JPH0317237A - Inorganic fiber reinforced metal-matrix composite - Google Patents

Abstract

PURPOSE:To obtain the metal-matrix composite having excellent mechanical strength by regulating an inorganic fiber constituted of a carbonaceous material prepd. under specified conditions and showing a crystal arraying state, crystalline carbon in a nonoriented state and an amorphous phase having specified compsn. as a reinforcing material. CONSTITUTION:The high strength high elastic modulus inorganic fiber is composed of a carbonaceous material showing a crystal oriented state such as a radial structure or an anionic structure introduced from a polycyclic aromatic compound in a mesophase state constructing a polymer, crystalline carbon and/or amorphous carbon in a nonoriented state introduced from a polycyclic aromatic compound of optical isotropy including the unmolten part of an organic solvent constructing a polymer, and Si-C-O in which the proportion of the constitutional elements is regulated to, by weight, 30 to 70% Si, 20 to 60% C and 0.5 to 10% O is formed from an aggregate constituted of amorphous ultra-fine grains substantially constituted of Si, C and O and/or crystalline ultra-fine grains substantially constituted of beta-SiC having <=500Angstrom grain size and amorphous SiOX(O<=x<=2). By regulating the inorganic fiber as a reinforcing material and regulating a metal or an alloy as a matrix, the composite having excellent mechanical characteristics can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to mechanical V+E. High-quality inorganic fiber-reinforced metal composite materials (hereinafter sometimes abbreviated as "composite materials").

).

(Prior art and its problems) Due to its high toughness and mechanical properties, fiber-reinforced metal composite rice is mainly used as a structural material under high temperatures, engine parts, supersonic aircraft primary structural material, etc. It is expected that However, the strength of fiber-reinforced metal composite materials is considerably lower than the theoretical strength based on the composite law because the reinforcing fibers deteriorate due to the reaction between the Max-IJx metal and the reinforcing fibers during production. For example, it is known that when carbon fiber is used as the reinforcing fiber and aluminum is used as the matrix, aluminum carbide is produced due to the reaction between the carbon fiber and molten aluminum, resulting in a significant decrease in strength. For this reason, surface treatments have been carried out to provide a layer inert to aluminum on the surface of carbon fibers, but this has not yet resulted in satisfactory mechanical strength.

(Means for Solving the Problems) An object of the present invention is to provide a composite material with excellent mechanical strength that solves the above problems.

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 the matrix and inorganic fibers and with excellent reinforcing efficiency by the inorganic fibers. Furthermore, another object of the present invention is to provide a composite material in which the strength of the inorganic fibers is less reduced when the composite material is formed.

The composite material of the present invention has an inorganic fiber as a reinforcing material, a metal or an alloy as a matrix, the inorganic fiber is obtained from a silicon-containing polycyclic aromatic polymer, and the constituent components are Radial structure, onion structure derived from polycyclic aromatic compound in mesophase state that constitutes coalescence,
a carbonaceous material exhibiting at least one type of crystal orientation selected from the group consisting of a random structure, a core-radial structure, a skin-onion structure, and a mosaic structure; ii) an optically isotropic material containing an organic solvent insoluble component that inhibits the polymer; non-oriented crystalline carbon and/or amorphous carbon derived from a polycyclic aromatic compound; and iii) an amorphous phase consisting essentially of St, C and O and/or having a particle size of 500%. Practically speaking, it is an aggregate consisting of crystalline ultrafine particles made of β-SiC and amorphous SiOx (0<x≦2), and the proportion of the constituent elements is Si; 30 to 7
0% by weight, C: 20-60% by weight and O: 0.5-10
It is characterized by being a high-strength, high-modulus inorganic fiber made of a Si-C-0 material with a weight percent of Si-C-0.

First, the inorganic fiber in the present invention will be explained in detail. In the following explanation, "part" means "part by weight" and "%
j is "wt% J.

The inorganic fibers of the present invention have the above-mentioned structures i), ii) and iii) carana, Si; 0.01 to 29.
%, Ci70 ~99.9% and O; 0.001 ~1
0%, preferably S1; 0-1 to 25%,
C; 74-99.8% and O; O. Consisting essentially of ~8% OL.

Crystalline carbon, which is a component of this inorganic fiber, has a crystallite size of 500 or less, and is oriented in the fiber axis direction under a high-resolution electron microscope with a resolution of 1.5.
It is an ultrafine graphite crystal in which a fine lattice image corresponding to a 2-in (O O 2) plane can be observed. The crystalline carbon in the inorganic fibers can have a radial structure, an onion structure, a random structure, a core radial structure, a skin onion structure, a mosaic structure, a random structure including a partial radial structure, and the like. This is due to the presence of mesophase polycyclic aromatic compound (2) in raw rice.

Total sum of constituent components i) and ii) in this inorganic fiber 1
Composition for 00 copies $. The ratio of some iH) is 0.015~
200 parts, and the ratio of constituent components i) and ti) is 1
:0.02-4.

When the ratio of component iii) to 100 parts of the total of horizontal components i> and ti) is less than 0.015, it is almost the same as pitch fiber, and the effect of improving oxidation resistance and reducing reactivity with the matrix metal is Not enough, the above ratio is 20
If the amount exceeds 0 parts, fine graphite crystals will not be effectively produced and fibers with high elastic modulus will not be obtained.

In the continuous inorganic fiber of the present invention, microcrystals with a small interlayer spacing and three-dimensional arrangement are effectively formed,
Silicon atoms are distributed very uniformly so as to surround the microcrystals.

The inorganic fiber in the present invention is: (1) bonding unit (Si CHZ) or bonding unit (Si
CHz) and bond units (St-Si), with hydrogen in the side chain of the silicon atom. It has a side chain group selected from the group consisting of atoms, lower alkyl groups, phenyl groups, and silyl groups, and the total number of bonding units (Si CHz) versus bonding units (
At least a part of the silicon atoms of the organosilicon polymer in which the ratio of the total number of (Si-Si) is in the range of 1:0 to 20 is composed of an aromatic ring of petroleum-based or coal-based pitch or a heat-treated product thereof and a silicon-carbon Random copolymer 10 bonded via a linking group
and (2) a mesophase state obtained by heat treating petroleum-based or coal-based pitch, or a polycyclic aromatic compound consisting of both mesophase and optically isotropic phases (hereinafter, both are collectively referred to as "mesophase multi-phase"). A silicon-containing polycyclic aromatic polymer is obtained by heat-reacting and/or heat-melting 5 to 50,000 parts of a cyclic aromatic compound at a temperature in the range of 200 to 500'C. A first step, a second step of preparing a spinning dope of the silicon-containing polycyclic aromatic polymer and spinning it, and a third step of infusibleizing the spun yarn under tension or without tension.
and a fourth step of firing the infusible spun fiber bundle at a temperature in the range of 800 to 3000''C in vacuum or in an inert gas atmosphere.

Each of the above steps will be explained in more detail.

First step: The organosilicon polymer, which is one of the starting materials, can be synthesized by a known method. For example, polymethylsilane obtained by the reaction of dimethyldichlorosilane and metallic sodium is synthesized in an inert gas. Obtained by heating to 400°C or higher.

The organosilicon polymer has a bonding unit (Si CHz),
or a bonding unit (Si-CI.) and a bonding unit (Si-Si
), and the ratio of the total number of bond units (St-CH.) to the total number of bond units (Si-Si) is 1:O~20
is within the range of

The weight average molecule ffi (MW) of the organosilicon polymer is generally 300 to 1000, particularly 400 to 800. ) is preferred for preparing.

Another starting material, the polycyclic aromatic compound, is pitch obtained from petroleum and/or coal. Particularly preferred pitches are heavy oil obtained by fluid catalytic cracking of petroleum, and heavy oil distilled from the heavy oil. These are the distillate components or residual oils obtained by the above methods, and the pitch obtained by heat-treating them.

The above pitch contains 5 to 9 components insoluble in organic solvents such as benzene, toluene, xylene, and tetrahydrofuran.
The content is preferably 8% by weight. If pitch containing less than 5% by weight of the above-mentioned insoluble components is used as a raw material, inorganic fibers with excellent strength and elastic modulus cannot be obtained;
If more than % by weight of pitch is used as a raw material, the molecular weight of the copolymer will increase sharply, and coking may occur in some cases, making spinning difficult.

The weight average molecule it (MW) of this pitch is 100 to 3
It is 000.

The weight average molecular weight is a value determined as follows. That is, if the pinch does not contain organic solvent-insoluble matter for gel permeation chromatography (GPC) measurement, such as benzene, toluene, xylene, tetrahydrofuran, chloroform, and dichlorobenzene, it is directly measured by GPC, and the pitch is determined from the above-mentioned organic solvent-insoluble matter. If it contains, hydrogenation treatment is performed under mild conditions to convert the organic solvent-insoluble components to the organic solvent-soluble components listed in 7 above, followed by GPC measurement. The weight average molecular weight of the polymer containing organic solvent insoluble matter is a value obtained by performing the same treatment as above.

Random copolymer (1) is prepared by adding a petroleum-based or coal-based pinch to an organosilicon polymer and carrying out a heating reaction in an inert gas at a temperature preferably in the range of 250 to 500'C. be done.

The ratio of pitch used is 8 parts per 100 parts of organosilicon polymer.
Preferably, it is 3 to 49 oO parts.

If the ratio of pitch used is too small, the amount of silicon carbide in the resulting inorganic fiber will increase, making it impossible to obtain an inorganic fiber with a high modulus of elasticity; As the amount of components decreases, effects such as improvement of oxidation resistance and reduction of deterioration due to reaction with matrix metals are not fully exhibited.

If the reaction temperature of the above reaction is too low, the bond between silicon atoms and aromatic carbon will be difficult to form, and if the reaction temperature is too high, the formed random copolymer (1) will decompose and increase its molecular weight. occurs violently and is undesirable.

The mesophase polycyclic aromatic compound (2) is prepared by, for example, preparing petroleum-based or coal-based pitch in an inert gas at 300-50%
It can be prepared by heating to 0'C and performing condensation polymerization while removing the soft t fraction produced. If the condensation reaction temperature is too low, the elongation of the condensed ring will not be sufficient, and if the temperature is too high, an insoluble and infusible product will be produced due to coking.

Mesophase polycyclic aromatic compound (2) has a melting point of 20
The temperature is in the range of 0 to 400°C, and the weight average molecular weight is in the range of 200 to 10,000.

Among the mesophase polycyclic aromatic compounds (2), 20
Those having an optical anisotropy of 100% to 100% and containing 30 to 100% insoluble matter in benzene, toluene, xylene or tetrahydrofuran are particularly preferred in order to obtain inorganic fibers with excellent mechanical performance.

In the first step, the random copolymer (1) and the mesophase polycyclic aromatic compound (2) are heated at 200 to 500'C.
A spun polymer made of a silicon-containing polycyclic aromatic polymer is prepared by heat-melting and/or heat-reacting in a temperature range of .

The usage ratio of the mesophase polycyclic aromatic compound (2) is 5 to 500 parts per 100 parts of the random copolymer (1).
00 parts is preferable; if it is less than 5 parts, the mesophase content in the raw bottom material will be insufficient, making it impossible to obtain highly elastic burned yarn; and if it is more than 50,000 parts,
Due to a certain shortage of silicon, effects such as improvement in oxidation resistance and reduction in deterioration due to reaction with matrix metals are not fully manifested.

The weight average molecular weight of the silicon-containing polycyclic aromatic polymer is 2
00-1 ]. O O O, melting point 200-400
It is °C.

2nd step: The spinning polymer, which is a silicon-containing polycyclic aromatic polymer obtained in the 1st step, is heated and melted, and in some cases, it is filtered to remove substances that are harmful during spinning, such as microgels and impurities. This is then spun using a commonly used fiber spinning device.

The temperature of the spinning dope during spinning varies depending on the softening temperature of the raw material polymer, but a temperature in the range of 220 to 420'C is advantageous.

In the spinning device, a spinning tube is attached as necessary,
After setting the atmosphere in the spinning tube to one or more atmospheres selected from the group consisting of air, inert gas, hot air, hot inert gas, steam, and ammonia gas, the winding speed is increased to create a thin diameter. fibers can be obtained. The spinning speed in the melt spinning is determined by the average molecular weight of the raw materials,
Although it varies depending on the molecular weight distribution and molecular structure, 50 to 500
A range of 0 m/min is preferable.

Third step: The spun fibers obtained in the second step are rendered infusible by applying tension or non-tension.

A typical method for infusibility is to heat the above-mentioned shaped body in an oxidizing atmosphere. The infusibility temperature is preferably 50 to 4
The temperature is in the range 0 0'C. If the infusibility temperature is too low, the polymer constituting the matrix will not deform, and if the temperature is too high, the polymer will burn.

The purpose of infusibility is to make the polymer that makes up the spun fibers into a three-dimensional structure that is infusible and insoluble, so that they do not cool and melt during the next firing process and do not fuse with adjacent fibers. It is to be. Gases forming the oxidizing atmosphere during infusibility include air, ozone, oxygen, chlorine gas, bromine gas, ammonia gas, and mixed gases thereof.

As an infusibilization method different from the above, the spun fibers are infusibilized by irradiation with gamma rays or electron beams in an oxidizing or non-oxidizing atmosphere, under tension or without tension, while heating at a low temperature as necessary. method can also be adopted.

The purpose of irradiating with gamma rays or electron beams is to further polymerize the polymer that forms the spun fibers.
The purpose is to prevent the spun yarn from melting and losing its fiber shape.

The appropriate irradiation dose of T-rays or electron beams is 106 to 1010 rads.

Irradiation can be carried out in a vacuum, an inert gas atmosphere, or an oxidizing gas atmosphere such as air, ozone, oxygen, chlorine gas, bromine gas, ammonia gas, and mixtures thereof.

Infusibility by irradiation can be carried out at room temperature, and if necessary, infusibility can be achieved in a shorter time by heating in the temperature range of 50 to 200''C.

If infusibility is carried out without tension, the spun fibers will shrink and take on a wavy shape, but this can sometimes be corrected in the next firing process, and tension is not necessarily required. When applied, good results can be obtained if the tension is greater than that which can at least prevent the spun fibers from shrinking and becoming wavy during infusibility.

The tension applied during infusibility is 1 to 500 g.
/nun'' range is preferable; even if a tension of Ig/tmn or less is applied, it is not possible to apply tension that will not cause the fibers to slack, and if a tension of 500 g/ram2 or more is applied, the fibers will not loosen. May be severed.

Fourth step: By firing the infusible yarn obtained in the third step at a temperature in the range of 800 to 3000°C in a vacuum or inert gas atmosphere, inorganic fibers mainly composed of charcoal, bone, silicon, and oxygen are produced. is obtained.

In the firing process, it is not necessarily necessary to apply tension, but high-temperature firing while applying tension in the range of 0.00 l to 100 kg/m" yields high-strength inorganic fibers with less bending. be able to.

It is estimated that during the heating process, mineralization becomes intense from about 700°C, and mineralization is almost completed at about 800°C. Therefore, it is preferable to perform the burning ceremony at a temperature of 800"C or higher. Also, since obtaining a temperature higher than 3000°C requires expensive equipment, burning at a temperature higher than 3000°C or the cost It's not practical from a surface point of view.

The distribution state of silicon in the inorganic fiber of the present invention can also be controlled by the atmosphere during firing and the size and concentration of mesophase in the raw material. For example, when the mesophase is lengthened to a large extent, the silicon-containing polymer is easily extruded into the fiber surface phase, and a silicon-rich layer can be formed on the fiber surface after firing.

Incidentally, the constituent component ij) of the inorganic fiber is Si-C-O
The morphology of the l+yJ quality can be controlled by the mineralization temperature in the fourth step.

When it is desired to obtain an amorphous substance consisting essentially of St, C, and 0, it is preferable to set the mineralization temperature to 800 to io o o'c, and to obtain an amorphous substance consisting essentially of β-SiC and amorphous Sin. ．．
(However, if it is desired to obtain 0<x≦2, a temperature of 1700°C or higher is suitable.

Further, when a mixed system of each aggregate is desired, the temperature can be appropriately selected from the above intermediate temperatures.

Further, the amount of oxygen in the inorganic fiber of the present invention can be controlled, for example, by the infusibility conditions in the fourth step.

For the inorganic fibers, for example, a method of orienting the fiber itself in a uniaxial direction or a multiaxial direction, a plain weave, a satin weave, a patterned weave,
The composite material of the present invention can be manufactured by applying methods such as using it as various fabrics such as twill weave, leno weave, and three-dimensional fabric, or using it as chopped fiber.

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.

The composite material of the present invention can be manufactured by the following conventional method for manufacturing fiber-reinforced metal composite rice. In other words, (1) diffusion bonding method (2) melt infiltration method (3) thermal spraying method (
4) Electrolytic deposition method (5) Extrusion and hot roll method (6)
Chemical vapor deposition method (7) Various methods of sintering method.

(1) According to the diffusion bonding method, inorganic fibers and matrix metal wires are arranged alternately in one direction, and the upper and lower sides are covered with a thin film of matrix metal, or only the lower part is covered with the thin film, and the upper part is covered with organic bonds. A composite material of the inorganic fiber and the matrix metal can be produced by covering the composite layer with a matrix metal powder mixed with an agent to form a composite layer, laminating several layers, and then applying pressure under heat.

The organic binder is preferably one that volatilizes and dissipates before the temperature is raised to a temperature that destroys the matrix metal and carbide; for example, CMC, paraffin, resin, 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,
In particular, since the metal-coated fibers have good wettability with the matrix metal, 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 (1) 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 (1) above.

(5) According to the extrusion and hot roll methods, fibers are arranged in one direction, sandwiched between matrix metal foils, and passed between heated rolls if necessary to bond the fibers and the matrix metal. Let's join,
Composite materials can be manufactured.

(6) According to the chemical vapor deposition method, fibers are placed in a heating furnace and a mixed gas of, for example, aluminum chloride and hydrogen gas is introduced to thermally decompose the fibers, and aluminum metal is precipitated on the surface of the fibers to form a composite. do. Furthermore, a composite material can be manufactured by arranging these metal-deposited fibers in layers and using the diffusion bonding method described in (1) above. (7) According to the sintering method, the gaps between the arranged fibers are filled with matrix metal powder, which is then heated and sintered with or without pressure to form a composite material. The tensile strength (σC) of a composite material manufactured from inorganic fibers and a metal matrix is expressed by the following formula.

σC=σfvf+σN VM σC: Tensile strength of composite material σ,: Tensile strength of inorganic fiber σe: Tensile strength of metal matrix ■,: Volume percentage of inorganic fiber ■N: Volume percentage of metal matrix As shown in the above formula The strength of the composite material increases as the volume ratio of inorganic fibers in the composite material increases. Therefore, in order to manufacture a composite material with high strength, it is necessary to increase the volume ratio of the inorganic fibers to be composited. However, when the volume ratio of inorganic fibers exceeds 70%, the amount of metal matrix is small and the gaps between the inorganic fibers cannot be sufficiently filled with the metal matrix. The strength shown will no longer be exerted. In addition, as the volume ratio of inorganic fibers in the composite material decreases, the strength of the composite paddy decreases, as shown in the previous part.
It is necessary to combine % or more of inorganic fibers. Therefore, as described above, in producing the inorganic fiber-reinforced metal composite material of the present invention, the best effects can be obtained when the composite ratio of inorganic fibers is 10 to 70% by volume.

When manufacturing composite materials, as mentioned above, it is necessary to heat the metals near or above their melting temperature to combine them with the reinforcing fibers, which reduces the strength of the fibers due to the reaction between the non-mIa fibers and the molten metals. However, when the inorganic fibers of the present invention are immersed in molten metals, the rapid fiber deterioration that is observed with ordinary carbon fibers is not observed, and therefore, composite materials with excellent mechanical strength can be obtained. Obtainable.

Next, methods for measuring various mechanical properties used in the present invention will be described. (a) Initial reaction deterioration rate b) In the case of metals and alloys with a melting point of 1200'C or less, inorganic fibers are immersed in molten metal heated to a temperature 50°C higher than the melting point of the metal used for 1 minute, 5 After soaking for 10 minutes, 10 minutes, and 30 minutes, the fibers are extracted and the tensile strength of the fibers is measured. From this result, the relationship between the immersion time and the tensile strength of the fibers, that is, the reaction deterioration curve, was determined, and the initial reaction deterioration rate (kg/IIIls" ・se
c-').

In the case of metals and alloys whose melting point is higher than 12oO°C, inorganic fibers and metal foil are laminated and heated in vacuum to a temperature of (melting point of metal foil) x (0.6 to 0.7). , 5
The fibers are held under a pressure of 2 kg/kg for 5, 10, 20, and 30 minutes, 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 each of the immersion time and the holding time of 30 minutes in (a), and dividing (initial strength - 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, the better the compatibility between the fibers and the matrix, and the greater the reinforcing effect of the fibers. show.

The fiber strength reduction rate indicates the degree of reaction between fibers and 71.lix when manufacturing fiber reinforced metal over a long period of time,
The smaller this value is, the better the compatibility between the fiber and the matrix, and the greater the reinforcing effect of the fiber.

(C) Interlaminar shear strength test A test method for determining interlaminar shear stress with a radius of curvature of 6I! I
IOX on the two pins (length 20m + i) of ffIφ
A composite material of 12 x 2 mm inorganic fibers oriented in a uniaxial direction is placed, and the tip radius of curvature is 3. The material is compressed with a 5 mmφ indenter and tested using the so-called three-point bending method, and the interlaminar shear stress (kg/mm") is measured. Shear stress (kg/mm")
”).

(d) Fatigue test A round bar of 10φ x 100m+ is manufactured so that the axial direction of the composite material in which inorganic fibers are uniaxially oriented is the long sleeve direction, and this is processed into a specified rotary bending fatigue test piece. is 1. A 5 kg m rotary bending fatigue test was conducted to determine the fatigue strength of 107 times, which was defined as fatigue.

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

(Effects of the Invention) Since the inorganic fibers of the present invention have little fiber strength deterioration due to reaction with molten metals, the inorganic fiber-reinforced metal composite material obtained by the present invention has excellent mechanical properties such as tensile strength,
Due to its high modulus of elasticity, excellent heat resistance, and abrasion resistance, it can be used as materials for textiles, chemicals, machinery, construction machinery, marine development (including space), and automobiles. It is used as a variety of materials such as food materials and food materials.

Due to its excellent abrasion resistance, it can be used for various materials such as composite textile materials, composite chemical materials, mechanical industry materials, construction machinery materials, marine development (including space) materials, automobile materials, food materials, etc. used as.

(Example) The present invention will be explained below with reference to Examples.

Reference Example 1 (Manufacture of Inorganic Fiber I) 2.5j2 of anhydrous xylene and 400 g of sodium were placed in a 5-liter three-necked flask, heated to the boiling point of xylene under a nitrogen gas stream, and 1 liter of dimethylsilane was added dropwise over 1 hour. After the addition was completed, the mixture was heated under reflux for 10 hours to form a precipitate. The precipitate was filtered and washed with methanol and then water to obtain 420 g of boridimethylsilane as a white powder.

400 g of this boridimethylsilane was charged into 32 three-necked flasks equipped with a gas inlet tube, a stirrer, a condenser, and a distillation tube, and was heated to 420 g under a nitrogen flow of 50 Id/min while stirring.
After heating at °C, 350 g of a colorless and transparent slightly viscous liquid was obtained in a distillation receiver.

The number average molecular weight of this liquid was 470 as measured by vapor pressure osmosis.

When the infrared absorption spectrum of this substance was measured, it was found that 6
Si-CH.50~900c+a-' and 1250cm-'. absorption, St-H absorption at 2100Cll-', St-H absorption at around 1020cm-' and 1355cm-'
-CH, -Si absorption, 2900cm-' and 2950c
C-H absorption was observed at m-', and when the far-infrared absorption spectrum of this substance was measured, it was found to be 380c+s-
Since absorption of Si-St is observed in
It turned out to be an organosilicon polymer consisting of bond units (Si--St) and having hydrogen atoms and methyl groups in silicon side chains.

According to the measurement results of nuclear magnetic resonance analysis and infrared absorption analysis, this organosilicon polymer has a ratio of the total number of (S i CHz ) bond units to the total number of (Si-Si) bond units of approximately 1:
It was confirmed that the polymer was No. 3.

300 g of the above organosilicon polymer was treated with ethanol to remove low molecular weight substances to obtain 40 g of a polymer having a number average molecular weight of 200.

When the infrared absorption spectrum of this substance was measured, absorption peaks similar to those above were observed, and this substance mainly consists of (Sj CHz) bond units and (St-Si) bond units, and has hydrogen atoms and silicon side chains. It turned out to be an organosilicon polymer with methyl groups.

From the measurement results of nuclear magnetic resonance analysis and infrared absorption analysis, this organosilicon polymer is a polymer in which the ratio of the total number of (St CHI) bond units to the total number of (Si-St) bond units is approximately 7:1. This was confirmed.

On the other hand, among petroleum fractions, substances with a boiling point higher than that of light oil are removed using silica.
Fluid catalytic cracking and rectification were performed at a temperature of 500°C in the presence of an alumina-based cracking catalyst, and a residue was obtained from the bottom of the column. Hereinafter, this residue will be referred to as FCC slurry oil.

As a result of elemental analysis, this FCC slurry oil had an atomic ratio of carbon atoms to hydrogen atoms (C/H) of 0.75, and an aromatic carbon ratio of 0.55 as determined by nuclear magnetic resonance analysis.

II! 100g of the above FCC slurry oil! The mixture was heated at 420°C for 2 hours under a nitrogen gas flow of 1/2 min to obtain 57 g of pitch from which light components had been removed at the same temperature. This light fraction removed pitch contained 60% xylene insoluble matter.

25 g of organosilicon polymer and 20 d of xylene were added to 57 g of this light fraction removed pitch, the temperature was raised while stirring, the xylene was distilled off, and the mixture was reacted at 400'C for 6 hours to give 43 g.
A random copolymer (1) was obtained.

As a result of infrared absorption spectroscopy, this reaction compound was found to be a St-H bond (IR:
2 1 0 0 cr') and a new St-C (
Carbon bond in benzene ring (IR: 1135C11-')
The organic silicon polymer was found to be a copolymer in which some of the silicon atoms were directly bonded to polycyclic aromatic rings.

This random copolymer (1) contained no xylene-insoluble portion, had a weight average molecular weight of 1400, and a melting point of 265°C. This was heated and melted at 300''C and left to stand, and the light portion was removed due to the difference in specific gravity to obtain 40 g of the remaining material. This is referred to as polymer (a).

In parallel with this, 400 g of the above FCC slurry oil was heated to 450'C under a nitrogen gas flow, and after distilling off the distillate at the same temperature, the residue was filtered while hot at 200'C. The infusible portion at the same temperature was removed to obtain 180 g of pitch from which light components were removed. 180 g of the obtained pitch from which light components were removed was subjected to condensation polymerization at 400° C. for 8 hours under a nitrogen stream while removing light components that were present during the reaction, and heat-treated pitch 80. 3 g was obtained. This heat-treated pitch has a melting point of 310°C, a xylene insoluble content of 97%, and a quinoline insoluble content of 2
It was a mesophase polycyclic aromatic polymer (2) with an optical anisotropy of 95% when observed with a polarized light microscope on the polished surface. This was heated and melted at 350°C and left to stand again, and the light portion was separated and removed due to the difference in specific gravity, and the remaining 80g
I got it.

This and 40 g of polymer (a) were mixed and melted and heated at 350° C. for one hour in a nitrogen atmosphere to obtain a silicon-containing polycyclic aromatic polymer in a uniform state.

This polymer has a melting point of 290°C, and 2i! /
0.5 min at 450°C under nitrogen gas flow. Heat for 5 hours,
After distilling off the distillate at the same temperature, the residue was filtered while hot at 200''C to remove the infusible portion at the same temperature to obtain 57 g of light fraction-removed pitch.

This light-removed pitch contained 25% xylene insolubles.

A metal nozzle with a nozzle diameter of 0.15M was used to obtain 57g of this light matter removal pitch as obtained in Reference Example 1, and 360
Melt spinning is carried out at "C", and the obtained spun yarn is placed in the air,
Oxidized and made infusible at 300°C, further in an argon atmosphere,
Burning was performed at 1300° C. to obtain inorganic fiber I with a diameter of IO μm.

This fiber had a tensile strength of 295 kg/wx'' and a tensile modulus of 26 t/rBm'', and as observed from the fracture surface, it clearly had a radial structure.

Reference Example 2 (Manufacture of inorganic fiber H) 51 g of random copolymer (
1) was obtained.

As a result of infrared absorption spectroscopy, this reaction compound was found to be a Si-H bond (IR:
2 1 0 0c+a-') and new Si-
C (benzene ring carbon) bond (IR: 1135cm-'
), it was found that the organosilicon polymer was a copolymer in which some of the silicon atoms were directly bonded to polycyclic aromatic rings.

This random copolymer (1) does not contain xylene-insoluble parts, has a weight average molecular weight of 1400, a melting point of 265°C,
The softening point was 310"C.

On the other hand, 180 g of the light component-removed pitch was heated at 400°C for 8 hours under a nitrogen stream while removing the light components that were present during the reaction.
Time-condensation polymerization was performed to obtain 97.2 g of heat-treated pitch.

This heat-treated pitch has a melting point of 263°C and a softening point of 308°C.
The mesophase polycyclic aromatic polymer (2) contained 77% of 1-xylene insoluble matter and 31% of quinoline insoluble matter, and had an optical anisotropy of 75% when observed with a polarizing microscope on the polished surface.

This mesophase polycyclic aromatic polymer (2) 9 0
g and 6.4 g of the random copolymer (1) were mixed and melted and heated at 380'C for one hour in a nitrogen atmosphere to obtain a silicon-containing polycyclic aromatic polymer in a uniform state.

This polymer has a melting point of 267°C and a softening point of 3l5°C.
It contained 70% xylene insoluble matter. The above-mentioned silicon-containing polycyclic aromatic polymer is used as a raw material for spinning, and a nozzle diameter of 0.
Melt spinning was performed at 360'C using a 15rra metal nozzle, and the resulting spun yarn was heated at 300°C in air.
Oxidized and made infusible with "C, and further in an argon atmosphere, 1 3
0 0 ”C inorganic fiber with a diameter of 8μm■
I got it.

This fiber has a tensile strength of 320 kg/in. ” ,
The tensile modulus was 2 6 t/ms2, and the observation of the fracture surface clearly showed that it had a radial structure.

This inorganic fiber (1) was pulverized, then melted with alkali and treated with hydrochloric acid to form an aqueous solution, and then subjected to high frequency plasma emission spectrometry analysis. As a result, the silicon content in this inorganic fiber (1) was found to be 0.95%.

Reference Example 3 (Production of inorganic fiber (■)) 97 g of mesophase polycyclic aromatic compound (2) and 3 g of random copolymer (1) were mixed, and 400'
A silicon-containing polycyclic aromatic polymer was obtained in the same manner as in Reference Example 2, except that the polymer was melted and heated with C.

This polymer has a melting point of 272°C and a softening point of 319°C.
It contained 71% xylene insoluble matter.

The above-mentioned high molecular weight material was spun and infusible in the same manner as in Reference Example 2, and then calcined at 2500°C in an argon atmosphere to give a diameter of 7.2 μm.
An inorganic fiber ■ was obtained.

This fiber had a tensile strength of 335 kg/am" and a tensile modulus of 53 t/mm".

This inorganic fiber (1) was pulverized, then melted with alkali and treated with hydrochloric acid to form an aqueous solution, and then subjected to high frequency plasma emission spectrometry analysis. As a result, the silicon content in this inorganic fiber (1) was found to be 0.42%.

Reference Example 4 (Manufacture of silicon carbide fiber) The silicon carbide fiber obtained only from polycarbosilane used in Comparative Example 7 was manufactured as follows.

3 parts by weight of polyborosiloxane was added to 100 parts by weight of boridimethylsilane synthesized by dechlorination condensation of dimethyldichlorosilane with metallic sodium, and 350 parts by weight of polyborosiloxane was added to
Thermal condensation was carried out at °C to obtain a polycarbosilane having a main chain skeleton mainly composed of carbosilane units of the formula (SiCHz) and having a hydrogen atom and a methyl group on the silicon atom of the carbosilane unit. This polymer was melt-spun, made infusible at 190'C in air, and then burned out at 1300'C in nitrogen, resulting in a fiber diameter of 1.
3μ, tensile strength 300kg/InIIl2, tensile modulus 16t/IIIff! A silicon carbide fiber consisting mainly of silicon, carbon and oxygen was obtained.

Example 1 Thickness 0. A-free fibers I were arranged in a uniaxial direction on 5 mOl of pure aluminum foil (JIS standard 1070), the above aluminum foil was placed on top of the aluminum foil, and the fibers and aluminum were heated by hot rolling at a temperature of 670°C. A composite foil was manufactured by combining the following. 27 sheets of this composite foil were stacked, left for 10 minutes under vacuum at a temperature of 670°C, and then hot pressed at 600°C to produce an inorganic fiber reinforced aluminum ξ composite material.

For inorganic fibers, the initial reaction deterioration rate (kg/plate 2 sec-') and fiber strength reduction rate (%) were measured, and for composite materials, the tensile strength in the fiber direction (kg
/Il11”), tensile modulus in the fiber direction (t/+n
m"), interlaminar shear strength (kg/ffll"), tensile strength in the direction perpendicular to the fibers Ckg/rm"), and fatigue limit/tensile strength were measured. The results are shown in Table 1. It was 30% by volume.

A carbon fiber-reinforced aluminum ξ composite material was produced in the same manner, and the above characteristic values were measured. The results are also listed in Table 1. In addition, ■, was 3o volume %.

Example 2 A fiber-reinforced metal was manufactured in the same manner as in Example 1 except that aluminum alloy foil (JIS standard 6061) was used, and the above characteristic values were measured. The results are shown in Table 2.

Comparative Example 1 Instead of the inorganic fiber used in the present invention, fibers with a tensile strength of 30
Example 1 and Comparative Example 2 except that commercially available PAN-based carbon fiber with a weight of 0 kg/2 and an elastic modulus of 2 1 t/tra2 were used.Except that the carbon fiber described in Comparative Example 1 was used instead of the inorganic fiber. A carbon fiber-reinforced aluminum composite material was manufactured in the same manner as in Example 2, and the above characteristic values were measured. The results are also listed in Table 2. Example 3 Inorganic fibers I 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 were layered and arranged, the gaps between the layers were filled with titanium powder and shaped under pressure.
After pre-baking at ℃ for 3 hours, it was further calcined at 1150℃ under an argon atmosphere for 3 hours while applying a pressure of 200 kg/c-.
After hot pressing for an hour, an inorganic fiber reinforced titanium composite material was obtained.

For inorganic fibers, the initial reaction deterioration rate (kg/a
m"・see-') and fiber strength reduction rate (%), and for composite materials, the tensile strength in the fiber direction (kg
/mm''), glabellar shear strength (kg/mm''), tensile strength in the direction perpendicular to the fibers (kg/m''), and fatigue limit/tensile strength were measured. The results are shown in Table 3. The tensile strength of the obtained composite material in the fiber direction is 120 kg/nu
n'', which was approximately twice the tensile strength of titanium metal alone.Comparative Example 3: The tensile strength of titanium metal alone was 45% by volume. A carbon fiber-reinforced titanium composite material was manufactured in the same manner as in Example 3, and the above characteristic values were measured.The results are also listed in Table 3.

Example 4 Titanium alloy (Ti-6Af-4V) was applied to inorganic fibers I arranged in a uniaxial direction using a thermal spraying device. 1-10
It was coated to a thickness of μ. The inorganic fibers were stacked and arranged, the gaps between the stacks were filled with titanium powder and shaped under pressure, and the compact was preliminarily baked at 520°C for 3 hours in a hydrogen gas atmosphere, and then heated at 1150°C in an argon atmosphere. ℃, 200kg/
Hot pressing was carried out for 3 hours while applying a pressure of C- to obtain an inorganic fiber reinforced titanium composite material.

For inorganic fibers, the initial reaction deterioration rate (kg/12
・sec-') and fiber strength reduction rate (%), and for composite materials, glabellar shear strength (kg/Peng2),
The tensile strength (kg/mm") in the direction perpendicular to the fibers and the fatigue limit/tensile strength were measured. The results are shown in Table 4.
■, was 45% by volume.

Comparative Example 4 A carbon fiber-reinforced titanium composite material was produced in the same manner as in Example 4, except that the carbon fibers described in Comparative Example 1 were used instead of the inorganic fibers, and the above characteristic values were measured. The results are also listed in Table 4.

Example 5 Thickness 0. The inorganic fibers I were arranged in a uniaxial direction on 5 m of pure magnesium foil, the magnesium foil was placed on top of the inorganic fibers, and the fibers were hot rolled at a temperature of 670'C.
We have manufactured a composite foil that combines fiber and magnesium. 27 sheets of this composite foil were stacked, left for 10 minutes under vacuum at a temperature of 670°C, and then hot pressed at 600°C to produce an inorganic fiber-reinforced magnesium composite material.

For inorganic fibers, the initial reaction deterioration rate (kg/m
m"・sec-') and fiber strength reduction rate (%), and for composite materials, interlaminar shear strength (kg/mm")
The tensile strength (kg/+nm") in the direction perpendicular to the fibers and the fatigue limit/tensile strength were measured. The vf was 30% by volume. The results are shown in Table 5.

Comparative Example 5 A carbon fiber-reinforced magnesium composite material was produced in the same manner as in Example 5, except that the carbon fibers described in Comparative Example 1 were used instead of the inorganic fibers, and the above characteristic values were measured. The results are also listed in Table 5.

Example 6 Thickness 0. The inorganic fibers I were arranged in the axle direction on a 5 mm magnesium alloy foil (JIS standard A891), the above magnesium alloy foil was placed on top of it, and the fibers and magnesium alloy were rolled by hot rolling at a temperature of 670°C. A composite foil was manufactured by combining the following. 27 sheets of this composite foil were stacked, left for IO minutes under vacuum at a temperature of 670°C, and then hot pressed at 600°C to produce an inorganic fiber reinforced magnesium composite material.

For inorganic fibers, the initial reaction deterioration rate (kg/mm”
・sec-') and fiber strength reduction rate (%), and for composite materials, glabella shear strength (kg/mu"),
The tensile strength in the direction perpendicular to the fiber (kg/m+++") and fatigue limit/tensile strength were measured. The results are shown in Table 6.

Note that ■, was 30% by volume.

Comparative Example 6 A carbon fiber-reinforced magnesium composite material was produced in the same manner as in Example 6, except that the carbon fibers described in Comparative Example 1 were used instead of the inorganic fibers, and the above characteristic values were measured. The results are also listed in Table 6.

Comparative Example 7 A silicon carbide fiber-reinforced aluminum composite material was produced in the same manner as in Example 1 except that the silicon carbide fibers obtained in Reference Example 3 were used.

The tensile strength of the composite material obtained was comparable to that of the composite material obtained in Example 1, but the tensile modulus was 6.
．． 3t/+am". Note that V was 30% by volume.

Example 7 Pure aluminum V4 (JIS
Composite foil made by arranging inorganic fibers in a uniaxial direction on top of Standard 1070), covering the aluminum foil above, and hot rolling the fibers and aluminum at 670'C i degrees. was manufactured. Stacked 27 sheets of this composite foil, left it for 10 minutes under vacuum at a temperature of 670°C, and then heated it for 60 minutes.
An inorganic fiber reinforced aluminum composite material was produced by hot pressing at 0°C.

For inorganic fibers, the initial reaction deterioration rate (kg/m
sec-') and fiber strength reduction rate (%), and for composite materials, the tensile strength in the fiber direction (kg
/mm”), tensile modulus in the fiber direction (1/mm”),
Glabellar shear strength (kg/mm''), tensile strength perpendicular to the fibers (kg/+w''), and fatigue limit/tensile strength were measured. The results are shown in Table 7 together with the results of Comparative Example 1. Shown in the results.

Note that Vf was 30% by volume. Comparative example 2
The results are also shown in Table 8.

Example 8 Fiber-reinforced metal Example 9 Titanium metal was applied to inorganic fibers arranged in a uniaxial direction using a thermal spraying device in the same manner as in Example 7 except that aluminum alloy foil (JIS standard 606 1) was used. The coating was applied to a thickness of 0.1 to 10 microns. The inorganic fibers are stacked and arranged, the gaps between the stacks are filled with titanium powder, and the molded body is heated for 520 min in a hydrogen gas atmosphere.
After preliminarily calcining at .degree. C. for 3 hours, the material was hot pressed for 3 hours at 1150.degree. C. under an argon atmosphere while applying a pressure of 200 kg/cm" to obtain an inorganic fiber-reinforced titanium composite material.

For inorganic fibers, the initial reaction deterioration rate (kg/t2
・Sec-') and fiber strength reduction rate (%) are measured, and for composite materials, the tensile strength in the fiber direction (kg/mm") is measured.
), glabellar shear strength (kg/Shi2), tensile strength in the direction perpendicular to the fibers (kg/ms"), and fatigue limit/tensile strength were measured. The results are shown in Table 9 together with the results of Comparative Example 3. Ta.

The tensile strength of the obtained composite material in the fiber direction was 122 kg/
mm", which was approximately twice the tensile strength of titanium metal alone. Note that vf was 45% by volume.

Example 10 Titanium alloy (Ti-6Al-4V) was coated with 0.1 to 10 µm of inorganic fibers arranged in a uniaxial direction using a thermal spraying device.
It was coated to a thickness of . The inorganic fibers were layered and arranged, the gaps between the layers were filled with titanium powder, and the formed body was pre-fired at 520°C for 3 hours in a hydrogen gas atmosphere.
Further, at 1150"C under argon atmosphere, 200
Hot pressing was carried out for 3 hours while applying a pressure of kg/c to obtain an inorganic fiber reinforced titanium composite material.

For inorganic fibers, the initial reaction deterioration rate (kg/m”
・Measure the fiber strength reduction rate (%)
For composite materials, glabellar shear strength (kg/m”)
The tensile strength (kg/mm") perpendicular to the fibers and the fatigue limit/tensile strength were measured. The results are shown in Table 10 together with the results of Comparative Example 4.

In addition, ■, was 45 volume%. Example 11 Thickness 0. 5 tm of pure magnesium foil, the inorganic fibers ■ were arranged in a uniaxial direction, the above-mentioned magnesium foil was placed on top of it, and a composite foil made of fibers and magnesium was formed by hot rolling at a temperature of 670°C. Manufactured. 27 sheets of this composite foil were stacked, left for IO minutes under vacuum at a temperature of 670°C, and then hot pressed at 600°C to produce an inorganic fiber reinforced magnesium composite material.

For inorganic fibers, the initial reaction deterioration rate (kg/m”
・Measure the fiber strength reduction rate (%)
For the composite materials, glabellar shear strength (kg/am"), tensile strength perpendicular to the fibers (kg/mad"), and fatigue limit/tensile strength were measured. Note that Vf was 30% by volume. The results are shown in Table 11 together with the results of Comparative Example 5.

For inorganic fibers, the initial reaction deterioration rate (k&/Kaku2
・Sec-') and fiber strength reduction rate (%) are measured, and for composite materials, glabellar shear strength (kg/nu"), tensile strength in the direction perpendicular to the fibers (kg/mm"), and fatigue limit/tensile strength are measured. was measured. The results are shown in Table 12 together with the results of Comparative Example 6. Note that ■, was 30% by volume.

Example 12 Thickness 0. 5 tm of magnesium alloy M (JIS standard A891), the inorganic fibers (■) were arranged in a uniaxial direction, the above-mentioned magnesium alloy foil was placed over it, and the fibers and the magnesium alloy were heated by hot rolling at a temperature of 670°C. A composite product was manufactured by combining the following. Layering 27 sheets of this composite foil,
After standing under vacuum at a temperature of 670'C for 10 minutes, the material was further hot-pressed at 600°C to produce an inorganic fiber-reinforced magnesium composite material. Example 13 An inorganic fiber-reinforced aluminum composite material was produced in the same manner as in Example 7 except that the inorganic fibers (① obtained in Reference Example 3) were used. Note that Vf was 30% by volume.

The tensile strength of the resulting composite material was comparable to that obtained in Example 7, but the tensile modulus was 15.2 t/mm''.

Claims (1)

[Scope of Claims] An inorganic fiber-reinforced metal composite material having inorganic fibers as a reinforcing material and a metal or alloy as a matrix, wherein the inorganic fibers are inorganic fibers obtained from a silicon-containing polycyclic aromatic polymer; The constituent component is i) at least one selected from the group consisting of a radial structure, an onion structure, a random structure, a core radial structure, a skin onion structure, and a mosaic structure derived from a polycyclic aromatic compound in a mesophase state constituting the polymer; ii) non-oriented crystalline carbon and/or amorphous carbon derived from an optically isotropic polycyclic aromatic compound containing an organic solvent-insoluble component constituting the polymer; and iii) an amorphous phase consisting essentially of Si, C and O and/or crystalline ultrafine particles consisting essentially of β-SiC with a particle size of 500 Å or less and amorphous SiO_x (0< x≦2)
It is an aggregate consisting of Si, and the proportion of the constituent elements is Si; 30 ~
70% by weight, C: 20-60% by weight and O: 0.5-1
An inorganic fiber-reinforced metal composite material characterized by being a high-strength, high-modulus inorganic fiber made of a Si-C-O material of 0% by weight.