JPH0413824A - Fiber reinforced metal matrix composite - Google Patents

Abstract

PURPOSE:To improve strength, elasticity, and heat resistance buy reinforcing a metal matrix with an inorganic fiber of boron-containing silicon nitride in which, e.g. the proportions between respective elements are specified, respectively. CONSTITUTION:This fiber reinforced metal matrix composite is constituted by reinforcing metal matrix with inorganic fiber. The above inorganic fiber contains silicon, nitrogen, and boron as essential components and also contains oxygen, carbon, and hydrogen as optional components, and the proportions between the above elements are limited so that N/Si, B/Si, O/Si, C/Si, and H/Si are regulated to 0.05-2.5, 0.01-3, <=2, <=1.5, and <=0.1, respectively, represented by atomic number ratio. Further, the above inorganic fiber is composed of an amorphous substance or such an amorphous substance containing microcrystalline phase of <=2000Angstrom crystallite size.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a fiber-reinforced metal composite material, and more specifically to a high-strength, high-elasticity, and high-heat-resistant metal composite reinforced with boron-containing silicon nitride inorganic fibers. Regarding materials.

[Conventional technology]

BACKGROUND ART Fiber-reinforced metal composite materials have been known that use inorganic fibers such as silica fibers, alumina fibers, or carbon fibers as reinforcement materials to improve the properties of metals such as aluminum, magnesium, and titanium.

However, those using silica fiber as a reinforcing material have a low elastic modulus and cannot be said to have very high strength, and those using alumina fiber have poor compatibility and wettability with metals, so they have poor strength and elasticity. The effect of improving the carbon fiber properties is not sufficient, and furthermore, those using carbon fibers have a large reactivity with metals, which causes problems such as a decrease in the strength of the metals.

In addition, silicon carbide fiber obtained by spinning, infusible, and firing polycarbosilane is effective as a metal reinforcing material.
Special Publication No. 58-9824, No. 58-43461, No. 5
No. 9-19982, No. 60-424, No. 60-100
It is disclosed in publications such as No. 98, No. 60-10099, No. 60-10100, and No. 60-41136.

However, the strength of this silicon carbide fiber decreases significantly when it is immersed in metals such as molten aluminum during compounding, and furthermore, the strength decreases even further due to the reaction with the metal proceeding at high temperatures. has.

In addition, conventional inorganic fiber-reinforced metal composite materials generally require various surface treatments on the reinforcing fibers in order to prevent strength deterioration, and also require low-temperature and long-time treatment steps during the composite process, such as hot pressing. This involves the problem of a significant drop in productivity.

[Problem to be solved by the invention]

The present invention provides an inorganic fiber-reinforced metal composite material that has excellent properties such as high strength, high elasticity, and high heat resistance, and is inexpensive to manufacture, unlike the conventional inorganic fiber-reinforced metal composite materials. The purpose is to

[Means to solve the problem]

In order to achieve the above object, the present invention is a fiber-reinforced metal composite material made by reinforcing a metal matrix with inorganic fibers, and the inorganic fibers contain silicon, nitrogen and boron as essential components, and contain oxygen, carbon and hydrogen. As an arbitrary component, the ratio of each element expressed in atomic ratio is N/Si0.05 to 2.5, B
/Si 0.01~3.0/St2.0 or less, C/
Provided is a fiber-reinforced metal composite material characterized by having Si of 1.5 or less and N/Si of 0.1 or less. This boron-containing silicon nitride reinforcing fiber is preferably amorphous or amorphous containing a microcrystalline phase with a crystallite size of 2000 Å or less, and further has an X-ray small-angle scattering intensity of 1° and 0.
At 5°, each is preferably 1 to 20 times as large as that of air.

The present inventors found that the above-mentioned specific inorganic fiber has excellent wettability with metal materials, low reactivity, and extremely high high temperature strength. The present invention was completed based on the finding that a fiber-reinforced metal composite material having excellent heat resistance and excellent heat resistance can be obtained.

The inorganic fiber used as the reinforcing material for the inorganic fiber-reinforced metal composite material of the present invention is an inorganic fiber containing silicon, nitrogen, and boron as essential components and oxygen, carbon, and hydrogen as optional components. It does not matter whether it is crystalline or amorphous, but it is preferably substantially amorphous.

That is, it is amorphous as determined by X-ray diffraction analysis, or contains a microcrystalline phase with a crystallite size (measured using the X-ray diffraction half-width method (JONES method)) of 2000 Å or less in all directions. preferable. A particularly preferable crystallite size is 1
000 Å or less, and the more preferable crystallite size is 5
00 Å or less.

Further, the proportion of the microcrystalline phase is set so that the small-angle X-ray scattering intensity does not exceed 20 times that of air.

The ratio of each element constituting the inorganic fiber used in the present invention is expressed as an atomic ratio: N/St O, 05 to 2.5 B/S i 0.01 to 30/S i 2.0 or less C/S i 1.5 or less H/S i O, 1 or less, and the preferable atomic ratio is: N/S' 0.1-2.3 B/S' 0.05-2 0/S' 1.7 or less C /S' 1.2 or less H/S' 0.05 or less. More preferable atomic ratios are: N/S° 0.5-2.0 B/S' 0.1-1 0/S' 1.5 or less C/S' 0.5 or less H/S' 0.01 or less It is.

If the element ratio is not within the above range, the reinforcing fiber of the ceramic composite material cannot exhibit sufficient tensile strength, elastic modulus, and heat resistance.

Further, according to studies conducted by the present inventors, it has been found that it is extremely effective for the inorganic fibers used as reinforcing fibers for metal composite materials to have a specific small-angle scattering intensity.

The properties required of reinforcing fibers for metal composite materials are that the small-angle scattering intensity is in the range of 1 to 20 times the scattering intensity of air at 1° and 0.5°, respectively. A preferable small-angle scattering intensity ratio is 1 to 10 times, and a more preferable intensity ratio is in the range of 1 to 5 times both at ■6 and 0.5 degrees.

The small-angle scattering intensity detects the presence of micropores, that is, voids, or holes inside the inorganic fiber. If micropores exist in the fiber, small-angle scattering occurs due to the uneven distribution of electron density in the system. is observed.

The measurement of small-angle scattering intensity is generally performed by the method described in Experimental Chemistry Course 4 Solid State Physics J (1956) edited by the Chemical Society of Japan, but in the measurement of inorganic fibers according to the present invention, the method described below method is adopted.

Connect PSPC (Position Sensing Proportional Counter)-5 to the RJ-200B model manufactured by Rigaku Denki Co., Ltd., and set the tube voltage to 45 kV.
Tube current 95mA, first and second slits each 0.21
Use 1IIIφ, 0.15mmφ, 0.0
The scattering intensity was measured by integrating it every 2° for 1000 seconds. As a sample, cut out 18 mg of fiber with a length of 15 mm, and cut it into 10 mm.
Paste it evenly inside the slit of length x 4 mm width, 1
The intensity ratio CI (silicon nitride fiber)/BI (air)] was calculated by comparing the air scattering intensities at degrees and 0.5 degrees. The reinforcing inorganic fiber used in the present invention has a crosslinking bond represented by the following formula (i) or (ii) or (iii) or (iv) in polysilazane, and has B/S
Polyborosilazane with an i atomic ratio in the range of 0.01 to 3 and a number average molecular weight of about 200 to 500.000 (Patent Application No.
-69169) and firing the spun fibers.

(iii) -0-B-0-; In the above formula, R6 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an alkylamino group. group, hydroxyl group, or amino group, and R7 is a residue bonded to the nitrogen atom of the group having a nitrogen atom among R6, and in formula (iv), a total of three nitrogen atoms and a boron atom each. At least two of the six atoms are used for crosslinking, and R6 can be attached to the remaining atoms.

This polyborosilazane mainly has the general formula (I) (wherein R1, R2, and R3 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group,
Alternatively, it represents a group other than these groups in which the group directly bonded to silicon is carbon, an alkylsilyl group, an alkylamino group, or an alkoxy group.

However, at least one of R1, R2, and R3 is a hydrogen atom. ) Polysilazane with a number average molecular weight of about 100 to 50,000 and having a main skeleton consisting of units represented by the formula % ()
: (In these formulas, R4 may be the same or different,
A hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an alkylamino group, a hydroxyl group, or an amino group having 1 to 20 carbon atoms, and L is B(R')3 It is a compound that forms a complex with. ) The reaction of polysilazane obtained by reacting the boron compound with the boron compound and the structure of the polymer compound obtained by the reaction depend on the type of the boron compound.

For example, when a boron alkoxide is used as the boron compound, the resulting polyborosilazane has a hydrogen atom bonded to at least some silicon atoms and/or a hydrogen atom bonded to a nitrogen atom in the main skeleton of the polysilazane and the boron alkoxide. It is a compound characterized by having a side chain group or a cyclic or crosslinked structure in which the silicon atom and/or nitrogen atom are fused with boron alkoxide through reaction. For details, please refer to Japanese Patent Application No. 1-69169, but in short, this polyborosilazane is produced by reacting polysilazane with a boron compound represented by formulas (I) to (V) to obtain a boron-containing polymer with a high molecular weight. It is a compound containing a polysilazane structure.

The polysilazane used as a raw material for producing polyborosilazane in the present invention is a polysilazane having at least 5t-H bond or N-H bond in the molecule, but not only polysilazane alone, but also combinations of polysilazane and other polymers. Copolymers and mixtures of polysilazane and other compounds can also be used.

The polysilazane used includes those having a chain, cyclic, or crosslinked structure, or those having a plurality of these structures simultaneously in the molecule, and these can be used alone or in a mixture.

A brief list of typical polysilazane is as follows.

In the general formula (I), a compound having a hydrogen atom in R'lR" and R3 is perhydropolysilazane, and its production method is described, for example, in JP-A-60-145903, D, 5ey
Communication of Am
,Cer,Soc,.

C-13, January 1983. has been reported.

- A method for producing a polysilazane having a hydrogen atom in R' and R2 and a methyl group in R3 in formula (I) is D, 5eyfer
th et al. Polym, Prepr, Am, Chem,
Soc,, Div.

Polym, Chem, 25, 10 (1984)
has been reported.

- A method for producing polyorgano(hydro)silazane having hydrogen atoms in R1 and R3 and an organic group in R2 in formula (I),
D, 5eyferth et al. Polym, Prepr, +
Am.

Chem, Soc, Div, Polym, Chem
,, 25 + 10 (1984), JP-A-61-89
It is reported in Publication No. 230.

- Polysilazane other than formula (I) can also be used,
For example, 5eyferth et al.
ion of Am, Cer, Soc,, C-132+
These include polyorgano(hydro)silazane reported in July 1984.

There are no particular restrictions on the polysilazane used, and any available polysilazane can be used, but from the viewpoint of reactivity with boron compounds, R+, Rz and R3 in formula (I) are preferably groups with low steric hindrance. That is, R1, R2 and R3 are hydrogen atoms and C8~.

An alkyl group of 1 is preferable, and a hydrogen atom and an alkyl group of CI~2 are more preferable.

The boron compound to be used is not particularly limited, but from the viewpoint of reactivity, R4 in formulas (II) to (V) is preferably a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group with a CI of ~2°; Halogen atoms and C1-1
More preferred are alkyl groups and alkoxy groups of .degree., and most preferred are hydrogen atoms and halogen atoms, and alkyl and alkoxy groups of 01 to 4.

The mixing ratio of polysilazane and boron compound is B(/S
i atomic ratio is from o, ooi to 60, preferably from 0.01 to 5, more preferably from 0
．． Add so that it becomes 05 to 2.5.

The reaction can be carried out without a solvent, but it is more difficult to control the reaction than when using an organic solvent, and a gel-like substance may be produced, so it is generally better to use an organic solvent. As the solvent, hydrocarbon solvents such as aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, halogenated hydrocarbons, aliphatic ethers, and alicyclic ethers can be used. In order to obtain a high molecular weight polyborosilazane, it is preferable to react the polysilazane and the boron compound under basic conditions.

The reaction temperature is preferably within a range where the reaction system is a liquid system. To further increase the molecular weight of polyborosilazane, it is possible to carry out the reaction at a temperature higher than the boiling point of the solvent, but in order to prevent gelation due to thermal decomposition of polyborosilazane, generally 40%
The temperature is preferably below 0°C, preferably between 78°C and 300''C.

The pressure is preferably normal pressure. Although there are no particular restrictions on pressurization, it is not preferable to use reduced pressure because low-boiling components are distilled off and the yield decreases.

The reaction time is generally about 30 minutes to one day, but in order to further increase the molecular weight of polyborosilazane, it is preferable to extend the reaction time.

The reaction atmosphere is preferably a dry inert atmosphere such as dry nitrogen, dry argon, etc. in order to prevent oxidation and hydrolysis of the boron compound and polysilazane as raw materials or the polyborosilazane as a product.

This reaction is advantageous in that it does not require expensive catalysts such as noble metals.

The polyborosilazane product and the boron compound as the starting material can be separated by distillation of the boron compound under reduced pressure, gel permeation chromatography, or high-speed FF 1-body chromatography. , some silicon-hydrogen bonds of the polysilazane are condensed with hydrogen atoms or halogen atoms or organic groups of a boron compound to form a new silicon-(oxygen)-boron bond or silicon-nitrogen-boron bond, and/or , polysilazane is a polymer having a structure in which some nitrogen-hydrogen bonds are also condensed with a boron compound.

Next, the polyborosilazane obtained above is made into a spinning solution, which is then spun and fired to produce inorganic fibers.

Specifically, the solvent for the spinning solution used is one that does not show reactivity with the polyborosilazane, and such non-reactive solvents include hydrocarbons, halogenated hydrocarbons, ethers, Sulfur compounds etc. can be used.

A spinning solution containing polyborosilazane exhibits sufficient spinnability by itself to be suitable for dry spinning without the addition of an organic polymer. However, the addition of organic polymers is not necessarily excluded, and in some cases, a trace amount of organic polymers may be added.

Prior to spinning, the spinning solution is subjected to treatments such as defoaming and filtration to remove substances contained in the solution that have a harmful effect on spinning, such as gels and impurities.

Dry spinning is convenient, but centrifugal spinning, blow spinning, etc. can also be used. In dry spinning, fibers can be obtained continuously by discharging a spinning solution from a spinneret into a spinning tube to form fibers, and winding the fibers. In this case, the spinneret hole diameter, discharge speed and winding speed vary depending on the use of the composite material, but - for boat fishing, spinneret hole diameter (diameter): 0.035-0.5 ml11, preferably 0.0
5 to 0.3 mm, winding speed: 30 to 5000 m/min, preferably 60 to 2500 m/min. The atmosphere inside the spinning tube may be at least one gas selected from dry air, ammonia, and an inert gas, or at least one gas selected from dry air, ammonia, and an inert gas, or water vapor or at least one of the above-mentioned non-reactive solvents may be allowed to coexist in the atmosphere. By heating the fibers, the infusibility of the fibers in the spinning tube and the solidification caused by drying are controlled.

The temperature of the spinning solution is usually 20 to 300°C, preferably 30°C.
~200℃, and the atmospheric temperature inside the spinning cylinder is usually 20℃.
-300°C, preferably 40-250°C.

Spinning solvent remains in the dry-spun and wound fibers, so it is removed by drying and heating the fibers using dry air, ammonia, or inert gas under normal atmospheric conditions or vacuum conditions. . The heating temperature is usually in the range of 20° to 500°C. Furthermore, by tensioning the fibers during this drying, it is possible to prevent warpage, twisting, and bending that occur in the fibers during solidification. Tension is usually 1g/llllff
It is within the range of 12 to 50 kg/InIfi2.

The polyborosilazane spun fiber obtained as described above is white, but has high strength even before firing, so the fiber can be first processed into a form such as yarn or woven fabric, and then fired. .

The method for producing inorganic fibers is suitable as a method for producing continuous fibers, but it can also be applied to producing short fibers. Such short fibers can be produced by cutting the final continuous fibers obtained by firing, by cutting continuous fibers of precursor, that is, polyborosilazane, to make short fibers, and then firing them to make inorganic short fibers. is polyborosilazane (
It can be produced by directly spinning a precursor (precursor) into short fibers and firing the resulting short fibers.

Polyborosilazane is fired under an atmospheric gas or in a vacuum. Nitrogen is convenient as an atmospheric gas, but
Argon and ammonia can also be used. Further, a mixed gas of nitrogen, ammonia, argon, hydrogen, etc. can also be used.

The firing temperature is generally within the range of 700 to 1900°C. The firing time may be 0.2 hours or more.

In this firing process, the volatile components in the fibers are 300 to 6
Most of it vaporizes in the temperature range of 00°C, causing the fibers to shrink and generally cause kinks and bends, but this can be prevented by applying tension to the fibers during firing. can.

In this case, the tension is usually Ig/mm2 to 50k
g/mm 2 range is used.

The polysilazane used as a raw material for polyborosilazane, especially the silicon nitride fiber obtained by firing the polysilazane fiber previously disclosed by the applicant, is generally amorphous and has poor high-temperature strength such as elastic modulus. It has the characteristics of being excellent. For example, it remains amorphous even if held at 1200°C to 1300°C for about 1 hour. However, boron-containing silicon nitride fibers obtained by firing polyborosilazane fibers have even better heat resistance, and are preferably 1500°C or higher.
It exhibits the remarkable property of remaining amorphous even when heated to temperatures above 700°C. -For boat fishing, polycrystalline materials have lower mechanical strength than amorphous materials because the grain boundaries are the source of fracture. The inorganic fiber obtained by firing polyborosilazane is 1700
Since it remains amorphous even at °C, it has excellent high-temperature mechanical strength.

Being amorphous at 1700°C is considered to be almost the theoretical maximum value for the St-N system, and considering that even for the crystalline St-N system, 1700°C is close to the upper limit of its heat resistance. This effect is extremely excellent.

The inorganic fibers obtained above can be obtained by (1) arranging the fibers themselves in a uniaxial or multiaxial direction; (2) weaving the fibers into three-dimensional fabrics such as hand weaving, satin weaving, twill weaving, mosaic weaving, mixed weaving, etc. It is preferable to employ means such as method (3) of using the fiber as a chopped fiber to produce a more multidimensional fabric to exhibit its preferable characteristics.

In addition, in order to improve wettability with metal-containing matrices, the fiber surface is coated with a matrix metal such as titanium.
It may be coated with a boron compound or a silicone boron compound. As the coating method, conventionally known methods such as chemical vapor deposition, thermal spray deposition, sputtering deposition, vacuum deposition, electroplating, powder baking, and electroless plating can be arbitrarily employed.

The metals used as the matrix include those commonly used in composites of this type, such as copper, silver, gold, zinc, magnesium, aluminum, titanium, tin,
Any metal such as germanium, silicon, lead, iron, cobalt, nickel, zirconium, indium, or an alloy thereof can be used.

Metals preferably used in the present invention are copper, magnesium,
These include aluminum, titanium, iron, cobalt and nickel.

As described above, the inorganic fiber reinforced metal composite material of the present invention has
Although it is characterized by using a specific inorganic fiber as a reinforcing material, other known inorganic fibers can also be used in combination depending on the purpose and use of the inorganic fiber reinforced metal composite material.

Examples of inorganic fibers that can be used in combination include glass fiber, carbon fiber, poron fiber, silicon carbide fiber, alumina fiber, silica-alumina fiber, boron nitride fiber, boron carbide fiber, silicon carbide-titanium carbide fiber, etc. .

The proportion of inorganic fiber used as a reinforcing material varies depending on the form of the fibers used, such as the array structure, woven structure, and the type of metal used, but it is usually 10 to 90% of the total composite material.
It is appropriate that the amount is 25% to 70% by volume.

In order to obtain the inorganic fiber-reinforced metal composite material of the present invention, conventionally known fiber-reinforced composite material manufacturing methods such as (1) diffusion bonding, (2) liquid infiltration method, (3) thermal spraying method, and (4) electrodeposition method are used. law,
(5) extrusion and hot roll method, (6) chemical vapor deposition method, and (7) sintering method may be employed.

These manufacturing methods will be explained below.

(1) According to the diffusion bonding method, inorganic fibers and matrix metal wires are arranged alternately in one direction, and the top and bottom are covered with a thin film of matrix metal, or only the bottom is covered with the thin film and the top is covered with an organic bond. A composite material is produced by covering the matrix metal powder mixed with the agent to form a composite layer, laminating several layers, and then applying pressure under heat to produce a composite material with the matrix metal and the inorganic fibers. 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, 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 heating them under pressure.

(2) According to the liquid 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 wettability 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 (1) above.

(4) According to the electrolytic deposition method, a matrix metal is electrolytically deposited on the surface of inorganic fibers 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 method, inorganic fibers are arranged in one direction, sandwiched between matrix metal foils to form a sandwich, and then passed between heated rolls if necessary to combine the inorganic fibers and the matrix. Composite materials can be manufactured by joining metals.

(6) According to the chemical vapor deposition method, inorganic fibers are placed in a heating furnace, and a mixed gas of, for example, aluminum chloride and hydrogen gas is introduced to thermally decompose, and aluminum metal is precipitated on the surface of the inorganic fibers to form a composite. shall be.

Further, the metal-deposited fibers can be layered and arranged to form a composite material by the diffusion bonding method described in (1) above.

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

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Reference example 1 Internal volume 1! A four-loaf flask was equipped with a gas blowing tube, mechanical stirrer, and dewar condenser. After the inside of the reactor was replaced with deoxygenated dry nitrogen, 490 ml of degassed dry pyridine was placed in a four-necked flask and cooled on ice. Next, when 51.6 g of dichlorosilane was added, a white solid adduct (SilbCl z・2 C5
HsN) was generated. The reaction mixture was ice-cooled, and while stirring, 51.0 g of purified ammonia was blown into the reaction mixture through a sodium hydroxide tube and an activated carbon tube.

After the reaction was completed, the reaction mixture was centrifuged, washed with dry pyridine, and further filtered under a nitrogen atmosphere to obtain filtrate 850. The solvent was distilled off from the 5th filtrate under reduced pressure to obtain 0.102 g of solid resin perhydropolysilazane.

The number average molecular weight of the obtained polymer was 980 as measured by GPC. Also, the IR of this polymer
Examining the (infrared absorption) spectrum (solvent: dry 0-xylene; concentration of perhydropolysilazane = 10.2 g/l), the wave number (cm-') is 3350 (apparent extinction coefficient ε-0,557 jl! g- 'cl') and 1175
Absorption based on NH of i 2170 (ε=3.14) Absorption based on SiH; Absorption based on SiH and 5iNSi of 1020 to 820 was confirmed. In addition, the 'HNMR (proton nuclear magnetic resonance) spectrum (60 MHz, solvent coci3/reference material TM) of this polymer was
When examining S), it was confirmed that all of them exhibited a wide range of absorption. i.e. 64.8 and 4.4 (br,
5in); 1.5 (br.

Absorption of NH) was confirmed.

Sanshitan I Inner volume 1! A four-round flask was equipped with a glass blowing tube, mechanical stirrer, and dewar condenser.

After purging the inside of the reactor with deoxidized dry nitrogen, 300 g of dry dichloromethane and 24.3 g (0,211 mo j2 ) of methyldichlorosilane were placed in a four-bottle flask.
and cooled on ice. 18.1 g of ammonia purified through a sodium hydroxide tube and an activated carbon tube while stirring
(1,06 moA) was blown into the cell.

After the reaction was completed, the reaction mixture was centrifuged, washed with dry dichloromethane, and filtered under a nitrogen atmosphere. When the solvent is distilled off from the filtrate under reduced pressure, a colorless transparent methyl (hydro) is produced.
8.81 g of silazane was obtained. The number average molecular weight of this product was 380 as measured by GPC.

Notes: Pyridine solution of perhydropolysilazane obtained in Main Reference Example 1 (concentration of perhydropolysilazane: 5.50% by weight)
) and 34.0cc (0,3
01mo 1 ) with an internal volume of 1! The mixture was placed in an autoclave, and the reaction was carried out at 160°C for 4 hours with stirring.

After cooling to room temperature, dry 0-xylene 500 was added and the solvent was removed at a pressure of 3 to 5 mmHg and a temperature of 50 to 70°C to obtain 43 g of polyborosilazane having a number average molecular weight of 2200 in the form of a white solid.

After dissolving this polyporosilazane in 0-xylene, the solvent was removed using a rotary evaporator. When the solution became sufficiently stringable, the vacuum distillation was stopped.

This solution was transferred to a defoaming container of a dry spinning device to obtain a spinning solution. After degassing at 60°C for about 4 hours, it was discharged at 40°C through a nozzle with a diameter of 0.1 mm into a spinning tube in an air atmosphere at 120°C, and then spun at a speed of 100 m/min. It was wound up to obtain fibers with an average fiber diameter of about 10,1111.

This fiber was heated from room temperature to 600°C in an ammonia atmosphere while applying an attractive force of 500 g/mm''.
The temperature was raised at 80°C/hour, and the atmosphere was changed to nitrogen.
The temperature was raised to 1,700°C over 3 hours, maintained at 1,700°C for 1 hour, and fired to obtain black fibers. The diameter of this contact was approximately 71 RIl, the tensile strength was 200 kg/mm2, and the elastic modulus was 33 ton/mm2. X-ray diffraction measurements of the obtained fibers confirmed that the fibers were amorphous.

The elemental analysis results of the obtained fibers showed that, on a weight basis, Si:4
3.1%, N: 34.8%, C: 0.6%, 0
: 11.8%, B: 7.80%.

Furthermore, the fibers obtained by firing at 1800°C have an X-ray diffraction pattern of 2θ-20°, 23°26
．． 5', 31', 34.5', 35°,
α-3iJa near 39°, 42', 43.5'
A broad peak that seems to be related to 2θ=23
．． 5°, 27', 33.5', 36'41.
5°, a broad peak that seems to be related to β-3isNa appears near α-5i3N4 and β
It was found that -5iJa microcrystals were formed.

In addition, the X-ray scattering intensity ratio of the obtained fibers was 1° and 0.5
In all cases of 6, it was 20 or less.

Kokokando 5! 600 d of dry 0-xylene and 50 g (0,427 mo 1 ) of boron trichloride were placed in a four-bottle flask and cooled on ice under a stream of nitrogen gas to form an 0-xylene solution of perhydropolysilazane obtained in Reference Example 1. (Concentration of perhydropolysilazane: S, tO weight %) 600 d was added dropwise over 1 hour. After the addition is complete, stir at 30°C for 5 hours.29
) The reaction was repeated. Add 450 d (2,13 m
1.1.1-3.3.3 of ) Hexamethyldisilazane was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was heated under reflux for 4 hours to form a precipitate. This precipitate was filtered and the solvent of the filtrate was distilled off under reduced pressure to obtain 52 g of polyborosilazane having a number average molecular weight of 3,200 in the form of a pale yellow solid.

After dissolving this polyborosilazane in O-xylene, the solvent was removed using a rotary evaporator. When the solution became sufficiently stringable, the vacuum distillation was stopped. This solution was transferred to a defoaming container of a dry spinning device to obtain a spinning solution. After standing at 60°C for about 4 hours to degassing, it was discharged at 60°C from a nozzle with a diameter of 0.1 mm into a spinning tube under a nitrogen atmosphere at 80°C, and wound at a speed of 100 m/min. A fiber with a diameter of about 12 mm was obtained.

While applying a tension of 500 g/nun'' to this fiber, it was heated from room temperature to 1700''C under a nitrogen atmosphere for 3
The temperature was raised at a rate of 00°C/hour and held at 1700°C for 1 hour to obtain black fibers. The diameter of this fiber is approximately 9
Made of ceramic with a tensile strength of 180 kg/mm and an elastic modulus of 30 tons.
/mm2. From X-ray diffraction measurements of the obtained fibers,
It was confirmed that it was amorphous. The elemental analysis results of the obtained fibers were as follows: Si: 46.8%, N: 40.3%, C: 1 on a weight basis.
．． 80%, 0:2.2%, B: 7.75%.

Furthermore, the fiber obtained by firing at 1800°C has an X-ray diffraction pattern of 2θ-20°, 23°26.
5°, 31', 34.5°, 35°, 39°
, 42°, and a broad peak that seems to be related to α-3iJ4 around 43.56, and 2θ = 23.5°.
, 27°, 33.5°, 36°, 41.5°, broad peaks that seem to be related to β-5iJ4 appear, and α-3i3N4 and β-5i3N4
It was found that microcrystals were formed.

In addition, the X-ray scattering intensity ratio of the obtained fibers was 1° and 0.5
° was 20 or less in all cases.

Reference 1 Pyridine solution of methylhydrosilazane obtained in Reference Example 2 (concentration of methylhydrosilazane, 6.40% by weight)
and 6001d and decaborane 15 g (0,123 mo
1) into an autoclave with an internal volume of 12 and heated to 80°C.
The reaction was carried out with stirring for 3 hours. After cooling to room temperature,
When the solvent was distilled off under reduced pressure in the same manner as in Example 1, polyborosilazane 39 with a number average molecular weight of 2400 was obtained as a light brown solid.
I got g.

After dissolving this polyborosilazane in 0-xylene, the solvent was removed using a rotary evaporator. When the solution became sufficiently stringable, the vacuum distillation was stopped.

This solution was transferred to a defoaming container of a dry spinning device to obtain a spinning solution. After standing at 60°C for about 4 hours to defoam, it was discharged at 40°C from a nozzle with a diameter of 0.1 mm into a spinning tube in an air atmosphere at 100°C, and wound at a speed of 200 m/min. Fibers with an average fiber diameter of 10,11111 were obtained.

While applying a tension of 300 g/am2 to this fiber,
60”C from room temperature to 600’C under ammonia atmosphere
/ hour, and then changed the atmosphere to nitrogen to 1700
The temperature was raised to 1,700°C for 3 hours and then fired at 1700°C for 1 hour to obtain black fibers. The diameter of this fiber is approximately 8/
ff11, the tensile strength was 280 kg/mm'', and the elastic modulus was 40 ton/mm''. X of the obtained fiber
It was confirmed by line diffraction measurement that it was amorphous. The elemental analysis results of the obtained fibers are based on weight, S i :
40.2%, N: 41.5%, C:O, S%, O
: 3.2%, B: 14.3%.

Furthermore, the fiber obtained by firing at 1800°C has an X-ray diffraction pattern of 2θ=2o″, 23°26.5
°, 31°, 34.5", 35', 39'
, 42°, and 43.5°, there are broad peaks that are thought to be related to α-5i3N4, and 2θ = 23.5°.
, 27@, 33.5" and 36°41.5', broad peaks that seem to be related to β-3iJ4 appear, and α-3i3N4 and β-5isN
It was found that microcrystals of a were formed.

In addition, the X-ray scattering intensity ratio of the obtained fibers was 1° and 0.5
° was 20 or less in all cases.

A four-loaf flask with a reference coal tank internal volume of 10j2, a gas blowing pipe,
A mechanical stirrer and dewar condenser were installed. After the inside of the reactor was replaced with deoxygenated dry air, 4900 d of degassed dry pyridine was placed in a fourth flask and cooled on ice. Next, when 744 g of dichlorosilane is added, a white solid adduct (SiHzCfz・2C
3H3N) was generated. The reaction mixture was ice-cooled, and while stirring, 735 g of purified ammonia was blown into the reaction mixture through a sodium hydroxide tube and an activated carbon tube, and then heated to 100''C.

After the reaction is completed, the reaction mixture is centrifuged, washed with dry pyridine, and further filtered under nitrogen atmosphere to obtain filtrate 5.
Obtained 100 relatives. The solvent was distilled off from the filtrate 5d under reduced pressure to obtain 0.249 g of resinous solid perhydropolysilazane.

The number average molecular weight of the obtained polymer was 980 as measured by GPC.

Next, 5000 d of the obtained 5% perhydropolysilazane pyridine solution was added for 10 minutes! Place in a stainless steel autoclave, add 100 g of ammonia, and heat at 80°C for 3
The mixture was stirred for hours to cause a polycondensation reaction. After cooling to room temperature,
The gas was replaced with nitrogen. This modified perhydropolysilazane had a number average molecular weight of 2,400 and a weight average molecular weight of 20,000 (gel permeation chromatography method, polystyrene standard).

Add 50001 nl of xylene to this solution and heat it on a rotary evaporator at 60°C until the volume of the solution is 1000 d.
The residue was distilled off under reduced pressure. When this operation was repeated two more times, the amount of pyridine contained in the solution was 0.03% by weight (gas chromatography method).

Further, the solvent was removed using a rotary evaporator. Vacuum removal was discontinued when the solution became sufficiently stringy. This solution was transferred to a defoaming container of a dry spinning device to obtain a spinning solution. After standing at 60"C for about 2 hours to defoam, 30"
It was discharged from a nozzle with a diameter of 0.1 mm into a spinning tube in an air atmosphere at 130°C and wound at a speed of 300 m/min to obtain fibers with an average fiber diameter of 7 mm.

Next, while applying a tension of 500 g/mm2 to the spun fibers, the spun fibers were heated from room temperature to 900°C in a nitrogen atmosphere for 1 time.
The temperature was raised at 80°C/hour to obtain silicon nitride fibers.

The tensile strength of this silicon nitride fiber is 230 to 390 kg/
IIn112 (average 270 kg/nIn, elastic modulus is 2
0 to 73 ton/mm2 (average 28 ton/III
Elemental analysis of this silicon nitride fiber revealed that silicon was 58.1% by weight, nitrogen was 35.1% by weight, oxygen was 1.42% by weight, and carbon was 1.45% by weight. Ta.

5000 d of the pyridine solution of perhydropolysilazane obtained in Reference Example 1 was placed in a pressure-resistant reaction vessel with an internal volume of 10 f.
The reaction was carried out in a nitrogen atmosphere and in a closed system at 120° C. with stirring for 3 hours. During this time, a large amount of gas was generated, and the pressure increased by 2.0 kg/aft before and after the reaction. After leaving it to room temperature,
The gas was replaced with nitrogen. The number average molecular weight of this modified perhydropolysilazane was 1,950. Add 1000 d of ethylbenzene to this solution and
When the solvent was distilled off under reduced pressure at °C, a white powder was obtained.

Toluene was gradually added to the white powder to dissolve it, and when the solution became sufficiently stringable, the addition of toluene was stopped. This solution was transferred to a degassing container of a dry spinning device, left to stand at 60°C for about 4 hours to defoam, and then heated to 40°C with a diameter of 0.
．． The fibers were discharged from a 08 mm nozzle into a spinning tube under an argon atmosphere at 100° C. and wound at a speed of 1000 m/min to obtain fibers with an average fiber diameter of 10 −.゛Next, a tension of 500 g/mm2 was applied to the spun fibers, and N
The temperature was raised from room temperature to 1100°C at a rate of 200°C/hour in two atmospheres to obtain silicon nitride fibers.

The tensile strength of this silicon nitride fiber is 210 to 360 kg/
llll112, elastic modulus 35-75ton/llll1
It was 12.

A fourth flask with a main internal volume of 51 moxibustion charcoal was equipped with a gas blowing pipe, a mechanical stirrer, and a dewar condenser. After replacing the inside of the reaction system with deoxygenated dry nitrogen, 3000 d of degassed dry pyridine was placed in a four-neck flask and cooled on ice. Next, when 902.5 g of dichlorosilane was added, a white solid adduct (SiNzCj2z・2C2
N5N) was generated. The reaction mixture was ice-cooled, and while stirring, 255.2 g of purified ammonia mixed with nitrogen gas was blown into the reaction mixture through a sodium hydroxide tube and activated carbon.

After the reaction was completed, the reaction mixture was centrifuged, washed with dry methylene chloride, and then filtered under a nitrogen atmosphere to obtain 4700 d of filtrate.

Add polyethylene oxide (molecular weight 5 Xl06) to 4000 mN of the filtrate containing perhydropolysilazane 365.
After stirring vigorously for 1 hour, the solvent was distilled off under reduced pressure and circulated to obtain a pyridine solution containing 30% by weight of perhydropolysilazane as a spinning solution. After filtering and defoaming the spinning solution, white fibers were obtained by dry spinning in a nitrogen atmosphere.

This was dried at 50°C under reduced pressure for 4 hours, and then
After heat treatment at 100°C for 3 hours, ammonia atmosphere,
Heating at 900°C for 1 hour followed by heating at 105°C under nitrogen atmosphere.
Silicon nitride fibers were obtained by heating at 0°C for 5 hours.

When the obtained fiber was subjected to X-ray diffraction, it was confirmed that it was amorphous silicon nitride. In addition, the fiber diameter is 10 to 20
tensile strength of 90-350 kg/mm2, 9-
Elastic modulus of 30tOn/lllIn2 and 3~7X101
It had an electrical resistance of 2ΩCa+.

This MJf! LL Silicon nitride fibers having the following properties obtained in Reference Example 6 were arranged in a uniaxial direction on pure aluminum foil (1070) with a thickness of 0.5 mm, and the aluminum foil was covered on top of the silicon nitride fibers. L on the branch L N/si 1.27 C/ S i O,05B 0 / S i 0.043 H/St O,15 X Ha L Note 2 1° 1.2 0.5° 1.8 670° A composite foil made of fibers and aluminum was manufactured by hot rolling at a temperature of C. 27 sheets of this composite foil were stacked and left under vacuum at a temperature of 670°C for 10 minutes, and then hot pressed at 600°C to produce a silicon nitride fiber-reinforced aluminum composite material. The fiber content of this composite material is 30% by volume. The produced composite material had a tensile strength of 75 kg/mm'' and an elastic modulus of 11 ton/mm''.

Silicon nitride fiber N/S i 0.902 C/ S i O,013 0/ S i O,060 H/St O,0B X-ray ha LP' 1° 8.7 0.5° 11.4 The elementary fibers 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 silicon nitride fibers are layered and arranged, and the gaps between the 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 in an argon atmosphere. 200kg/C11 at 1150°C
Hot pressing was carried out for 3 hours while applying a pressure of I to obtain a silicon nitride fiber reinforced titanium composite material.

This composite material contained 45% by volume of silicon nitride fibers, and its tensile strength was 165 kg/mm'', which was approximately 2.8 times the strength of titanium.

Comparison coal J Silicon nitride fiber C/ Si O, 00B 0/St O, 07 H/St O, 07 Inlet wire small 5-loss tensile strength Le 1° 6 .8 0.5" 10.5 The basic fibers are cut into 1++ u++ lengths and chopped into 3% aluminum, 1% manganese, and 1.3% zinc.
, the balance is added to magnesium alloy powder consisting of magnesium, and after thoroughly mixing, a 70 x 5 stainless steel foil
Packed into a 0 x 10 mm mold and placed under an argon atmosphere at 490 °C.
It was molded by heating at °C and under a pressure of 200 kg/all for 1 hour, and finally, the stainless steel foil was removed and the surface was polished to produce a magnesium alloy composite material.

In the resulting composite material, 3 silicon nitrides were added as chops.
It contained 0% by volume, and its tensile strength was 52 kg/2 shells.

The boron-containing silicon nitride inorganic fibers obtained in Reference Example 3 were arranged in a uniaxial direction on pure aluminum foil (1070) with a thickness of 0.5 mm, and the aluminum foil was covered on top of the boron-containing silicon nitride inorganic fibers. 670
A composite foil made of fibers and aluminum was produced by hot rolling at a temperature of °C. After stacking 27 sheets of this composite foil and leaving it under vacuum at a temperature of 670°C for 10 minutes,
A boron-containing silicon nitride inorganic fiber-reinforced aluminum composite material was produced by hot pressing at °C. The fiber content of this composite material is 30% by volume. The manufactured composite material has a tensile strength of 76 kg/mm” and an elastic modulus of 12 ton/mm.
mm”, tensile strength perpendicular to the fiber is 6.5 kg/m
It was "m".

Furthermore, titanium metal was applied to the boron-containing silicon nitride inorganic fibers obtained in Reference Example 4 arranged in a uniaxial direction using a thermal spraying device.
．． 1~10I! It was coated to a thickness of In. The boron-containing silicon nitride inorganic fibers were arranged in layers, and the gaps between the layers were filled with titanium metal powder and pressure molded, and the molded body was pre-fired at 520°C for 3 hours in a hydrogen gas atmosphere. Furthermore, 200 kg/c at 1150°C under argon atmosphere
Hot pressing was carried out for 3 hours while applying a pressure of IiI to obtain a boron-containing silicon nitride inorganic fiber-reinforced titanium composite material. This composite material contains 45% by volume of boron-containing silicon nitride inorganic fibers, and has a tensile strength of 170%.
kg/mm” and exhibits approximately 2.9 times the strength of titanium.
Tensile strength perpendicular to the fibers is 18 kg/mm2
Met.

The boron-containing silicon nitride inorganic fiber obtained in Reference Example 5 was
Add the chopped material to a magnesium alloy powder consisting of 3% aluminum, 1% manganese, 1.3% zinc, and the balance magnesium, and mix thoroughly. 1
The mixture was packed in a 0 mm mold, heated at 490° C. in an argon atmosphere, and held under a pressure of 200 kg/c11i for 1 hour to form.Finally, the stainless steel foil was removed and the surface was polished to produce a magnesium alloy composite material. The resulting composite material contained 30% by volume of boron-containing silicon nitride as a chop.
The tensile strength was 53 kg/mm''.

〔Effect of the invention〕

The inorganic fiber-reinforced metal composite material obtained by the present invention has high strength and elastic modulus of the inorganic fibers used as reinforcing materials. The wettability between the metal-containing matrix and the metal-containing matrix is significantly improved, and the reactivity is also low, so that the combined effect is fully exhibited. Therefore, the composite material according to the present invention has extremely high tensile strength, high elastic modulus, and excellent heat resistance and abrasion resistance.

Furthermore, since the composite material of the present invention is inexpensive to manufacture, it can be used for aircraft, space development materials, ships, marine construction materials, land transportation equipment materials, construction and civil engineering materials, machining materials, medical care materials, nursing care materials, etc. can.

Claims (1)

[Scope of Claims] 1. A fiber-reinforced metal composite material made by reinforcing a metal matrix with inorganic fibers, the inorganic fibers having silicon, nitrogen and boron as essential components and oxygen, carbon and hydrogen as optional components; The ratio of each element is expressed as an atomic ratio of N/Si0.0
5 to 2.5, B/Si 0.01 to 3, O/Si 2.0 or less, C/Si 1.5 or less, and H/Si 0.1 or less. 2. The inorganic fiber is amorphous or has a crystallite size of 200
The composite material according to claim 1, which is amorphous and contains a microcrystalline phase of 0 Å or less. 3. The inorganic fiber has an X-ray small angle scattering intensity of 1° and 0.5
Composite material according to claim 1 or 2, each having a temperature of 1 to 20 times that of air at a temperature of 1 to 20 times that of air.