JPH0726166B2 - Inorganic fiber reinforced metal composite material - Google Patents

Description

TECHNICAL FIELD The present invention relates to an inorganic fiber reinforced metal composite material (hereinafter, may be abbreviated as “composite material”) having excellent mechanical properties.

(Prior art and its problems) Fiber-reinforced metal composite materials are practically used mainly as structural materials at high temperatures, such as engine parts and supersonic primary structural materials, due to their high toughness and mechanical properties. Is expected. However, the fiber-reinforced metal composite material is produced by the reaction between the matrix metal and the reinforcing fiber during its production.
Since the reinforcing fiber deteriorates, the strength is considerably lower than the theoretical strength according to the composite rule. For example, when carbon fibers are used as the reinforcing fibers and aluminum is used as the matrix, it is known that the reaction between the carbon fibers and the molten aluminum produces aluminum carbide, and the strength is significantly reduced. Therefore, although a surface treatment for forming a layer inert to aluminum on the surface of the carbon fiber is performed, it has not been possible to obtain a satisfactory mechanical strength.

(Means for Solving the Problem) An object of the present invention is to provide a composite material having excellent mechanical strength, which solves the above problems.

Another object of the present invention is to provide a composite material having excellent bond strength between a matrix made of metals and inorganic fibers.

Another object of the present invention is to provide a composite material having excellent compatibility between the matrix and the inorganic fibers and excellent strength efficiency due to the inorganic fibers.

Further, another object of the present invention is to provide a composite material in which the strength of the inorganic fiber is not significantly reduced when forming the composite material.

The composite material of the present invention comprises inorganic fibers as a reinforcing material, a metal or an alloy as a matrix, and the inorganic fibers are inorganic fibers obtained from a silicon-containing polycyclic aromatic polymer, the constituent components of which are i) Shows at least one crystal arrangement state 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 which constitutes a polymer. Carbonaceous, 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) From an amorphous phase consisting essentially of Si, C and O and / or crystalline ultrafine particles consisting essentially of β-SiC having a particle size of 500Å or less and amorphous SiO _x (0 <x ≦ 2) Na A high-strength, high-modulus inorganic material composed of Si—C—O material, which is an aggregate and whose proportions of constituent elements are Si; 30 to 70% by weight, C; 20 to 60% by weight, and O; 0.5 to 10% by weight. It is characterized by being a fiber.

First, the inorganic fiber in the present invention will be described in detail. In the following description, "part" is "part by weight",
"%" Is "% by weight".

The inorganic fiber of the present invention comprises the above-mentioned constituents i), ii) and ii.
i), Si; 0.01-29%, C; 70-99.9% and
O; 0.001-10%, preferably Si; 0.1-25%, C; 74-99.8
% And O; 0.01 to 8%.

The crystalline carbon, which is a constituent component of this inorganic fiber, has a crystallite size of 500 Å or less, and corresponds to a 3.2 Å (002) plane oriented in the fiber axis direction in a high resolution electron microscope having a resolution of 1.5 Å. It is an ultrafine graphite crystal that allows the observation of a fine lattice image. The crystalline carbon in the inorganic fiber may 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, or the like. This is due to the presence of the mesophase polycyclic aromatic compound (2) in the raw material.

Sum of constituents i) and ii) of this inorganic fiber 100
The ratio of constituent iii) to parts is 0.015 to 200 parts, and the ratio of constituents i) and ii) is 1: 0.02 to 4.

Component ii for 100 parts of the sum of components i) and ii)
When the ratio of i) is less than 0.015, it is almost the same as the pitch fiber, and the effect of improving the oxidation resistance and decreasing the reactivity with the matrix metal is not sufficient, and when the ratio exceeds 200 parts, the graphite fine Crystals are not effectively formed, and fibers having a high elastic modulus cannot be obtained.

In the continuous inorganic fiber in the present invention, microcrystals having a small layer spacing and a three-dimensional array are effectively generated,
Silicon atoms are distributed very uniformly so as to enclose the fine crystals.

The inorganic fiber in the present invention is mainly composed of 1) a bond unit (Si—CH ₂ ), or a bond unit (Si—CH ₂ ) and a bond unit (Si—Si), and a hydrogen atom or a lower alkyl group in a side chain of a silicon atom. Group having a side chain group selected from the group consisting of a phenyl group and a silyl group, a bond unit (Si-
The ratio of the total number of CH ₂ ) to the total number of bonding units (Si-Si) is 1: 0 to 20
At least a part of the silicon atoms of the organosilicon polymer in the range of 100 parts of a random copolymer bonded to the aromatic ring of a petroleum-based or coal-based pitch or a heat-treated product thereof through a silicon-carbon linking group, and (2) A polycyclic aromatic compound obtained by heat-treating a petroleum-based or coal-based pitch or composed of both phases of a mesophase and an optically isotropic phase (hereinafter, both are collectively referred to as “mesophase polycyclic aromatic compound”). The compound is sometimes referred to as a "compound".) 5 to 50,000 parts are heated and reacted and / or melted at a temperature in the range of 200 to 500 ° C to obtain a silicon-containing polycyclic aromatic polymer, the above-mentioned silicon. A second step of preparing and spinning a spinning dope of a polycyclic aromatic polymer containing the compound, a third step of infusibilizing the spinning dope under tension or no tension
And a fourth step of firing the infusibilized spun fiber bundle at a temperature in the range of 800 to 3000 ° C. in a vacuum or an inert gas atmosphere.

Each of the above steps will be described more specifically.

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 sodium metal is added in an inert gas at 400 It is obtained by heating to ℃ or more.

The organosilicon polymer, binding unit (Si-CH _2), or binding units (Si-CH ₂₎ primarily consists binding units (Si-Si), the total number pairing unit of coupling units (Si-CH ₂₎ (Si-S
The ratio of the total number of i) is in the range of 1: 0 to 20.

The weight average molecular weight (M _w ) of the organosilicon polymer is generally
Those of 300 to 1000, especially 400 to 800 are preferable for preparing the random copolymer (1) which is an intermediate raw material for obtaining an excellent carbon-based inorganic fiber.

Another starting material, a polycyclic aromatic compound, is a pitch obtained from petroleum and / or coal, and a particularly preferable pitch is a heavy oil obtained by fluid catalytic cracking of petroleum, and the heavy oil is distilled. The obtained distillate components or residual oil and the pitch obtained by heat-treating them.

The pitch contains 5 to 98% of insoluble components in organic solvents such as benzene, toluene, xylene, and tetrahydrofuran.
It is preferably contained in a weight percentage. When a pitch containing less than 5% by weight of the insoluble component is used as a raw material, the strength,
Inorganic fibers with excellent elastic modulus cannot be obtained, and when pitch of more than 98% by weight is used as a raw material, the molecular weight of the copolymer increases sharply and some coking may occur, making spinning difficult. Become.

The weight average molecular weight (M _w ) of this pitch is 100 to 3000.

The weight average molecular weight is a value determined as follows. That is, when the pitch does not contain the organic solvent insoluble matter for gel permeation chromatograph (GPC) measurement of benzene, toluene, xylene, tetrahydrofuran, chloroform and dichlorobenzene, GPC measurement is performed as it is,
When the pitch contains the above-mentioned organic solvent-insoluble matter, hydrogenation treatment is performed under mild conditions to change the above-mentioned organic solvent-insoluble matter into the above-mentioned organic solvent-soluble component, and then perform GPC measurement. The weight average molecular weight of the polymer containing the organic solvent insoluble matter is a value obtained by performing the same treatment as above.

Random copolymer (1) is preferably obtained by adding petroleum-based or coal-based pitch to an organosilicon polymer, and preferably in an inert gas.
It is prepared by reacting by heating at a temperature in the range of 250 to 500 ° C.

The ratio of the pitch used is 83 to 4 per 100 parts of the organosilicon polymer.
It is preferably 900 parts.

If the use ratio of the pitch is too small, the carbon-silicon component in the obtained inorganic fiber will increase, and the inorganic fiber having a high elastic modulus will not be obtained, and if the ratio is too large, the carbon-silicon component will increase. Therefore, the effects of improving the oxidation resistance and reducing the reaction deterioration with the matrix metal are not sufficiently exhibited.

If the reaction temperature of the above reaction is excessively low, the bond between the silicon atom and the aromatic carbon becomes difficult to form, and if the reaction temperature is excessively high, the generated random copolymer (1) decomposes and becomes high in molecular weight. It does not happen.

The mesophase polycyclic aromatic compound (2) is prepared, for example, by heating petroleum-based or coal-based pitch in an inert gas at 300 to 500 ° C. and polycondensating while removing the produced soft fraction. You can

If the polycondensation reaction temperature is too low, the condensed ring will not grow sufficiently, and if the temperature is too high, an insoluble and infusible product will be produced by coking.

The melting point of mesophase polycyclic aromatic compound (2) is 200.
~ 400 ℃, the weight average molecular weight of 200 ~ 10
It is 000.

Among the mesophase polycyclic aromatic compounds (2), 20-
Having 100% optical anisotropy, 30-100% benzene,
Those containing an insoluble matter in toluene, xylene or tetrahydrofuran are particularly preferable in order to obtain an inorganic fiber excellent in mechanical performance.

In the first step, the random copolymer (1) and the mesophase polycyclic aromatic compound (2) are heated and melted and / or reacted in the temperature range of 200 to 500 ° C. to form a silicon-containing polycyclic aromatic polymer. Prepare a spinning polymer.

The mesophase polycyclic aromatic compound (2) is preferably used in an amount of 5 to 50,000 parts per 100 parts of the random copolymer (1), and if it is less than 5 parts, the mesophase content in the product will be insufficient, resulting in a high content. If an elastic fired yarn cannot be obtained, and if it is more than 50,000 parts, the effects of improving the oxidation resistance and reducing the reaction deterioration with the matrix metal are not sufficiently exhibited due to lack of the silicon component.

The weight average molecular weight of the silicon-containing polycyclic aromatic polymer is 20
It has a melting point of 200 to 400 ° C. at 0 to 11000.

Second step: The silicon-containing polycyclic aromatic polymer obtained in the first step is melted by heating, and in some cases, this is filtered to remove microgels, impurities and other substances harmful to the spinning. This is spun by a commonly used synthetic fiber spinning device. The temperature of the spinning dope during spinning varies depending on the softening temperature of the raw polymer, but a temperature in the range of 220 to 420 ° C is advantageous.

In the spinning device, a spinning tube is attached if necessary,
After making the atmosphere in the spinning cylinder one or more atmospheres selected from the group consisting of air, inert gas, hot air, heat inert gas, steam, and ammonia gas, a small diameter is obtained by increasing the winding speed. Fibers can be obtained. The spinning speed in the melt spinning varies depending on the average molecular weight of the raw material, the molecular weight distribution, and the molecular structure, but is 50 to 5000.
It is preferably in the range of m / min.

Third step: The spun fiber obtained in the second step is infusibilized under the action of tension or no tension.

A typical infusibilizing method is a method of heating the molded body in an oxidizing atmosphere. The temperature of infusibilization is preferably 50 to 400
The temperature is in the range of ° C. If the infusibilization temperature is too low, the polymer forming the matrix will not stick, and if the temperature is too high, the polymer will burn.

The purpose of infusibilization is to make the polymer that constitutes the spun fiber into an infusible or insoluble state of a three-dimensional structure so that it will not melt during the firing of the next step and will not fuse with adjacent fibers. Is. Examples of the gas forming the oxidizing atmosphere at the time of infusibilization include air, ozone, oxygen, chlorine gas, bromine gas, ammonia gas, and mixed gas thereof.

As another infusibilizing method different from the above, the spun fiber is infusibilized by γ-ray irradiation or electron beam irradiation while heating at low temperature in an oxidizing atmosphere or a non-oxidizing atmosphere under tension or no tension as necessary. Methods can also be employed.

The purpose of irradiating this γ ray or electron beam, by further polymerizing the polymer forming the spun fiber,
This is to prevent the spinning raw yarn from melting and losing the fiber shape.

The appropriate irradiation dose of gamma rays or electron beams is 10 ⁶ to 10 ¹⁰ rads.

Irradiation can be performed in a vacuum, an inert gas atmosphere, or an oxidizing gas atmosphere such as air, ozone, oxygen, chlorine gas, bromine gas, ammonia gas, or a mixed gas thereof.

The infusibilization by irradiation can be performed at room temperature, and if necessary, the infusibilization can be achieved by heating while heating in the temperature range of 50 to 200 ° C.

If the infusibilization is carried out under no tension, the spun fiber will have a wavy shape due to shrinkage, but in some cases it can be corrected in the firing step of the next step, tension is not always necessary, but tension acts In such a case, a good result can be obtained by applying a tension higher than the tension that can at least prevent the spun fiber from contracting and becoming wavy during infusibilization.

When infusibilizing, the tension applied is 1 to 500 g / mm ²
The range is preferable, and even if a tension of 1 g / mm ² or less is applied, it is not possible to give tension that does not cause the fiber to sag, and
The fiber may break when a tension of 0 g / mm ² or more is applied.

Fourth step: The infusible yarn obtained in the third step is fired at a temperature in the range of 800 to 3000 ° C. in a vacuum or an inert gas atmosphere to obtain an inorganic fiber mainly composed of carbon, silicon and oxygen. .

In the firing step, it is not always necessary to apply tension, but high-temperature inorganic fiber with less bending can be obtained by firing at high temperature while applying tension in the range of 0.001 to 100 Kg / mm ² .

In the heating process, mineralization becomes severe from about 700 ℃,
It is estimated that mineralization is almost completed at about 800 ° C. Therefore, the firing is preferably performed at a temperature of 800 ° C. or higher. Moreover, since an expensive apparatus is required to obtain a temperature higher than 3000 ° C., firing at a temperature higher than 3000 ° C. is impractical in terms of cost.

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

The form of the Si—C—O substance that is the constituent component iii) of the inorganic fiber can be controlled by the mineralization temperature in the fourth step.

If it is desired to obtain substantially Si, C, an amorphous consisting O, and mineralization temperature is preferably set to 800 to 1000 ° C., substantially beta-SiC and amorphous Si0 _x (where To obtain 0 <x ≦ 2), a temperature of 1700 ° C. or higher is suitable.

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

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

For the inorganic fiber, for example, a method of orienting the fiber itself in a uniaxial direction or a polyaxial direction, a method of using various kinds of woven fabrics such as plain weave, satin weave, dummy weave, twill weave, three-dimensional woven fabric, or the like, or The composite material of the present invention can be manufactured by applying the method of using as chopped fiber or the like.

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

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

The composite material of the present invention can be manufactured by the following ordinary method for manufacturing a fiber-reinforced metal composite material. That is, (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 sintering methods Is the way.

(1) According to the diffusion bonding method, inorganic fibers and matrix metal wires are alternately arranged in one direction, and the upper and lower parts thereof 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 an organic bond. It is possible to form a composite layer by covering with a matrix metal powder mixed with an agent to form a composite layer, stacking the layers several times, and then applying pressure under heating to produce a composite material of inorganic fibers and a matrix metal.

The organic binder is preferably one that volatilizes and dissipates before being heated to a temperature at which matrix metals and carbides are formed, and for example, CMC, paraffin, resin, mineral oil and the like can be used.

In addition, a matrix metal powder admixed with an organic binder may be arranged and laminated on the periphery of the inorganic fiber, and the mixture may be pressed under heating to obtain a composite material.

(2) According to the melt infiltration method, it is possible to fill a gap between inorganic fibers arranged with molten aluminum, aluminum alloy, magnesium, magnesium alloy, titanium or titanium alloy to obtain a composite material. in this case,
In particular, since the wettability between the metal-coated fiber and the matrix metal is good, it is possible to completely fill the gaps between the arranged fibers with the matrix metal.

(3) According to the thermal spraying method, the matrix metal can be applied to the surface of the arranged inorganic fibers by plasma spraying or gas spraying to produce a tape-shaped composite material. It can be used as it is, or the tape-shaped composite material can be further laminated, and the composite material can be manufactured by the diffusion bonding method (1).

(4) According to the electrolytic deposition method, a matrix metal can be electrolytically deposited on the surface of the fiber to form a composite, which can be further laminated and arranged, and the composite material can be formed by the diffusion bonding method of the above (1).

(5) According to the extrusion and hot roll method, fibers are arranged in one direction, sandwiched between matrix metal foils to form a sandwich, and the fibers and the matrix metal are passed through between heated rolls if necessary. Join them together,
Composite materials can be manufactured.

(6) According to the chemical vapor deposition method, the fiber is put into a heating furnace, and, for example, a mixed gas of aluminum chloride and hydrogen gas is introduced and thermally decomposed, and aluminum metal is deposited on the surface of the fiber to form a composite. To do. Further, by stacking and arranging the metal-deposited fibers, a composite material can be manufactured by the diffusion bonding method (1).

(7) According to the sintering method, the gaps between the arranged fibers can be filled with the matrix metal powder, and then heat-sintered with or without pressure to obtain a composite material.

The tensile strength (σ _c ) of a composite material produced from inorganic fibers and a metal matrix is represented by the following formula.

_{σ c = σ f V f +} σ M V M σ c: tensile strength of the composite sigma _f: tensile strength of the inorganic fibers sigma _M: metal matrix tensile strength V _f: volume percentage of the inorganic fibers V _M: volume of the metal matrix Percentage As shown by the above equation, the strength of the composite material increases as the volume ratio of the inorganic fibers in the composite material increases. Therefore, in order to manufacture a composite material having high strength, it is necessary to increase the volume ratio of the inorganic fibers to be composited. However, when the volume ratio of the inorganic fibers exceeds 70%, the amount of the metal matrix is so small that the gaps between the inorganic fibers cannot be sufficiently filled with the metal matrix. The strength as shown is not exerted. Further, as the volume ratio of the inorganic fibers in the composite material is reduced, the strength of the composite material decreases as shown by the above equation, so 10% or more of the inorganic material is required to obtain a practical composite material. It is necessary to compound the fibers. Therefore, as described above, in the production of the inorganic fiber-reinforced metal composite material of the present invention, the composite ratio of the inorganic fiber is 10
The best effect is obtained when the amount is ~ 70% by volume.

When manufacturing a composite material, as described above, it is necessary to heat the metals near or above the melting temperature to form a composite with the reinforcing fibers, which causes a decrease in fiber strength due to the reaction between the inorganic fibers and the molten metals. Although a problem, when the inorganic fiber of the present invention is immersed in molten metals, the rapid deterioration of the fiber as observed in ordinary carbon fiber is not observed, and thus a composite material having excellent mechanical strength is obtained. be able to.

Next, methods for measuring various mechanical properties used in the present invention will be described.

(A) Initial reaction deterioration rate a) In the case of metals and alloys having a melting point of 1200 ° C. or less 1 minute, 5 minutes, 10 minutes in a molten metal heated to a temperature 50 ° C. higher than the melting point of the metal using inorganic fibers, Immerse for 30 minutes, then extract the fibers and measure the tensile strength of the fibers. From this result, the relationship between the immersion time and the tensile strength of the fiber, that is, the reaction deterioration curve is obtained, and the initial reaction deterioration rate (kg / mm ² · sec ⁻¹ ) is obtained from the tangent line at the immersion time of 0 minutes.

B) In the case of metals and alloys whose melting point is higher than 1200 ° C: Inorganic fiber and metal foil are laminated, and this is heated to a temperature of (melting point of metal foil) x (0.6 to 0.7) in vacuum, and 5 kg / mm ²
It is held under pressure for 5 minutes, 10 minutes, 20 minutes, 30 minutes, and then the fibers are extracted and the fiber tensile strength is measured. From this result, the initial reaction deterioration rate is obtained by the same procedure as in (a).

b) Reduction rate of fiber strength The reduction rate of fiber strength is obtained in (a) by determining the fiber strength after 30 minutes of immersion time and 30 minutes of holding time.
It is calculated by dividing the above fiber strength) by the initial strength.

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

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

(C) Interlaminar shear strength test A composite method in which 10 × 12 × 2 mm inorganic fibers are uniaxially oriented on two pins (length 20 mm) with a curvature radius of 6 mmφ in the test method for determining the interlaminar shear stress. Place the material and the radius of curvature of the tip
It is compressed with an indenter of 3.5 mmφ and a test is performed by a so-called three-point bending method to measure the interlaminar shear stress (kg / mm ² ). It is indicated by shear stress (kg / mm ² ).

(D) Fatigue test A 10φ x 100mm round bar is manufactured so that the axial direction of the composite material in which the inorganic fibers are oriented uniaxially becomes the major axis direction, and this is processed into a predetermined rotational bending fatigue test piece. And the capacity is 1.5 kgm
The rotating bending fatigue test was performed and the fatigue strength was calculated 10 ⁷ times as the fatigue.

The ratio of fatigue strength to tensile strength is an index indicating the strength of bond between the matrix and the fiber.

(Effects of the Invention) The inorganic fiber of the present invention is less likely to deteriorate in fiber strength due to reaction with molten metals, so that the inorganic fiber-reinforced metal composite material obtained by the present invention has excellent mechanical properties such as tensile strength,
Due to its high elastic modulus and excellent heat resistance and abrasion resistance, it is a material for synthetic fibers, a material for synthetic chemistry, a material for machinery industry, a material for construction machinery, a material for marine development (including space), a material for automobiles. It is used as various materials such as food materials.

Due to its excellent abrasion resistance, it is used as various materials such as synthetic fiber materials, synthetic chemical materials, machinery industry materials, construction machinery materials, marine development (including space) materials, automobile materials, food materials, etc. To be done.

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

Reference Example 1 (Production of Inorganic Fiber I) 2.5 l of anhydrous xylene and 40 parts of sodium were placed in a 5 l three-neck flask.
0 g was added, the mixture was heated to the boiling point of xylene under a nitrogen gas stream, and dimethyldichlorosilane 1 was added dropwise over 1 hour.
After completion of the dropping, the mixture was heated under reflux for 10 hours to form a precipitate. The precipitate was filtered, washed with methanol and then with water to obtain 420 g of white powdery polydimethylsilane.

This polydimethylsilane 400g, a gas introduction pipe, a stirrer,
Charge a 3 liter three-necked flask equipped with a condenser and a distillation tube,
Heat treatment was carried out at 420 ° C. under a nitrogen stream of 50 ml / min while stirring to obtain 350 g of a colorless transparent slightly viscous liquid in the distilling receiver.

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

The infrared absorption spectrum of this substance was measured and found to be 65
Absorption of Si-CH ₃ at 0-900 cm ^-1 and 1250 cm ^-1 , Si at 2100 cm ^-1
Absorption of -H, Si-CH ₂ -Si absorption of the of 1020 cm ^-1 and near 1355 cm ^-1, absorption of CH was observed at 2900 cm ^-1 and 2950 cm ^-1,
Further, when the far-infrared absorption spectrum of this substance was measured, absorption of Si-Si was observed at 380 cm ^-1 , and thus the obtained liquid substance was mainly composed of (Si-CH ₂ ) bond units and (Si-Si). It was found to be an organosilicon polymer having a bonding unit and having a hydrogen atom and a methyl group in the side chain of silicon.

From the results of nuclear magnetic resonance analysis and infrared absorption analysis, this organosilicon polymer shows that the total number of (Si—CH ₂ ) bond units is
It was confirmed that the polymer had a ratio of the total number of -Si) bond units of approximately 1: 3.

300 g of the above organosilicon polymer was treated with ethanol to remove low molecular weight substances, and 40 g of a polymer having a number average molecular weight of 1200 was obtained.

Measurement of the infrared absorption spectrum of this material, the absorption peak similar to that described above was observed, the material consists predominantly (Si-CH ₂₎ coupling units and (Si-Si) bond unit, hydrogen on the side chain of the silicon It was found to be an organosilicon polymer having atoms and methyl groups.

From the results of nuclear magnetic resonance analysis and infrared absorption analysis, this organosilicon polymer shows that the total number of (Si—CH ₂ ) bond units is
It was confirmed that the polymer had a ratio of the total number of -Si) bond units of about 7: 1.

On the other hand, among petroleum fractions, high boiling point substances above light oil are
Fluid catalytic cracking / rectification was carried out at a temperature of 500 ° C. in the presence of an alumina cracking catalyst to obtain a residue from the bottom of the column. Hereinafter, this residue is referred to as FCC slurry oil.

As a result of elemental analysis, the 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 by nuclear magnetic resonance analysis.

100 g of the above FCC slurry oil was heated at 420 ° C. for 2 hours under a nitrogen gas flow of 1 / min, the distillate at the same temperature was distilled off, and the residue was filtered while hot at 150 ° C. The portion was removed to obtain 57 g of a light component removal pitch.

The light content removal pitch contained 60% xylene insoluble matter.

25 g of the organosilicon polymer and 20 ml of xylene were added to 57 g of the light content removing pitch, the temperature was raised with stirring, and xylene was distilled off, followed by reacting at 400 ° C. for 6 hours to obtain 43 g of a random copolymer (1). .

As a result of infrared absorption spectrum measurement, this reaction product was found to have Si-H bond (IR: 2100 cm ^-1 decrease) existing in the organosilicon polymer, and new Si-C (carbon of benzene ring) bond (I
The formation of R: 1135 cm ^-1 ) revealed that the organosilicon polymer was a copolymer having a part of silicon atoms directly bonded to the polycyclic aromatic ring.

This random copolymer (1) did not contain a xylene-insoluble portion, had a weight average molecular weight of 1400, and had a melting point of 265 ° C. This was heated and melted at 300 ° C. and allowed to stand, and the light portion was removed due to the difference in specific gravity to obtain 40 g of the rest. This is called a polymer (a).

In parallel with this, 400 g of the above FCC slurry oil was heated to 450 ° C. under a nitrogen gas stream, the distillate at the same temperature was distilled off, and the residue was filtered while hot at 200 ° C. The fused portion was removed to obtain 180 g of a light material removal pitch. 180 g of the obtained light content removing pitch was subjected to polycondensation at 400 ° C. for 8 hours in a nitrogen stream while removing the light content produced by the reaction to obtain a heat treatment pitch of 80.3 g.

This heat treatment pitch has a melting point of 310 ° C, xylene insoluble content of 97%,
It was a mesophase polycyclic aromatic polymer (2) containing 20% of quinoline insoluble matter and having an optical anisotropy of 95% by observation with a polarizing microscope of the polished surface. This was again heated, melted and left to stand at 350 ° C., and the light portion was separated and removed due to the difference in specific gravity, and 80 g of the rest was obtained.

This is mixed with 40 g of polymer (a) and the mixture is mixed in a nitrogen atmosphere for 3
The mixture was melted and heated at 50 ° C. for 1 hour to obtain a silicon-containing polycyclic aromatic polymer in a uniform state.

This polymer had a melting point of 290 ° C. and contained 70% xylene-insoluble matter.

Using the silicon-containing polycyclic aromatic polymer as a raw material for spinning, using a metal nozzle having a nozzle diameter of 0.15 mm, melt spinning at 360 ° C., the obtained spinning raw yarn is oxidized in air at 300 ° C.,
It was made infusible and further fired at 1300 ° C. in an argon atmosphere to obtain an inorganic fiber I having a diameter of 10 μm.

This fiber had a tensile strength of 295 kg / mm ² and a tensile elastic modulus of 26 t / mm ² , and had a clearly radial structure from the observation of the fracture surface.

Reference Example 2 (Production of Inorganic Fiber II) 200 g of the FCC slurry oil obtained in Reference Example 1 was heated at 450 ° C. for 0.5 hours under a nitrogen gas flow of 2 l / min, and the distillate was distilled off at the same temperature. Was hot filtered at 200 ° C. to remove the infusible portion at the same temperature to obtain 57 g of a light material removal pitch.

The light content removal pitch contained 25% xylene insoluble matter.

25 g of the organosilicon polymer obtained in Reference Example 1 and 20 ml of xylene were added to 57 g of this light component removal pitch, the temperature was raised with stirring, xylene was distilled off, and the mixture was allowed to react at 400 ° C. for 6 hours to give 51 g of random copolymerization. Coalescence (1) was obtained.

As a result of infrared absorption spectrum measurement, this reaction product was found to have Si-H bonds (IR: 2100 cm ^-1 ) present in the organosilicon polymer.
And the formation of a new Si-C (carbon of benzene ring) bond (IR: 1135cm ^-1 ) was observed, so that some of the silicon atoms of the organosilicon polymer were directly bonded to the polycyclic aromatic ring. It was found to be a copolymer having a portion.

This random copolymer (1) does not contain a xylene-insoluble portion, has a weight average molecular weight of 1400, a melting point of 265 ° C and a softening point of 3
It was 10 ° C.

On the other hand, 180 g of the light content removal pitch was subjected to polycondensation at 400 ° C. for 8 hours under a nitrogen stream while removing the light content produced by the reaction to obtain a heat treated pitch of 97.2 g.

This heat-treated pitch contains a melting point of 263 ° C, a softening point of 308 ° C, xylene insoluble content of 77%, and quinoline insoluble content of 31%. It was a group polymer (2).

90 g of this mesophase polycyclic aromatic polymer (2) and 6.4 g of the random copolymer (1) were mixed, and under a nitrogen atmosphere,
It was melted and heated at 380 ° C. for 1 hour to obtain a silicon-containing polycyclic aromatic polymer in a uniform state.

This polymer has a melting point of 267 ° C, a softening point of 315 ° C and 70%.
It contained xylene insoluble matter.

Using the silicon-containing polycyclic aromatic polymer as a raw material for spinning, using a metal nozzle having a nozzle diameter of 0.15 mm, melt spinning at 360 ° C., the obtained spinning raw yarn is oxidized in air at 300 ° C.,
It was made infusible and was further fired at 1300 ° C. in an argon atmosphere to obtain an inorganic fiber II having a diameter of 8 μm.

This fiber had a tensile strength of 320 kg / mm ² and a tensile elastic modulus of 26 t / mm ² , and had a clearly radial structure from the observation of the fracture surface.

The inorganic fiber II was ground, alkali-melted, treated with hydrochloric acid to form an aqueous solution, and then subjected to high-frequency plasma emission spectroscopic analysis. As a result, it was found that the silicon content in the inorganic fiber II was 0.95%.

Reference Example 3 (Production of Inorganic Fiber III) Mesophase polycyclic aromatic compound (2) 97 g and random copolymer (1) 3 g were mixed and silicon-containing was carried out in the same manner as in Reference Example 2 except that the mixture was melt-heated at 400 ° C. A polycyclic aromatic polymer was obtained.

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

The above high molecular weight material was spun and infusibilized in the same manner as in Reference Example 2 and then fired at 2500 ° C. in an argon atmosphere to obtain an inorganic fiber III having a diameter of 7.2 μm.

The tensile strength of this fiber was 335 kg / mm ² , and the tensile elastic modulus was 53 t / mm ² .

This inorganic fiber III was ground, alkali-melted, treated with hydrochloric acid to obtain an aqueous solution, and then subjected to high-frequency plasma emission spectroscopic analysis. As a result, it was found that the silicon content in this inorganic fiber III was 0.42%.

Reference Example 4 (Production of Silicon Carbide Fiber) The silicon carbide fiber obtained from only polycarbosilane used in Comparative Example 7 was produced as follows.

To 100 parts by weight of polydimethylsilane synthesized by dechlorinating and condensing dimethyldichlorosilane with sodium metal, 3 parts by weight of polyborosiloxane was added and heat-condensed at 350 ° C. in nitrogen to obtain the compound represented by the formula (Si—CH ₂ A polycarbosilane having a main chain skeleton mainly composed of carbosilane units, and having a hydrogen atom and a methyl group in the silicon atom of the carbosilane units was obtained. This polymer is melt-spun and blown in air at 190
Infusibilization treatment at ℃, followed by firing in nitrogen at 1300 ℃, fiber diameter 13μ, tensile strength 300kg / mm ² , tensile elastic modulus 16t / mm ² silicon carbide mainly composed of silicon, carbon and oxygen Fiber was obtained.

Example 1 On a 0.5 mm thick pure aluminum foil (JIS standard 1070),
Inorganic fibers I were arranged in a uniaxial direction, the aluminum foil was covered on the inorganic fibers I, and a hot roll at a temperature of 670 ° C. was used to produce a composite foil in which the fibers and aluminum were composited. Twenty-seven of these composite foils were stacked, left under vacuum at a temperature of 670 ° C. for 10 minutes, and then hot pressed at 600 ° C. to produce an inorganic fiber-reinforced aluminum composite material.

For inorganic fibers, initial reaction deterioration rate (kg / mm ² · sec
^-1 ) and fiber strength reduction rate (%), and for composite materials, tensile strength in the fiber direction (kg / mm ² ), tensile elastic modulus in the fiber direction (t / mm ² ), interlaminar shear strength ( kg / mm ² ), tensile strength in the direction perpendicular to the fiber (kg / mm ² ), and fatigue limit / tensile strength were measured. The results are shown in Table 1. Note that V _f is 30
It was% by volume.

Comparative Example 1 Instead of the inorganic fiber used in the present invention, the tensile strength was 300 k.
A carbon fiber-reinforced aluminum composite material was produced in the same manner as in Example 1 except that a commercially available PAN-based carbon fiber having a g / mm ² and an elastic modulus of 21 t / mm ² was used, and the characteristic values were measured. The results are also shown in Table 1. The V _f was 30% by volume.

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

Comparative Example 2 A carbon fiber-reinforced aluminum composite material was produced in the same manner as in Example 2 except that the carbon fiber described in Comparative Example 1 was used instead of the inorganic fiber, and the characteristic values were measured. The results are also shown in Table 2.

Example 3 Titanium metal was coated on the inorganic fibers I arranged in a uniaxial direction with a thickness of 0.1 to 10 μm by using a thermal spraying device. The inorganic fibers were laminated and arranged, the gaps between the laminated layers were filled with titanium powder and pressure-molded, and the molded body was subjected to hydrogen gas atmosphere at 520 ° C. for 3
After pre-baking for 1 hour, it is further heated to 1150 ° C in an argon atmosphere.
Then, hot pressing was performed for 3 hours while applying a pressure of 200 kg / cm ² , to obtain an inorganic fiber reinforced titanium composite material.

For inorganic fibers, initial reaction deterioration rate (kg / mm ² · sec
^-1 ) and fiber strength reduction rate (%) were measured. For composite materials, tensile strength in the fiber direction (kg / mm ² ), interlaminar shear strength (kg / mm ² ), tensile strength in the direction perpendicular to the fiber ( kg / mm ² ) 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 / mm.
^{At 2} , it was about twice the tensile strength of titanium metal alone. The V _f was 45% by volume.

Comparative Example 3 A carbon fiber-reinforced titanium composite material was produced in the same manner as in Example 3 except that the carbon fiber described in Comparative Example 1 was used instead of the inorganic fiber, and the characteristic values were measured. The results are also shown in Table 3.

Example 4 An inorganic fiber I arranged in a uniaxial direction was coated with a titanium alloy (Ti-6Al-4V) to a thickness of 0.1 to 10 μm by using a thermal spraying device. The inorganic fibers were laminated and arranged, the gap between the laminated layers was filled with titanium powder and pressure-molded, and the molded body was pre-baked at 520 ° C. for 3 hours in a hydrogen gas atmosphere, and then at 1150 ° C. in an argon atmosphere. Hot pressing was performed for 3 hours while applying a pressure of 200 kg / cm ² to obtain an inorganic fiber reinforced titanium composite material.

For inorganic fibers, initial reaction deterioration rate (kg / mm ² · sec
^-1 ) and fiber strength reduction rate (%), and for composite materials, interlaminar shear strength (kg / mm ² ), tensile strength in the direction perpendicular to the fiber (kg / mm ² ), and fatigue limit / tensile strength Was measured. The results are shown in Table 4. The V _f 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 fiber described in Comparative Example 1 was used instead of the inorganic fiber, and the characteristic values were measured. The results are also shown in Table 4.

Example 5 Inorganic fibers I are uniaxially arranged on a pure magnesium foil having a thickness of 0.5 mm, the magnesium foil is covered on the inorganic fibers I, and the fibers and magnesium are combined by a hot roll at a temperature of 670 ° C. The produced composite foil was manufactured. After stacking 27 sheets of this composite foil and leaving them under vacuum at a temperature of 670 ° C for 10 minutes,
An inorganic fiber reinforced magnesium composite material was manufactured by hot pressing at 00 ° C.

For inorganic fibers, initial reaction deterioration rate (kg / mm ² · sec
^-1 ) and fiber strength reduction rate (%), and for composite materials, interlayer shear strength (kg / mm ² ), tensile strength in the direction perpendicular to the fiber (kg / mm ² ), and fatigue limit / tensile strength did. The V _f was 30% by volume. The results are shown in Table 5.

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

Example 6 On a magnesium alloy foil (JIS standard A891) having a thickness of 0.5 mm, inorganic fibers I were arranged in a uniaxial direction, the magnesium alloy foil was covered with the inorganic fibers I, and a hot roll at a temperature of 670 ° C. was used. , A composite foil in which a fiber and a magnesium alloy were composited was manufactured. 27 sheets of this composite foil are piled up, left under vacuum at a temperature of 670 ° C for 10 minutes, and then hot pressed at 600 ° C,
An inorganic fiber reinforced magnesium composite material was produced.

For inorganic fibers, initial reaction deterioration rate (kg / mm ² · sec
^-1 ) and fiber strength reduction rate (%), and for composite materials, interlayer shear strength (kg / mm ² ), tensile strength in the direction perpendicular to the fiber (kg / mm ² ), and fatigue limit / tensile strength did. The results are shown in Table 6. The V _f 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 fiber described in Comparative Example 1 was used instead of the inorganic fiber, and the characteristic values were measured. The results are also shown 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 fiber obtained in Reference Example 3 was used.

The tensile strength of the obtained composite material was similar to that of the composite material obtained in Example 1, but the tensile modulus was 6.
It was 3 t / mm ² . The V _f was 30% by volume.

Example 7 On a pure aluminum foil (JIS standard 1070) having a thickness of 0.5 mm,
Inorganic fibers II were arranged in a uniaxial direction, the aluminum foil was covered on the inorganic fibers II, and a hot roll at a temperature of 670 ° C. was used to produce a composite foil in which the fibers and aluminum were composited. Twenty-seven of these composite foils were stacked, left under vacuum at a temperature of 670 ° C. for 10 minutes, and then hot pressed at 600 ° C. to produce an inorganic fiber-reinforced aluminum composite material.

For inorganic fibers, initial reaction deterioration rate (kg / mm ² · sec
^-1 ) and fiber strength reduction rate (%), and for composite materials, tensile strength in the fiber direction (kg / mm ² ), tensile elastic modulus in the fiber direction (t / mm ² ), interlaminar shear strength ( kg / mm ² ), tensile strength in the direction perpendicular to the fiber (kg / mm ² ), and fatigue limit / tensile strength were measured. The results are shown in Table 7 together with the results of Comparative Example 1. The V _f was 30% by volume.

Example 8 A fiber reinforced metal was produced in the same manner as in Example 7 except that an aluminum alloy foil (JIS standard 6061) was used, and the characteristic values were measured. The results are shown in Example 8 together with the results of Comparative Example 2.
Shown in the table.

Example 9 An inorganic fiber II arranged in a uniaxial direction was coated with titanium metal to a thickness of 0.1 to 10 μm by using a thermal spraying device. The inorganic fibers were laminated and arranged, the gaps between the laminated layers were filled with titanium powder and pressure-molded, and the molded body was subjected to hydrogen gas atmosphere at 520 ° C. for 3
After pre-baking for 1 hour, it is further heated to 1150 ° C in an argon atmosphere.
Then, hot pressing was performed for 3 hours while applying a pressure of 200 kg / cm ² , to obtain an inorganic fiber reinforced titanium composite material.

For inorganic fibers, initial reaction deterioration rate (kg / mm ² · sec
^-1 ) and fiber strength reduction rate (%) were measured. For composite materials, tensile strength in the fiber direction (kg / mm ² ), interlaminar shear strength (kg / mm ² ), tensile strength in the direction perpendicular to the fiber ( kg / mm ² ) and fatigue limit / tensile strength were measured. The results are shown in Table 9 together with the results of Comparative Example 3.

The tensile strength of the obtained composite material in the fiber direction is 122 kg / mm.
^{At 2} , it was about twice the tensile strength of titanium metal alone. The V _f was 45% by volume.

Example 10 A titanium alloy (Ti-6Al-4V) having a thickness of 0.1 to 10 μm was coated on an inorganic fiber II arranged in a uniaxial direction by using a thermal spraying device. The inorganic fibers were laminated and arranged, the gap between the laminated layers was filled with titanium powder and pressure-molded, and the molded body was pre-baked at 520 ° C. for 3 hours in a hydrogen gas atmosphere, and then at 1150 ° C. in an argon atmosphere. Hot pressing was performed for 3 hours while applying a pressure of 200 kg / cm ² to obtain an inorganic fiber reinforced titanium composite material.

For inorganic fibers, initial reaction deterioration rate (kg / mm ² · sec
^-1 ) and fiber strength reduction rate (%), and for composite materials, interlaminar shear strength (kg / mm ² ), tensile strength in the direction perpendicular to the fiber (kg / mm ² ), and fatigue limit / tensile strength Was measured. The results are shown in Table 10 together with the results of Comparative Example 4.

The V _f was 45% by volume.

Example 11 On a pure magnesium foil having a thickness of 0.5 mm, inorganic fibers II were uniaxially arranged, and the magnesium foil was covered thereon, and the fibers and magnesium were combined by a hot roll at a temperature of 670 ° C. The produced composite foil was manufactured. After stacking 27 sheets of this composite foil and leaving them under vacuum at a temperature of 670 ° C for 10 minutes,
An inorganic fiber reinforced magnesium composite material was manufactured by hot pressing at 00 ° C.

For inorganic fibers, initial reaction deterioration rate (kg / mm ² · sec
^-1 ) and fiber strength reduction rate (%), and for composite materials, interlayer shear strength (kg / mm ² ), tensile strength in the direction perpendicular to the fiber (kg / mm ² ), and fatigue limit / tensile strength did. The V _f was 30% by volume. The results are shown in Table 11 together with the results of Comparative Example 5.

Example 12 A 0.5 mm thick magnesium alloy foil (JIS standard A891) was uniaxially arranged with inorganic fibers II, and the magnesium alloy foil was covered on the inorganic fibers II by a hot roll at a temperature of 670 ° C. , A composite foil in which a fiber and a magnesium alloy were composited was manufactured. 27 sheets of this composite foil are piled up, left under vacuum at a temperature of 670 ° C for 10 minutes, and then hot pressed at 600 ° C,
An inorganic fiber reinforced magnesium composite material was produced.

For inorganic fibers, initial reaction deterioration rate (kg / mm ² · sec
^-1 ) and fiber strength reduction rate (%), and for composite materials, interlayer shear strength (kg / mm ² ), tensile strength in the direction perpendicular to the fiber (kg / mm ² ), and fatigue limit / tensile strength did. The results are shown in Table 12 together with the result of Comparative Example 6. Note that V _f is
It was 30% by volume.

Example 13 An inorganic fiber-reinforced aluminum composite material was produced in the same manner as in Example 7 except that the inorganic fiber III obtained in Reference Example 3 was used. The V _f was 30% by volume.

The tensile strength of the obtained composite material was about the same as that obtained in Example 7, but the tensile elastic modulus was 15.2 t / mm ² .

Front page continuation (72) Inventor Masaki Shibuya 5 1978, Kogushi, Ube, Ube City, Yamaguchi Prefecture Masaki Okui, Examiner, Ube Laboratory, Ube Industries, Ltd.

Claims (1)

[Claims] 1. An inorganic fiber reinforced metal composite material comprising an inorganic fiber as a reinforcing material and a metal or alloy as a matrix, wherein the inorganic fiber is an inorganic fiber obtained from a silicon-containing polycyclic aromatic polymer, The 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 which constitutes the polymer. A carbonaceous material showing a crystalline alignment state, ii) a non-oriented crystalline carbon and / or amorphous material derived from an optically isotropic polycyclic aromatic compound containing an organic solvent insoluble component constituting the polymer Carbon, and iii) crystalline amorphous particles consisting essentially of Si, C and O and / or crystalline ultrafine particles consisting essentially of β-SiC having a particle size of 500 Å or less and amorphous S Si-C-, which is an aggregate composed of iO _x (0 <x ≦ 2), in which the proportion of constituent elements is Si; 30 to 70% by weight, C; 20 to 60% by weight, and O; 0.5 to 10% by weight. An inorganic fiber reinforced metal composite material, which is a high-strength, high-modulus inorganic fiber made of an O substance.