JPH01213472A - Production of fiber molded product - Google Patents

Abstract

PURPOSE:To provide a fiber molded product having excellent adhesivity to a matrix metal, by immersing carbon fiber bundles in an organic solvent containing an organic silicon polymer and the fine powder of the metal, etc., preliminarily molding the immersed carbon fiber bundles and subsequently calcining the pre-molded product to combine the carbon fibers with each other with the resultant silicon carbide ceramic. CONSTITUTION:Carbon fiber bundles are immersed in an organic solvent solution which is prepared by dissolving an organic silicon polymeric compound, e.g., cyclic polysilane or chain polysilane, containing silicon and carbon atoms. as main structural components and dispersing the fine powder of a metal or ceramic in the resultant solution, thereby impregnating the carbon fiber bundles with the polymeric compound, followed by preliminarily molding the impregnated carbon fiber bundles. The pre- molded product is thermally calcined to pyrolyze the organic silicon polymer impregnated in the bundles into silicon carbide ceramic, thereby providing a rigid fiber bundle molded product wherein the carbon fibers are combined with each other and coated with the silicon carbide ceramic through the fine powder of the metal or ceramic. The molded product is again immersed in an organic solvent containing the organic silicon polymer and thermally calcined once or more to provide a fiber-reinforced metal composite material retaining a high tensile strength, high rigidity and heat resistance.

Description

[Detailed description of the invention] The present invention is suitably used when obtaining fiber reinforced metal composite materials (FRM) by pressure casting, vacuum casting, etc. using continuous carbon fibers. The present invention relates to a method of manufacturing a fiber molded article.

Fiber-reinforced metal composite materials (FRM), which are currently being developed using conventional technology, have excellent properties such as being lightweight and maintaining high strength, high rigidity, and high heat resistance up to high temperature ranges. It is a material that has been actively researched in recent years.

Its manufacturing method includes ■A method in which fibers are immersed in molten metal and cast.

■Matrix metal is thermally sprayed and electrodeposited on the fiber surface.

A method of attaching fibers by vapor deposition, etc., and then diffusion bonding the fibers by hot pressing, etc.

■Mix fibers and matrix metal powder.

Known methods include sintering by rolling or extrusion, and (2) arranging fibers between matrix metal foils and molding by heating and pressurizing.

The above method (■) involves directly creating fiber moldings and casting molds of the desired shape, and pouring molten metal into them, making it possible to manufacture composite materials with complex shapes in a short process and with extremely high productivity. be. However, in composite materials with a metal matrix, the reinforcing fibers and metal must be combined at high temperatures, which causes the reinforcing fibers to react with the matrix and deteriorate, resulting in the strength of the composite material being lower than that of the composite material. The result is much lower than the expected value. For example, carbon fiber, which is a typical reinforcing fiber, is manufactured industrially in large quantities at low cost, and has a lower density and higher specific strength and specific modulus than other ceramic fibers, making it a lighter material. However, this carbon fiber is difficult to wet with light metals such as aluminum, and when it reacts at high temperatures, brittle aluminum carbide and other substances are formed at the interface. It has the serious drawback that the expression of the reinforcing mechanism is impaired.

Therefore, as a method to suppress the deterioration of reinforcing fibers and the formation of aluminum carbide during composite formation, a matrix metal is attached to the reinforcing fiber surfaces at low temperatures in advance.
Various attempts have been made, including the Ω method and the methods (1) and (2) in which the metal is composited at a temperature that does not melt the metal. However, these methods require complicated operations for surface treatment of fibers, arrangement of fibers, etc., and have the disadvantage that hot pressure production equipment is complicated and productivity is poor. In addition, these methods cannot produce composite materials with complex shapes, so it is necessary to first obtain a composite intermediate material in the form of an extremely thin wire or extremely thin plate, and then further heat it at a low temperature that does not melt the matrix metal. , a method of pressurizing and molding into the desired shape has been adopted, resulting in an unavoidable long process and high cost, and industrial production using the above methods The current situation is that this is not being done.

On the other hand, in view of these points, in method (1), which is advantageous as an industrial manufacturing method, a thin film is formed on the surface of the reinforcing fibers so that the reinforcing fibers and the matrix metal are easily wetted and the reinforcing fibers are not deteriorated by reaction. is being attempted.

Silicon carbide is the most suitable material for this film, and by forming a silicon carbide film, it is possible to improve wettability and adhesion and to suppress reactions with matrix metal or air.

Methods for forming a film on the surface of the reinforcing fibers include conventional techniques for coating the surface of a carbonaceous material with a silicon carbide material, such as A, a chemical vapor deposition method (CVD) using an organic silicon halide or a silicon compound, and a hydrocarbon. The following methods are known: method B), method B, method of coating the surface of a carbonaceous material with an organosilicon polymer compound, and heating and firing it to form a silicon carbide film.

Among these methods, method A includes methods disclosed in Japanese Patent Publication No. 60-5682, Japanese Patent Application Publication No. 57-111289, Japanese Patent Application Publication No. 57-118082, and Japanese Patent Application Publication No. 58-31167, etc. These methods are similar to method (1) described above, and have the disadvantage that they require complicated chemical vapor deposition equipment and have extremely low productivity, making the reinforcing fibers very expensive.

In addition, as method B, Tokoku No. 57-22915, Tokoku No. 7115, Tokko Sho 57, and Tokoku No. 60-
No. 14820, Special Publication No. 17948, Special Publication No. 1983
There are methods disclosed in Japanese Patent Laid-Open No. 52-91917, No. 17.950, and the like.

Among these, the method described in Japanese Patent Publication No. 57-22915 is
Organic silicon polymer compounds are applied to the surfaces of crucibles, electrodes, etc. made of carbon materials and fired to form a film of silicon carbide substances, which improves oxidation and corrosion resistance in the air. The purpose is to Furthermore, Japanese Patent Publication No. 57-7115 also describes a method for coating reinforcing fibers for composite materials, and this method uses -B-0- which is different from the organosilicon polymer compound used in the present application.
The coating is performed using a resin composed of 8L-0- bonds, which is different from silicon carbide. In addition, Japanese Patent Publications No. 60-14820, Japanese Patent Publication No. 61-17948, and Japanese Patent Publication No. 61-17950 disclose a method of forming a ceramic film by coating and firing an organic silicon polymer compound on the surface of carbon fibers. has been done.

However, these methods.

(a) An organic silicon polymer compound whose main skeleton components are silicon, oxygen, and boron is used, and the film after firing has a very high oxygen content, and the various advantages mentioned above of the silicon carbide film are fully realized. It is not demonstrated.

(b) In the method of coating the fiber surface, a silicon oxide intermediate layer is provided and an extraction operation is performed using a solvent that does not dissolve the organosilicon polymer compound, which makes the structure of the fiber coating complex and lengthens the process. There is a disadvantage.

(c) The fibers adhere to each other and there is no gap for the matrix metal to penetrate, and the composite is not reinforced sufficiently.

(d) Although it is suitable as a method to obtain a molded object with a simple shape as an intermediate material such as an extremely thin wire shape made of several thousand fibers bundled together, these intermediate materials cannot be used to make various complex parts shapes. A method is required in which the material is placed in a mold having a desired shape and then heated under pressure, resulting in a longer process and an unavoidable increase in cost.

Furthermore, JP-A-52-91917 discloses a method in which the surface of carbon fibers is coated with an organosilicon polymer compound whose main skeleton components are silicon and carbon and fired. It has the disadvantage that the comrades are bonded to each other and there is no gap for the matrix metal to penetrate, and it is suitable for obtaining molded bodies with relatively simple shapes such as extremely thin wires or extremely thin plates; In order to form a part, these intermediate materials are placed in a mold of the desired shape and then composited with a matrix again, which requires a long process similar to the above.

As mentioned above, with the conventional technology, it is not easy to bundle 10 million to 10 million continuous fibers and mold them into a desired shape. It is also difficult to create a structure in which the fibers do not stick together, and it is also difficult to obtain a fiber molded product that maintains the desired shape and maintains its shape even when cast under high pressure when manufacturing composite materials. This is extremely difficult, and at present no satisfactory method has yet been proposed for industrially advantageously producing a fiber molded product that is excellent as a single reinforcing fiber.

In manufacturing a fiber-reinforced metal composite material using a casting method using carbon fibers, the present inventors formed a silicon carbide film on the surface of the reinforcing fibers to improve the bond between the reinforcing fibers and the matrix metal. It can improve wettability and reactivity, and
We are actively investigating a manufacturing method for a fiber molded body that can easily bundle and mold a large amount of reinforcing fibers, and that allows the matrix metal to easily penetrate between the R vertebrae of the fiber molded body of the parentheses to obtain a high-strength composite material. As a result, it has been found that a fiber molded article that satisfies the above conditions can be obtained in an extremely simple and extremely short process using the method described below.

That is, when producing a fiber molded body for carbon fiber reinforced gold JiIIIP11 composite material, an organosilicon polymer compound having silicon and carbon as main skeleton components, especially general formula (1) (however, R
' and R'' represent a hydrogen atom, an alkyl group, a phenyl group, and a trialkylsilyl group, respectively.

n represents an integer of 4 or more. ), or a cyclic polysilane represented by the general formula (II) (wherein R1 and R2 each represent a hydrogen atom, an alkyl group, a phenyl group, or a trialkylsilyl group, and R3゜R4 each represent a hydrogen atom, an alkyl group, a phenyl group, A trialkylsilyl group, a hydroxyl group, an alkoxy group, and n is an integer of 30 or more. 3 in an atmosphere of being chosen
An organosilicon polymer compound whose main skeleton components are silicon and carbon obtained by heating to a temperature in the range of 00°C or more and 2000°C or less is dissolved in an organic solvent,
Further, a carbon fiber bundle is immersed in a solution prepared by adding and dispersing fine powder of metal or ceramics to impregnate the carbon fiber bundle with the solution, and then the carbon fiber bundle is preformed into a desired shape. The organosilicon polymer compound impregnated into the carbon fiber bundle by heating and firing is thermally decomposed into a silicon carbide ceramic, and the silicon carbide ceramic is bonded between the carbon fibers via the fine powder of the metal or ceramic. By bonding, carbon fibers coated with carbon fiber surfaces are extremely effective as fiber-reinforced metal composite materials with aluminum, magnesium, or their alloys as a matrix, especially as fiber moldings when manufacturing composite materials using high-pressure casting methods. It was found that a bundle molded body can be obtained.

Furthermore, when the fiber molded body obtained in this way is immersed again in a solution of the same organosilicon polymer compound dissolved in an organic solvent, and the process of drying and firing is repeated at least once, the molded fiber body is produced by a casting method. The inventors have discovered that it is possible to obtain a fiber molded body that can be used as a highly reliable composite material that has very high strength and little variation, and has led to the present invention.

According to the present invention, a carbon fiber bundle is immersed in a solution in which an organosilicon polymer compound and a fine metal or ceramic powder are dissolved and dispersed in an organic solvent, and then formed into a desired shape, dried, and fired. Just by itself.

The metal or ceramic fine powder is interposed between the fibers to prevent the fibers from adhering to each other, creating a gap between the fibers in which the matrix metal can enter. The fibers are strongly bonded through the fine powder, and it is possible to obtain a fiber molded body with high shape retention that does not deform even when the fiber bundle is handled during manufacturing or under pressure during the casting process.

Furthermore, since the surface of the carbon fiber is coated with silicon carbide ceramics converted from an organic silicon polymer compound, the wettability of the carbon fiber with metal is improved, and the reaction between the molten metal and the carbon fiber is also suppressed. When this carbon fiber is cast and composited with a matrix metal, an extremely strong composite material can be obtained. In addition, according to the present invention,
By immersing the fiber molded body again in a solution of an organosilicon polymer compound, drying, and firing, it is possible to obtain a composite material with even higher strength, that is, extremely close to the theoretical strength expected from the composite side. To easily obtain a composite material having a desired part shape by manufacturing a fiber molded body, which is molded into a desired shape, and simply by casting the fiber molded body under pressure in melting metal. Can be done.

Accordingly, the present invention provides carbon fibers in a solution prepared by dissolving an organosilicon polymer compound whose main skeleton components are silicon and carbon in an organic solvent, and further adding and dispersing fine powder of metal or ceramics thereto. The carbon fiber bundle is impregnated with the solution by dipping the bundle, and then the carbon fiber bundle is preformed into the desired shape and then heated.

The organosilicon polymer compound impregnated into the carbon fiber bundle by firing is thermally decomposed into a silicon carbide ceramic, and the carbon fibers are bonded with the silicon carbide ceramic through a fine metal or ceramic powder. , a method for manufacturing a fiber molded body characterized by coating the surface of carbon fibers, and after manufacturing the fiber molded body by the above method, an organic silicon polymer compound having silicon and carbon as main skeleton components is added to an organic solvent. Provided is a method for producing a fiber molded body, which comprises repeating the steps of immersing the fiber molded body in a dissolved solution, drying, heating, and firing the fiber molded body at least once or more.

The present invention will be explained in detail below.

The organosilicon polymer compound having silicon and carbon as main skeleton components used in the present invention is variously selected, and is not particularly limited. ) An organosilicon compound having a polysilane skeleton selected from chain polysilanes represented by the formula is thermally decomposed by heating to a temperature of 300°C to 2000°C in an atmosphere selected from inert gas, hydrogen gas, and vacuum. One or more compounds selected from polycarbosilane polymers, polysilphenylene polymers, and mixtures thereof obtained by performing a polycondensation reaction are preferably used.

In the production method of the present invention, the organosilicon polymer compound is first dissolved and diluted in an organic solvent. In this case, the organic solvent may be an aliphatic hydrocarbon such as hexane,
Solvents such as aromatic hydrocarbons such as toluene and xylene, ethers such as ethyl ether and tetrahydrofuran, and halogenated hydrocarbons such as methyl chloroform can be suitably used. In addition, when dissolving the organosilicon polymer compound in these organic solvents, the concentration of the organosilicon polymer compound will be 0.5 to 50% (wt%, the same hereinafter), particularly 1 to 30%, although it is not particularly limited. It is preferable to dissolve it in such a manner. If the concentration of the organosilicon polymer compound is lower than 0.5%, the adhesion between the metal or ceramic fine powder and the fibers will be weak when the fiber bundle is molded and further heated and fired.
The fibers may fall apart due to the elasticity of the fibers and cannot be formed into a molded product.If the content is higher than 50%, the viscosity of the solution will become high and the solution will not be well impregnated between the fiber bundles.

The gaps formed by the fine powder interposed between the fibers may become smaller, making it difficult for the matrix to penetrate during casting. In the present invention, it is preferable to use fine powder of metals or ceramics such as titanium, boron nitride, etc., with an appropriate particle size depending on the diameter of the reinforcing fibers and the desired fiber volume content Vf. When the fiber volume content is 40% using m carbon fiber, it is desirable to use fine particles with an average particle size of about 10 pm, and when the fiber volume content is as low as 30% or less, use fine particles with a large average particle size. It's good to do.

Furthermore, the amount of metal or ceramic fine powder added depends on the desired fiber volume content Vf, etc.

It is selected as appropriate, but 1 to 20 g/! for the organic solvent in which the organosilicon polymer compound is dissolved! A range of is preferred.

In the production method of the present invention, a carbon fiber bundle is immersed in a solution containing the organosilicon polymer compound obtained in this way and fine powder of metal or ceramics, and the organic silicon polymer compound and metal are immersed between the fibers. Alternatively, after being impregnated with fine ceramic powder, it is taken out and preformed into a desired shape.

Here, the carbon fiber bundle is preferably made of carbonaceous or graphite continuous fibers industrially produced from polyacrylonitrile or pitch, and if the carbon fibers are sized in advance. It is preferable to use it after washing with an organic solvent.

There are no restrictions on the method or time of immersing the carbon fiber bundle in the above solution, but if the carbon fiber bundle is immersed in the solution while applying ultrasonic waves,
This method is extremely effective because not only the metal or ceramic fine powder is uniformly dispersed in the solution, but also the carbon fibers are loosened one by one and the fine powder is evenly incorporated between the fibers. The immersion time is determined by the degree of impregnation between the fibers and can be about 1 second to 60 minutes, but about 10 to 120 seconds is sufficient under the above-mentioned ultrasonic waves.

Furthermore, there are no limitations on the molding method, and examples include a method in which carbon fibers immersed in the above solution are drawn into a tube made of glass or fluororesin, and a fiber bundle is wrapped around the fiber bundle with string, tape, or carbon fibers made of the same material. One example is a method of molding. In this case, it is preferable to remove excess solution from the fiber bundle, and if the solvent is evaporated by heating under reduced pressure after forming the fiber bundle, the organic silicon polymer compound will cause the fiber to become a metal or ceramic fine material. It is possible to obtain a preformed body of carbon fiber bundles that are bonded to each other while maintaining a gap through the powder.

Next, in the manufacturing method of the present invention, the preformed carbon fiber bundle obtained as described above is heated and fired to obtain a fiber molded body.

In this case, the heating and firing conditions are not particularly limited, and may be any conditions that allow the organosilicon polymer compound impregnated into the carbon fiber bundle to thermally decompose and transform into silicon carbide ceramics, and generally include inert gas, ammonia, etc. 700 to 1000°C in an atmosphere of gas, hydrogen gas, or a mixture of these gases or in vacuum,
In particular, a method of firing by heating to a temperature in the range of 700 to 950°C can be adopted.

In addition, in the above-mentioned series of molded body manufacturing processes,
There is no need for infusibility treatment, ie, treatment such as air oxidation, as shown in Japanese Patent No. 917, and therefore, according to the present invention, the shape retention of the molded product is not impaired. In addition, the above heating,
The amount of silicon carbide ceramics converted from the organosilicon polymer compound obtained from the polysilane of the formula (1) or [■] in the firing process reaches approximately 80% by weight, and therefore the bond between the fibers and the fine powder and the surface of the fibers are reduced. The amount of organosilicon polymer compound required for coating can be extremely small.

Furthermore, in the present invention, a re-coating step is performed in which the fiber molding thus obtained is immersed again in a solution in which an organosilicon polymer compound is dissolved in an organic solvent, and the steps of drying, heating, and baking are repeated at least once or more. By doing so, it is possible to obtain a fiber molded article whose tensile strength is higher when made into a composite material, and which can have a value extremely close to the theoretical strength expected from the composite side.

In this case, the solution for re-immersing the fiber molded product includes the above (1)
) or [■] formula dissolved in an organic solvent is preferably used, but the organosilicon polymer compound added to the solution used for this recoating is The organic silicon polymer compound may be the same as the above-mentioned organic silicon polymer compound added to the solution in which the carbon fiber bundle is immersed, or a different one may be used. Further, the amount of the organic silicon polymer compound added is not particularly limited, but the concentration in the solution is 0.5 to 3.
It is preferable to add 0%, especially 1 to 25%. If the concentration is lower than 0.5%, the effectiveness of recoating may not be improved, and if it is higher than 30%, it is economically disadvantageous. Note that it is not necessary to add fine metal or ceramic powder to the organosilicon polymer compound solution used for recoating.

The fiber molded body re-impregnated with the organosilicon polymer compound was dried and heated using the same method and conditions as above.

Can be fired.

The fiber bundle molded body obtained in this way is set in a mold and preheated in a nitrogen atmosphere, and then subjected to normal molding, such as injecting a molten amount of aluminum, magnesium, or an alloy thereof as a matrix and applying pressure. Composite materials can be easily obtained by this method.

As explained above, according to the method for manufacturing a fiber molded body of the present invention, continuous fibers of carbon fiber can be made into a fiber molded body having a desired shape. Because the silicon carbide ceramic maintains the gap and firmly adheres through the fine powder of A fiber molded body with high shape-retaining strength that can maintain a desired shape is obtained, and since the fiber surface is coated with silicon carbide ceramics at the same time as the fibers are bonded, this fiber molded body can be bonded to the matrix metal. In addition to having good wettability, it is difficult to react with the matrix metal and has excellent adhesion between the fiber and the matrix metal.

Furthermore, according to the present invention, by re-coating the obtained fiber molded body, a fiber molded body with higher shape retention and excellent reliability can be obtained.

Therefore, the manufacturing method of the present invention has various shapes similar to final parts, and can be composited with 7 trix metals and used widely as carbon fiber reinforced metal composites, in a simple and extremely short process. It can be manufactured with high productivity.

EXAMPLES The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples below.

[Example 1] (Preparation of polycarbosilane fR) Xylene 40Q was charged into a glass-lined reactor with an internal volume of 100Q, 10 kg (435 mol) of metallic sodium was added, and the temperature of the reactor was raised to 110'C. The sodium metal was melted, and 28 kg of dimethyldichlorosilane was injected into the solution over 5 hours using a metering pump while stirring. After reacting at 140° C. for 10 hours, the reaction solution was filtered, washed with water, salt was removed, and dried to obtain 12 kg of polydimethylsilane (yield: 95%). Next, a stainless steel reactor with an internal volume of 500 mQ was filled with 350 g of the obtained polydimethylsilane, the atmosphere inside the vessel was replaced with nitrogen gas, and the temperature was gradually raised to a pressure of 120 kg/lI.
Polymerization was carried out at n2G and a temperature of 430°C. The polymerization was completed in 20 hours, and 210 g (yield: 60%) of polycarbosilane was obtained.

(Preparation and soaking of a-fiber) Using the winder 1 shown in Fig. 1, carbon fiber 2 (Train Force M-40/6
000 filaments) was wound up, cut to a length of 140 ha, and bundled to obtain 10 fiber bundles 3 weighing approximately 6 g (approximately 606,000 filaments). Meanwhile, 200 g of polycarbosilane was dissolved in 800 g of xylene to prepare a 20% by weight solution of polycarbosilane, and an additional 9.6 g
Boron nitride powder with a particle size of 10Im (Shin-Etsu Chemical Co., Ltd.)
Next, as shown in FIG. 2, the above dispersion solution 5 was put into an ultrasonic cleaner 4 (Ultrasonic cleaner manufactured by Shimadzu Corporation), and The fiber bundle 3 is immersed in this dispersion solution 5,
It was impregnated with dispersion solution 5 for 3 minutes using an ultrasonic cleaner. Next, the fiber bundle was pulled out of the solution and inserted into a Pyrex glass tube 6 with an inner diameter of 8 mm, as shown in FIG. 3, to remove excess solution. Note that the fiber volume content Vf in this glass tube was 40%.

(Preliminary firing) The fiber bundle was placed in a glass tube and left at room temperature overnight to dry, then placed in an electric furnace as it was and under reduced pressure (1
After xylene was evaporated at 300° C. for 1 hour at a temperature of 0 to 20 Torr, the pressure was returned to atmospheric pressure by filling with argon gas. Then, in an argon gas flow, the temperature was increased to 2.5°C/
The sample was heated to 500° C. at a temperature increase rate of 100° C. and held at 500° C. for 1 hour. When the fiber bundle was pulled out from the glass tube after cooling, it was found that the pre-baking had completely hardened the fiber bundle and maintained the shape inside the tube, resulting in 10 preformed fiber bundles (diameter 8 mm x 140 Q). It was done.

(Final firing) As shown in FIG.
and heated to 2.5℃7'+i under argon gas 9 atmosphere.
Heating to 800°C at a heating rate of n.

Main firing was performed at 800°C for 1 hour. By this main firing, the polycarbosilane was decomposed into silicon carbide ceramics, and 10 very strong fiber bundle molded bodies were obtained. The weight of the molded body increased by 13% relative to the weight of the carbon fiber.

(Casting) After preheating the molded body to 500°C for several minutes in an N2 atmosphere,
Place it in a pressure casting mold and immediately bring it to a melting temperature of 800°C.
of aluminum alloy (AQ-7%Si) is injected, l
A pressure of OOOkgf/aJ was applied for 60 seconds.

The obtained composite was found to be in a uniformly dispersed state with almost no fiber aggregation or adhesion between fibers as seen in Reference Photo 1 from the cross-section l1Ii observation results. There was no deformation of the fiber bundle molded body during pressurization. Further, when the composite was subjected to a tensile test, high values of average tensile strength of 70 kg/wm2 and elastic modulus of 19 ton/m'' were obtained.

[Comparative Example 1] A fiber bundle molded body was produced under the same conditions as in Example 1 without using boron nitride powder, and then cast.

As can be seen from Reference Photo 2, in the obtained composite, the fiber bundles were aggregated in the center of the composite, and the aluminum alloy did not penetrate into the fiber bundles. Tensile strength is 32 kg
/ m", and the elastic modulus was 12 ton/m".

[Example 2] (Preparation of fiber molded product) Carbon fiber without sizing agent (Trading Card M-40)
-99/6000 filament) and operated in the same manner as in Example 1 to obtain 10 fiber bundles weighing about 6 g (about 606,000 filaments). On the other hand, polycarbosilane 20
0g of polycarbosilane was dissolved in 800g of xylene to prepare a 20% by weight solution of polycarbosilane, and further 11.3g of particle size 1
0- titanium powder was added to obtain a dispersion solution. This dispersion solution was placed in an ultrasonic cleaner, and subjected to the same processes as in Example 1, including dipping, molding, drying, and pre-baking and 2-piece firing, to obtain a Vf40
% fiber bundle molded bodies were obtained. The weight of the molded body increased by 12% relative to the weight of the carbon fiber.

(Recoating) 50 g of polycarbosilane was dissolved in 950 g of xylene to obtain a 5% by weight solution of polycarbosilane. The fiber bundle molded body was immersed in this solution, impregnated with the solution for 2 minutes using an ultrasonic cleaner, dried overnight at room temperature, and then placed in an electric furnace under reduced pressure (10 to 20 Torr). , 300
After evaporating xylene at ℃ for 1 hour, argon gas was filled in and the pressure was returned to atmospheric pressure. Next, the mixture was heated to 800°C at a temperature increase rate of 2.5°C/n+in under an argon gas flow, and maintained at 800°C for 1 hour. After cooling, 10 fiber bundle molded bodies were obtained.

(Casting) Using the obtained fiber bundle molded body, an aluminum alloy was cast under the same conditions as in Example 1.

As in Example 1, no fiber aggregation or deformation was observed in the obtained composite. Also, the tensile strength of the composite is 95 kg
/ mm2 and elastic modulus of 21 ton/nl112, which were extremely high and almost matched the values expected from the compound law.

[Example 3] (Preparation of fiber molded body! B2) Carbon fiber from which sizing agent was removed (Trading card M-40/60
00 filament) under the same conditions as Example 1,
Approximately 6 g (approximately 606,000 filaments) of fiber bundles were obtained. On the other hand, 300 g of polycarbosilane was mixed with 700 g of xylene.
A 30% by weight solution of polycarbosilane was dissolved in yA111! Further, a bed of nitriding boron powder with a particle size of 110 liters of 8.0 og was added to obtain a dispersion solution. This molecular Il solution was placed in an ultrasonic cleaner, and a carbon fiber bundle was immersed therein in the same manner as in Example 1, and molded using a Teflon tube with an inner diameter of 8 mm. After leaving it for about 10 minutes, it was pulled out from the Teflon tube and found that it retained its shape, so it was left to dry overnight. This was placed in an electric furnace and the xylene was evaporated under reduced pressure (10 to 20 Torr) at 300°C for 1 hour, then argon gas was filled in and the pressure returned to atmospheric pressure. It was heated to 800°C at a temperature increase rate of °C/min and held at 800°C for 1 hour to obtain a fiber bundle molded body with a Vf of 38%. The weight of the molded body increased by 18% compared to the weight of the carbon fiber.

(Recoating) 100 g of polycarbosilane was dissolved in 900 g of xylene to obtain a 10% by weight solution of polycarbosilane. The fiber bundle molded body was immersed in this solution and washed in an ultrasonic cleaner for 2 hours.
After being impregnated with the solution for a minute, it was dried at room temperature for a day and night, and then placed in an electric furnace under reduced pressure (1 O ~ 20 Torr).
After evaporating xylene at 300° C. for 1 hour, argon gas was filled in and the pressure was returned to atmospheric pressure. Then, the temperature was increased to 850°C at a heating rate of 2.5°C/11in under an argon gas flow.
and held at 850° C. for 1 hour. After cooling, a fiber bundle molded body was obtained.

(casting) Casting was carried out under the same conditions as in Example 1.

As in Example 1, no fiber aggregation or deformation was observed in the obtained composite. The tensile strength of the composite is 82 kg/t
rtn2, elastic modulus 20 ton/arr", and measured compressive strength was 64 kg/m"
showed that.

[Example 4] (Preparation of fiber molded product) Carbon fiber from which sizing agent was removed (Trading Card M-30076
000 filaments) was operated under the same conditions as in Example 1 to obtain a fiber bundle of approximately 6 g (approximately 522,000 filaments). On the other hand, 8Qg of polycarbosilane was mixed with 920g of xylene.
g to prepare an 8% by weight solution of polycarbosilane, and further 10. A bed of nitriding boron powder with a particle size of 10-g was added to obtain a dispersion solution. This dispersion solution was placed in an ultrasonic cleaner, immersed in the same manner as in Example 1, and molded into a Teflon tube with an inner diameter of 8 tones. After being left for about 10 minutes, it was pulled out from the Teflon tube and left to dry day and night. This was placed in an electric furnace and heated under reduced pressure (10 to 2 Q Torr).
), xylene was evaporated at 300'C for 1 hour, then returned to atmospheric pressure by filling with N2 gas, and then heated to 760°C at a heating rate of 2.5°C/l1ir1 in a N2 gas stream. Then, hold at 760'C for 1 hour to reduce Vf to 40%.
A fiber bundle molded body was obtained. The weight of the molded body increased by 11% compared to the weight of the carbon fiber.

(Recoating II) 100 g of polycarbosilane was dissolved in 900 g of xylene to obtain a 10% by weight solution of polycarbosilane. The fiber bundle molded body was immersed in this solution and washed in an ultrasonic cleaner for 2 hours.
After impregnating with the solution for a minute, it was dried at room temperature for a day and night, and then placed in an electric furnace under reduced pressure (10 to 20 Torr) for 30 minutes.
After evaporating xylene at 0° C. for 1 hour, N2 gas was filled in and the pressure was returned to atmospheric pressure. Then under N2 gas flow 2
．． Heating to 750°C at a temperature increase rate of 5°C/lll1n,
It was held at 750°C for 1 hour. After cooling, a fiber bundle molded body was obtained.

(casting) Casting was carried out under the same conditions as in Example 1.

As in Example 1, no fiber aggregation or deformation was observed in the obtained composite. The tensile strength of the composite is 63 kg/us2
, the elastic modulus was 12 ton/+m2, and the compressive strength was extremely high at 108 kg/no''.

[Example 5] (Condition of fiber molded body 11%) Carbon fiber without sizing agent (Trading Card M-40)
-99/6,000 filaments) was wound up in the same manner as in Example 1 to obtain a fiber bundle of about 30 g (about 2,800,000 filaments).

On the other hand, 200 g of polycarbosilane was dissolved in 800 g of xylene to prepare a 20% by weight solution of polycarbosilane, and 9.6 g of particle size 10. titanium powder was added to obtain a dispersion solution. Next, a carbon fiber bundle was immersed in this dispersion solution in the same manner as in Example 1, and then inserted into a glass tube with an inner diameter of 17 m+s.
The periphery was wrapped with zero filament yarn and molded into a rod shape. - After drying day and night, place in an electric furnace and heat to 800°C at a temperature increase rate of 2.5°C/win in an argon gas atmosphere, hold at 800°C for 1 hour, and set a diameter of 17 cm at a Vf of 40%.
A fiber bundle molded body of mm+ was obtained. The weight of the molded body increased by 13% relative to the weight of the carbon fiber.

(Recoating) 100 g of polycarbosilane was dissolved in 900 g of xylene to obtain a 10% by weight solution of polycarbosilane. The fiber bundle molded body was immersed in this solution and washed in an ultrasonic cleaner for 2 hours.
After being impregnated with the solution for a minute, it was dried at room temperature for a day and night, and then placed in an electric furnace under reduced pressure (10 to 20 Torr) for 3
After evaporating xylene at 00° C. for 1 hour, argon gas was filled in and the pressure was returned to atmospheric pressure. Next, it was heated to 800° C. at a temperature increase rate of 2.5° C./ff1 inch under an argon gas flow and held at 800° C. for 1 hour. After cooling, a fiber bundle molded body was obtained.

(casting) Casting was carried out under the same conditions as in Example 1.

As in Example 1, no fiber aggregation or deformation was observed in the obtained composite. The tensile strength of the composite is 93kg/lll
112, and the elastic modulus was 20 ton/mm2.

[Brief explanation of the drawing]

Figure 1 is a perspective view of a winder used to bundle continuous fibers, Figure 2 is a perspective view of a fiber bundle immersed in a solution in an ultrasonic cleaner, and Figure 3 is a perspective view of a winder used to bundle continuous fibers. As shown in the figure, a cross-sectional view shows a state in which a soaked fiber bundle is inserted into a Pyrex glass tube and the solution is removed from the fiber bundle. Figure 4 is a schematic cross-sectional view of an electric furnace used when firing the fiber bundle. be. 1... Winder, 2... Carbon fiber, 3... Carbon fiber bundle, 4... Ultrasonic cleaner, 5... Solution containing fine powder of organosilicon polymer compound and metal or ceramics. 6... Pyrex glass tube, 7... Preformed body, 8... Electric furnace, 9... Argon gas. Applicant Honda Motor Co., Ltd. Shin-Etsu Chemical Co., Ltd. Agent Patent Attorney Takashi Kojima Figure 3 Figure 4

Claims (1)

[Claims] 1. In a solution prepared by dissolving an organosilicon polymer compound whose main skeleton components are silicon and carbon in an organic solvent, and further adding and dispersing a fine metal or ceramic powder thereto. The carbon fiber bundle is impregnated with the solution by dipping the carbon fiber bundle, and then the carbon fiber bundle is preformed into a desired shape, and then heated and fired to impregnate the organic silicon polymer compound into the carbon fiber bundle. production of a fiber molded body, characterized in that carbon fibers are bonded to each other by the silicon carbide ceramic through fine metal or ceramic powder, and the surface of the carbon fiber is coated. Method. 2. After producing a fiber molded body by the method according to claim 1, the fiber molded body is immersed in a solution of an organic silicon polymer compound having silicon and carbon as main skeleton components dissolved in an organic solvent, and then dried. , heating and firing steps are repeated at least once or more.