsu4゜4.5 ii
An amorphous inorganic fiber (2) was obtained. The elemental composition of the inorganic fiber is Si 46.4% by weight, Zr
6.0% by weight, C3α4% by weight, and 015.2% by weight.

[Reference Example 1] Manufacturing method of silicon carbide fiber The silicon carbide fiber obtained only from polycarbosilane used in the comparative example is manufactured as follows.

3 parts by weight of polyborosiloxane was added to 100 parts by weight of polymethylsilane synthesized by dechlorination condensation of dimethylsochlorosilane with metallic sodium, and 350 parts by weight of polyborosiloxane was added in nitrogen.
Thermal condensation was carried out at .degree. C. to obtain a polycarpodilane having a main chain skeleton mainly composed of ten carbosilane units having the formula +5j-CH and having a hydrogen atom and a methyl group on the silicon atom of the carbosilane unit. This polymer is melt-spun,
Infusible treatment was carried out at 190°C in air, and then calcined at 1300°C in nitrogen, resulting in a fiber diameter of 13μ and a tensile strength of 3.
A silicon carbide fiber mainly consisting of silicon, carbon and oxygen was obtained with a tensile modulus of elasticity of 16 t/d and a tensile modulus of elasticity of 16 t/d.

Reference Example 2 Inorganic fibers (I) used in the present invention and silicon carbide fibers obtained only from the polycarbosilane produced in Reference Example 1 were placed in a pure aluminum (i070) molten metal at 670°C.
After immersion for 0 minutes, the decrease in strength of the side fibers was compared.

While the fiber strength reduction rate of the inorganic fiber (I) was 20%, the fiber strength reduction rate of the silicon carbide fiber was 70%. That is, the inorganic fiber (I) has excellent compatibility with the aluminum matrix.

Example 1 Inorganic fibers (I) were arranged in a uniaxial direction on pure aluminum foil (i070"l) with a thickness of 0.5 m, and the aluminum foil was covered on top of the pure aluminum foil (i070"l). To the roll,
A composite foil made by combining fiber and aluminum was manufactured. 27 sheets of this composite foil were stacked and left under vacuum at a temperature of 670° C. for 10 minutes, and then hot-breathed at 600° C. to produce an inorganic fiber-reinforced aluminum composite material mainly consisting of silicon, titanium, carbon, and oxygen. The fiber content of this composite material is 30% by volume. A scanning electron micrograph of a cross section of the obtained composite material is shown in FIG. As shown in FIG. 1, it can be seen that the composite of inorganic fiber and aluminum is extremely good. The tensile strength of the manufactured composite material is 74
9/m", and the elastic modulus was 8,500 kg/m".

Comparative Example 1 Inorganic edge used in the present invention! A silicon carbide fiber-reinforced composite material was produced in the same manner as in Example 1 except that the silicon carbide fiber obtained in Reference Example 1 was used instead of (I). The fiber content of this composite material is 30% by volume. The resulting composite material has a tensile strength of 37.9/vs” and an elastic modulus of 61.
The strength is 1.3'00 kg/2, which is significantly lower than the composite material of the present invention of Example 1. This is because the strength of silicon carbide fibers decreases to about 50% of the original strength when immersed in molten aluminum at 670°C for 10 minutes.

Comparative Example 2 A carbon fiber-reinforced composite material was produced in the same manner as in Example 1, except that polyacrylonitrile-based and high-strength carbon fibers were used instead of the inorganic fiber (I) used in the present invention. The fiber content of this composite material is 30% by volume. The obtained composite material has a tensile strength of 25 klJ/m'', which is significantly lower than the composite material of the present invention of Example 1.

The initial reaction deterioration rate, fiber strength reduction rate, interlaminar shear strength, tensile strength perpendicular to the fibers, and ratio of fatigue limit to tensile strength obtained for the above aluminum composite materials are summarized in Table 1.

This shows that the inorganic fiber reinforced composite material of the present invention is superior to other reinforced fiber composite materials.

Example 2 Inorganic fibers (I) were arranged in a uniaxial direction on aluminum alloy foil (6061) with a thickness of 0.5, covered with aluminum alloy foil, and hot rolled at a temperature of 670°C. A composite foil made of fibers and aluminum alloy was manufactured using this method. 27 sheets of this composite foil were stacked and left under vacuum at a temperature of 670°C for 10 minutes, and then subjected to hot 7' heating at 600°C to produce an inorganic fiber-reinforced aluminum composite material mainly consisting of silicon, titanium, carbon, and oxygen. . The fiber content of this composite material was 30% by volume.

Comparative Example 6 Silicon carbide fiber reinforcement was carried out in the same manner as in Example 2, except that silicon carbide fiber obtained only from the polycarbosilane produced in Reference Example 1 was used instead of the inorganic fiber (I) used in the present invention. A composite material was produced.

The fiber content of this composite material was 30% by volume.

The initial reaction deterioration rate, fiber strength reduction rate, interlaminar shear strength, tensile strength in the direction perpendicular to the fibers, and the ratio of fatigue limit to tensile strength obtained for the above aluminum alloy composite materials are summarized in Table 2.

Table 2 shows that the inorganic fiber reinforced composite material of the present invention is superior to other reinforced fiber composite materials.

Example 3 Inorganic fibers (9) arranged in a uniaxial direction were coated with titanium metal to a thickness of 0.1 to 10 μm using a thermal spraying device.

The inorganic fibers are layered and arranged, and the gaps between the laminated layers are filled with titanium metal powder and pressure molded. The molded body is pre-fired at 520°C for 3 hours in a hydrogen gas atmosphere, and then further at 1150°C in an argon atmosphere. Then, 200 was hot pressed for 6 hours while applying a pressure of 51/i to obtain an inorganic fiber-reinforced titanium composite material mainly consisting of silicon, turconium, carbon, and oxygen. This composite material contains 45% by volume of inorganic fibers and has a tensile strength of 160%.
kg/art”, it showed approximately 2.7 times the strength of titanium.

Comparative Example 4 Silicon carbide fiber-reinforced titanium was produced in exactly the same manner as in Example 6, except that instead of using inorganic fibers (6), silicon carbide wax fibers obtained only from the polycarbosilane produced in Reference Example 1 were used. A composite material was produced. The tensile strength of the composite material obtained was 85 Yu/ml'', which is inferior to the composite material of the present invention obtained in Example 3.

The initial reaction deterioration rate, fiber strength reduction rate, interlaminar shear strength, tensile strength in the direction perpendicular to the fibers, and the ratio of fatigue limit to tensile strength obtained for the above titanium composite materials are shown in Table 3.

Table 3 It can be seen that the inorganic fiber reinforced composite material of the present invention is superior to other reinforced fiber composite materials.

Example 4 Titanium alloy (Ti-6Al-aV) was applied to 01 to 10 inorganic fibers (2) arranged in a uniaxial direction using a thermal spraying device.
It was coated to a thickness of μ. These inorganic fibers are layered and arranged, and the gaps between the layers are filled with titanium alloy powder and pressure molded.
After preliminarily firing the molded body at 520°C for 5 hours in a hydrogen gas atmosphere, it was further fired at 1150°C in an argon atmosphere for 20 hours.
Hot pressing was carried out for 3 hours while applying a pressure of 0 Yu/cfl to obtain an inorganic fiber-reinforced titanium alloy composite material mainly consisting of silicon, zirconium, carbon, and oxygen.

The fiber content of this composite material was 45% by volume.

Comparative Example 5 A silicon carbide fiber-reinforced titanium alloy was produced in exactly the same manner as in Example 4, except that instead of using inorganic fiber (2), silicon carbide fiber obtained only from the polycarbosilane produced in Reference Example 1 was used. A composite material was produced.

The initial reaction deterioration rate, fiber strength reduction rate, interlaminar shear strength, tensile strength perpendicular to the fibers, and ratio of fatigue limit to tensile strength obtained for the above titanium alloy composite materials are summarized in Table 4.

Table 4 This shows that the inorganic fiber reinforced composite material of the present invention is superior to other reinforced fiber composite materials.

Example 5 Inorganic fiber (
I) were arranged in a uniaxial direction, a magnesium foil was placed thereon, and a composite foil made of fibers and aluminum was produced by hot rolling at a temperature of 670°C. 27 sheets of this composite foil were stacked and left at a temperature of 670°C for 10 minutes in an argon atmosphere, and then hot pressed at 600°C to produce an inorganic fiber-reinforced magnesium composite material mainly consisting of silicon, titanium, carbon, and oxygen. The fiber content of this composite material is 30% by volume.

Comparative Example 6 A silicon carbide fiber-reinforced magnesium composite was prepared in exactly the same manner as in Example 5, except that instead of using inorganic fibers (■), silicon carbide fibers obtained only from the polycarbosilane produced in Reference Example 1 were used. manufactured the material.

Table 5: Initial reaction deterioration rate, fiber strength reduction rate, interlaminar shear strength, tensile strength perpendicular to the fibers, and fatigue limit obtained for the above magnesium composite materials It can be seen that it is superior to composite materials.

Example 6 Inorganic fibers (I) were arranged in a uniaxial direction on a magnesium alloy foil (4891) with a thickness of 0.5 dew, and the magnesium alloy foil was placed on top of the inorganic fibers (I), and heated at a temperature of 670°C. A composite foil made of fibers and magnesium alloy was manufactured in a roll. 27 sheets of this composite foil are stacked and left at a temperature of 670°C for 10 minutes in an argon atmosphere, and then hot pressed at 600°C to produce an inorganic fiber-reinforced magnesium alloy composite material mainly consisting of silicon, titanium, carbon, and oxygen. did. The fiber content of this composite material is 30% by volume
Met.

Comparative Example 7 A silicon carbide fiber-reinforced magnesium alloy was prepared in exactly the same manner as in Example 6, except that instead of using the inorganic fiber (I), silicon carbide fiber obtained only from the polycarbosilane produced in Reference Example 1 was used. A composite material was produced.

The initial reaction deterioration rate, fiber strength reduction rate, interlaminar shear strength, tensile strength in the direction perpendicular to the fibers, and the ratio of fatigue limit to tensile strength obtained for the above magnesium alloy composite materials are summarized in Table 6.

It can be seen from the table that the inorganic fiber reinforced composite material of the present invention is superior to other reinforced fiber composite materials.

Example 7 Inorganic fibers obtained from inorganic fiber (2) were plain woven (placing: 6 warps and 6 wefts, one yarn consists of 500 fibers) using a thermal spraying device to coat titanium metal α1. ~1
It was coated to a thickness of 0μ. The plain weave inorganic fibers are layered and arranged, and the gaps between the laminated plain weaves are filled with titanium metal powder and pressure molded.
After pre-calcining for an additional 1150 hours under an argon atmosphere.
C. for 5 hours while applying a pressure of 200 ky/d to obtain an inorganic fiber-reinforced titanium composite material mainly consisting of silicon, turconium, carbon, and oxygen. - This composite material contained 45% by volume of inorganic fibers, and its tensile strength was 100:9/m'', about 1.7 times the strength of titanium.

Comparative Example 8 Silicon carbide fiber-reinforced titanium was produced in exactly the same manner as in Example 2, except that the silicon carbide fiber obtained only from the polycarbosilane produced in Reference Example 1 was used for the inorganic fiber (2). A composite material was produced. The strength of the composite material obtained was 70 kg/m'', which is inferior to the composite material of the invention obtained in Example 2.

Example 8 Chopped inorganic fiber (I) cut into 1n length was added to magnesium alloy powder consisting of 3% aluminum, 1% manganese, 1.3% zinc, and the balance magnesium, and the mixture was thoroughly mixed. After that, stainless steel foil 70X50X
Packed into a 10 m mold and heated at 490°C under an argon atmosphere.
The magnesium alloy composite material was produced by holding it under a pressure of 200 ky/m for 1 hour and finally removing the stainless steel foil and polishing the surface.The resulting composite material contained chopped inorganic fibers. Contains 30% by volume of
Its tensile strength was 50 kg/tm''.

Comparative Example 9 A magnesium alloy composite material was obtained in the same manner as in Example 3, except that the silicon carbide fiber obtained only from the polycarbosilane produced in Reference Example 1 was used for the inorganic fiber (I). . The strength of the obtained composite material was 501 qr/m'', which is inferior to the composite material of the present invention obtained in Example 8.

[Brief explanation of drawings]

FIGS. 1A and 1B are scanning electron mirror photographs of a cross section of an aluminum composite material of inorganic fiber (I) according to the present invention.

Claims (1)

[Claims] 1. In an inorganic fiber-reinforced metal composite material having inorganic fibers as a reinforcing material and a metal or alloy as a matrix, α, the inorganic fibers are substantially composed of (i) Si, M, C, and O; amorphous,
or (ii) substantially β-SiC, MC, β-SiC and MC
A solid solution of MC_1_-_x each crystalline ultrafine particle having a particle size of 500 Å or less, and an aggregate consisting of amorphous SiO_2 and MO_2, or (iii
) A mixed system of the amorphous (i) above and the crystalline ultrafine particle aggregate (ii) (wherein M in the above formula represents Ti or Zr and represents 0<x<1). It is an inorganic fiber containing silicon, titanium or zirconium, carbon and oxygen, and b. The inorganic fiber in the composite material has an initial reaction deterioration rate of 0.3 kg/mm^2・sec^-^1 during manufacturing.
and the fiber strength reduction rate is 30% or less, c. The interlaminar shear strength of the composite material is 8 kg/mm^2
and d, the tensile strength in the vertical direction of the fibers of the composite material is 6 kg.
/mm^2 or more, and e, the ratio of the fatigue limit and tensile strength of the composite material is 0.4.
An inorganic fiber-reinforced metal composite material characterized by the above. 2. The metal is aluminum, magnesium, or titanium,
The inorganic fiber-reinforced metal composite material according to claim 1, wherein the alloy is an aluminum alloy, a magnesium alloy, or a titanium alloy. 3. The inorganic fibers include: Si: 30-60% by weight, Ti or Zr: 0.5-35
The inorganic fiber-reinforced metal composite material according to claim 1, having an elemental composition of C: 25 to 40 weight %, O: 0.01 to 30 weight %. 4. The inorganic fiber has a content of 10 to 7 in the composite material.
The inorganic fiber-reinforced metal composite material according to claim 1, which has a content of 0% by volume.