JPS6014820B2 - Manufacturing method for reinforced composite materials - Google Patents

Description

[Detailed description of the invention] The present invention relates to a novel method for manufacturing reinforced composite materials.

Until now, inorganic reinforcement materials such as inorganic fiber reinforcement materials have been
Many examples of composite materials made of various matrix materials such as ceramics and plastics have been reported.

Examples of carbon fiber include carbon fiber-aluminum, carbon fiber-magnesium monoxide, and carbon fiber-epoxy resin. However, it is known that in cases where carbon fiber is composited with aluminum, the aluminum matrix and carbon fiber react excessively, forming aluminum carbide at the boundary, resulting in a decrease in mechanical strength at high temperatures. Even in the case of carbon fiber magnesium monoxide composites, the surface of carbon fibers reacts excessively with magnesium oxide, and the difference in expansion coefficient between carbon fibers and magnesium oxide is large.
It has the disadvantage of causing cracks in the matrix. Furthermore, the wettability between carbon fiber and epoxy resin is not perfect. In this way, when the matrix is reactive or has a high melting point, the inorganic reinforcing material and the matrix react excessively, and in the case of plastics, wettability becomes a problem, and the resulting composite material is not necessarily satisfactory. The current situation is that this has not been achieved.

The object of the present invention is to provide a new reinforced composite material of excellent performance and a method for producing the same, which does not have the above-mentioned drawbacks.

According to the present invention, on the surface of the inorganic reinforcing material, [1] a polycarbosilane siloxane represented by the following formula (in the above formula, R, to R6 are each hydrogen, an alkyl group of C4 or less, and C4 or less).

an alkyl group, phenyl group, C5-C8 cycloalkyl group, benzyl group or vinyl group; n is 5-1000
0; and repeating x units and y units (including both random and flock) ■ Polycarbosiloxane represented by the following formula (in the above formula, R and R2 are respectively,
Hydrogen, an alkyl group of up to C4, a haloalkyl group of up to C4, a phenyl group, a cycloalkyl group of C5 to C8, a benzyl group, or a vinyl group, and n is 5 to 10,000)'31 Borosiloxane represented by the following formula Compound (in the above formula, R and R2 are each hydrogen, a C4 or less alkyl group, a C4 or less haloalkyl group, a phenyl group,
C5 to C8 cycloalkyl group, benzyl group or vinyl group; n is 1 to 10,000; and repetition of a units and b units includes both random and flock); ■ Borosiloxane compound represented by the following formula (In the above formula, R and R2 are each hydrogen, a C4 or less alkyl group, a C4 or less haloalkyl group, a phenyl group,
C5-C8 cycloalkyl group, benzyl group or vinyl group; n is 2-100; and repeating a units and b units (including both random and block), aliphatic polyhydric alcohol, aromatic By reacting one or more organic compounds selected from group alcohols, phenols, or aromatic carboxylic acids at a temperature within the range of 250 to 450°C in an atmosphere inert to the reaction. The resulting porosiloxane compound '51 is a porosiloxane compound represented by the following formula (in the above formula, R and R2 are hydrogen and C4, respectively).
The following alkyl groups, haloalkyl groups of up to C4, phenyl groups, C5-C8 cycloalkyl groups, benzyl groups or vinyl groups; n is 2 to 100; and the repetition of a units and b units is random, block (including both), Ni, Ti, Zr, Hf, V, Nb
, Ta, Cr, Mo, W, Co and other transition metals,
Powder of at least one metal selected from actenide metals and lanthanide metals and/or powder of alloys consisting of these metals, or persulfates, organic peroxides, or AI, Fe, B, Ga, ln. A modified porosi obtained by adding at least one halide as a catalyst and heating to 300 to 550°C in a non-oxidizing atmosphere.

A xane compound, and {6} borosilicate represented by the following formula.

xane compound (in the above formula, R and R2 are each hydrogen, a C4 or less alkyl group, a C4 or less haloalkyl group,
phenyl group, C5-C8 cycloalkyl group, benzyl group or vinyl group; n is 2-100; and repeating a units and b units (including both random and block), and aliphatic polyvalent One or more organic compounds selected from alcohol, aromatic alcohol, phenols, or aromatic carboxylic acids are mixed with Ni, Ti, Zr, Ni, Ti, Zr, etc. in an atmosphere inert to the reaction.
Powder of at least one metal selected from V, Nb, Ta, Cr, Mo, W, Co and other transition metals, actenide metals and lanthanide metals, and/or powder of alloys consisting of these metals, or In the presence of at least one catalyst selected from sulfates, organic peroxides, and halides of AI, Fe, B, Ga, and ln,
The above-mentioned noble borosiloxane compounds [11 to {6] obtained by reacting at a temperature within the range of ~450 oo
A first stage step of applying at least one semi-inorganic polymer compound of the group consisting of The second step of thermally decomposing the polymer compound produces an inorganic reinforcing material whose surface is mainly coated with SIC, and this surface-coated inorganic reinforcing material is covered with at least one matrix selected from metals, ceramics, and plastics. Provided is a method for manufacturing a reinforced composite material, which is characterized in that it is composited with a reinforced composite material.

The present invention will be explained in more detail below.

As mentioned above, reinforced composite materials comprising an inorganic reinforcing material and at least one kind of matrix selected from metals, ceramics, and plastics are known, but the characteristics of the reinforced composite material of the present invention are As the reinforcing material, an inorganic reinforcing material coated with a thermal decomposition product of a semi-inorganic polymer compound specific to the present invention is used, and such a technology is completely unknown in the past. In the reinforced composite material of the present invention, the surface of the inorganic reinforcement is covered with the thermal decomposition product of the semi-inorganic polymer compound specified in the present invention, so this part keeps the inside of the inorganic reinforcement stable and It has improved wettability with the matrix. Therefore, the composite material of the present invention not only has stronger strength (tensile, bending, impact resistance, etc.) at room temperature than conventional materials, but also maintains its strength at high temperatures without decreasing like conventional materials. It has the advantage of being The inorganic reinforcing material used in the reinforced composite material of the present invention is preferably an inorganic reinforcing material in the form of fibers, for example, it is preferable to use an inorganic reinforcing material in the form of continuous fibers, short fibers, or whiskers.

Further, as the inorganic reinforcing material, any known material can be used. Typical examples include amorphous, polycrystalline, single crystalline, or polyphase A glass. ,
C glass, E glass, S glass, alkali-resistant glass, silica glass, C, AI203, Be〇, Z^02, BN
, Si3N4, &C, SIC, B/W, SIC/W; or technique, Mo, W, AI, Cu, N
b, metals such as Ta, Ti, Cr, Cu, Fe, Ni,
Examples include alloys such as Ti-AI, Cu-Yama, Cu-Ni, and steel. Furthermore, the inorganic reinforcing material is not necessarily limited to having a fiber shape, but may be in the shape of flakes, chops, granules, or the like. In the reinforced composite material of the present invention, one or more of metal, ceramic, or plastic is used as the matrix, and the metal as the matrix has a melting point of 400.
℃ or above as metals, alloys, and ceramics such as oxides, carbides, monoxides, nitrides, shelvings, carbon, graphite, boron, cement, gypsum, mica, asbestos, and general ceramics; as plastics, polyester, epoxy, phenol, Polyacrylonitrile, polystyrene, polyimide, polyvinyl chloride, polyvinyl acetate and common plastics can be used.

The base material is not limited to these, and of course cermet, rubber, wood, etc. can also be used. The initial shape of the matrix may be powder, foil, plate, etc., but in the case of plastic, it may be in the form of a solution.

The matrix may be amorphous, polycrystalline, single crystalline, or polyphasic. Metals, ceramics, and plastics may be used alone or in combination depending on the purpose.
In the reinforced composite material of the present invention, the semi-inorganic polymer compound used to coat the surface of the inorganic reinforced material with a thermal decomposition product is mainly used in a non-oxidizing atmosphere to
By heating to a temperature of 00° C., it is converted into a ceramic mainly composed of SIC (amorphous state, B type, Q type, or a mixed phase thereof).

The above-mentioned semi-inorganic polymer compound that can be used in the present invention is a straight mirror-shaped, cyclic, ladder-shaped, cage-shaped, three-dimensional or mesh-shaped compound.

Regarding the manufacturing method of the semi-inorganic polymer compounds (1' to ①) specified in the present invention, the present inventors previously applied for Hakama Application No. 52-092584 and (Hakama Kaisho No. 54-28309).
, patent application No. 52-127630 (Special application No. 54-61299)
), Hakama Nukasho 53-054036 (Tsubaki Kaisho 54-1456
42), Hakama Gansho Kyukyu-054037 (Tokusekki Sho 54-1145
643).

Particularly preferred semi-inorganic polymer compounds for use in the method of the present invention include, for example, the following:

x:y=5:1~200:l n2500~10000 nZ5~10000 n et al. 2-100 n22~100 n et al. 2-100 can be mentioned.

In this case, the terminal group is a hydroxyl group, a methyl group, or a phenyl group. Preferably, the semi-inorganic polymer compound used in the present invention has a molecular weight of 400 to 200
By heating to a temperature of 0°C, mainly SIC (amorphous state, B type, Q type, or a mixed phase of these)
During the conversion into ceramic, the firing residue rate is particularly high, ranging from 40 to 85%.

Next, the method of the present invention for producing reinforced composite materials will be described. In the method of the present invention, first, a semi-inorganic polymer compound is applied to the surface of an inorganic reinforcing material. To carry out this coating, the semi-inorganic polymer compound is used, for example, benzene, toluene, xylene, hexane, ether, tetrahydride. Use a solution prepared by dissolving furan, dioxane, chloroform, methylene chloride, DMS○, DMF, and other semi-inorganic polymer compounds in a solvent, or a molten product obtained by directly heating and melting a semi-inorganic polymer compound without using a solvent. do. The coating can be carried out, for example, by the method described below. '1] Place the inorganic reinforcing material in a sealable container, evacuate it at room temperature or high temperature, and degas it.
Then, the melt or solution of the semi-inorganic polymer compound is poured into the container, and the inorganic reinforcing material is sufficiently immersed in the semi-inorganic polymer compound to form an impregnated coating.

Note that impregnation can be effectively performed by pressurizing the material using gas pressure (ie, press-fitting). (2) It can also be carried out by applying the melt or solution of the semi-inorganic polymer compound to the surface of the inorganic reinforcing material at room temperature or high temperature by spraying, brushing, etc.

(3- This can also be carried out by soaking the inorganic reinforcing material in a melt or solution of a semi-inorganic polymer compound placed in an open container. The semi-inorganic compound applied to the surface is thermally decomposed by heating to a temperature of ~2000 oo.

Heating is performed in a non-oxidizing atmosphere. The oxidizing atmosphere means, for example, an atmosphere such as nitrogen, argon, hydrogen gas, or a vacuum. Through this thermal decomposition, the semi-inorganic polymer compound is converted into a ceramic mainly composed of SIC (amorphous state, B type, Q type, or a mixed phase thereof). The inorganic reinforcing material having the surface coating obtained as described above is then composited into a matrix.

Any of the currently established methods can be used as the method for combining, but typical methods that can be used in the present invention are shown in the table below. As a method other than those shown in this table, for example, a mixed composite method (hybrid composite) can also be applied.
The ratio of the inorganic reinforcement to the matrix is determined by the volume % of the inorganic reinforcement based on the sum of the inorganic reinforcement and the matrix.
It is suitable that it is 5 to 90%, preferably 10 to 60%.

The reinforced composite material of the present invention has excellent strength at room temperature and good high-temperature properties, and can be suitably used, for example, in the following applications.

{1} Building materials - panels, domes, trailer houses, walls, ceiling materials, flooring materials, cooling towers, septic tanks, sewage tanks, water supply tanks, hot water supply piping, drainage pipes, heat conversion heat pipes, etc.■ Aircraft, space development equipment materials - fuselage,
Wings, helicopter drive shafts, jet engine compressors, rotors, stators, blades, compressor casings, housings, nose cones,
Rocket nozzles, brake materials, tire cords, etc. {3}
Materials for ships - Boats, yachts, fishing boats, work boats, etc. Materials for road transport equipment - Foreparts of wheels, side plates, water tanks, toilet units, seats, car bodies, containers, road equipment, guardrails, pallets, tank trucks tank,
Bicycles, motorcycles, etc. Corrosion-resistant equipment materials - Tanks, tower ducts, staffs, pipes, etc. Electrical materials Single-sided heating elements, varistors, igniters, thermocouples, etc.'7 Sports equipment - Boats, bows, skis, snowmobiles, Water skis, glider aircraft, tennis rackets, golf shafts, helmets, bats, racing jackets, etc. [8]
Mechanical elements - gaskets, gaskets, gears, brake materials, friction materials, abrasive materials, etc. Medical equipment materials - prosthetic legs, artificial limbs, etc. '10 Audio equipment materials - cantilevers, tone arms, speaker cones, voice coils (11) Materials for nuclear power Neutron absorbing material, neutron reflecting material (12) Electronic device parts printed wiring, parts bonding (room temperature, heating) (13) Vacuum parts production The present invention will be described below with reference to Examples.

Example 1 310 parts of boric acid and 1898 parts of diphenyldichlorosilane were placed in a three-necked flask together with 3 parts of n-butyl ether, and allowed to react at 100 o'clock for 18 hours while cooling to obtain a white precipitate.

After removing n-butyl ether, the precipitate was washed with methanol to remove unreacted boric acid, and then washed with water to obtain polydiphenylsiloxane compound 1680. 200 parts of this borodiphenylsiloxane compound, 20 parts of hydroquinone, and 1 part of ammonium persulfate were homogeneously mixed together, and heated in a nitrogen atmosphere at a heating rate of 50°C for 1 hour in a 500 M flask while shaking the mixture. The reaction was carried out at ○ for 1 hour to obtain a pale yellow semi-inorganic polymer compound. Carbon fiber East (2000 pieces) was immersed in a solution of the above semi-inorganic polymer compound dissolved in tetrahydrofuran at 1% by weight, and then pulled up and heated to 60% by weight in N2.
It was heated to 0qo.

This coated fiber was laminated on pure AI foil by 4 ol% (based on the whole) and placed in a steel die for 650 min in an argon stream.
Hot pressed on o/c, 100k9' ground. The bending strength of the obtained carbon fiber-aluminum composite material is shown in Table 2 below. For reference in Table 2, untreated carbon fibers were added to pure N foil at a concentration of 4 mol% (
The bending strength of the composite material obtained by hot pressing at 650° C. and 100 k9/h is shown in the lower row.

As can be seen from Table 2, the bending strength of the composite material of the present invention does not decrease even at 400° C., making it suitable for use at high temperatures.

Example 2 A bundle of 1,200 continuous silicon carbide fibers (synthesized from polycarbosilane) was immersed in a solution containing 7% by weight of the semi-inorganic polymer compound used in Example 1 dissolved in tetrahydrofuran, and then pulled up and placed in N2 gas. It was heated to 65,000 ℃.

After filling the coated fibers into a silica glass tube with one end sealed, molten AI (75000) was poured into the tube from the top and vacuumed to remove bubbles. The tensile strength of the obtained silicon carbide fiber (4Wol%)-aluminum composite material is shown in Table 3 below. The lower row shows the tensile strength of a composite material obtained by infiltrating untreated silicon carbide fibers with aluminum in the same manner as above. Table 3 Example 3 The carbon fiber coated with the thermal decomposition product of the semi-inorganic polymer compound used in Example 1 was composited with epoxy resin at 45 vol % and cured using a curing agent.

The bending strength of the obtained composite material was about 1.9 times lower than that of the composite material using untreated carbon fibers. Example 4 Glycerin 102 and dichlorodiphenylsilane 365
Dissolve the solution in 500% n-butyl ether and add 90~10%
The reaction was continued for 24 hours while heating and refluxing at 0°C.

Claims (1)

[Claims] 1. On the surface of the inorganic reinforcing material, (1) Polycarbosilane siloxane represented by the following formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (In the above formula, R_1 to R_6 are hydrogen, C_4, respectively)
The following alkyl groups, haloalkyl groups of up to C_4, phenyl groups, C_5 to C_8 cycloalkyl groups, benzyl groups or vinyl groups; n is 5 to 10,000; and the repetition of x units and y units is random, block (2) Polycarbosiloxane represented by the following formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(In the above formula,
R_1 and R_2 are hydrogen, an alkyl group of C_4 or less, a haloalkyl group of C_4 or less, a phenyl group, C
It is a cycloalkyl group, benzyl group or vinyl group of _5 to C_8, and n is 5 to 10,000. )(3) Borosiloxane compound represented by the following formula ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, R_1 and R_2 are hydrogen, an alkyl group of C_4 or less, C
Haloalkyl group of _4 or less, phenyl group, C_5 to C_
8 cycloalkyl group, benzyl group or vinyl group; n is 2 to 100; and the repetition of a unit and b unit includes both random and block) (4) A borosiloxane compound represented by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R
_1 and R_2 are hydrogen, an alkyl group of C_4 or less, a haloalkyl group of C_4 or less, a phenyl group, C_
5 to C_8 cycloalkyl group, benzyl group, or vinyl group; n is 2 to 100; and the repetition of the a unit and b unit includes both random and block), an aliphatic polyhydric alcohol, an aromatic Obtained by reacting one or more organic compounds selected from alcohols, phenols, or aromatic carboxylic acids at a temperature within the range of 250 to 450°C in an atmosphere inert to the reaction. Modified borosiloxane compound (5) Borosiloxane compound represented by the following formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(In the above formula,
R_1 and R_2 are hydrogen, an alkyl group of C_4 or less, a haloalkyl group of C_4 or less, a phenyl group, C
_5 to C_8 cycloalkyl group, benzyl group or vinyl group; n is 2 to 100; and repetition of a unit and b unit includes both random and block), Ni, Ti, Zr, Hf, V, N
b, powder of at least one metal selected from Ta, Cr, Mo, W, Co and other transition metals, actenide metals and lanthanide metals and/or powder of alloys consisting of these metals, or persulfate; , an organic peroxide, or a halide of Al, Fe, B, Ga, or In, as a catalyst, and heated to 300 to 550°C in a non-oxidizing atmosphere. Siloxane compounds, and (6) Borosiloxane compounds represented by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, R_1 and R_2 are hydrogen, an alkyl group of C_4 or less, a haloalkyl group of C_4 or less, respectively) phenyl group, C_5 to C_8 cycloalkyl group,
is a benzyl group or a vinyl group; n is 2 to 100; and the repetition of a units and b units includes both random and block), and an aliphatic polyhydric alcohol, an aromatic alcohol, a phenol, or an aromatic One or more organic compounds selected from group carboxylic acids are reacted with Ni, Ti, Zr, Hf in an atmosphere inert to the reaction.
, V, Nb, Ta, Cr, Mo, W, Co, and other transition metals, actenide metals, and lanthanide metal powders and/or alloy powders consisting of these metals, or In the presence of at least one catalyst selected from persulfates, organic peroxides, and halides of Al, Fe, B, Ga, and In, 25
Modified borosiloxane compounds (1) to (6) above obtained by reacting at a temperature within the range of 0 to 450°C
A first stage step of applying at least one semi-inorganic polymer compound of the group consisting of In the second step of thermally decomposing the polymer compound, an inorganic reinforcing material whose surface is mainly coated with SiC is produced, and this surface-coated inorganic reinforcing material is coated with at least one matrix selected from metals, ceramics, and plastics. A method for manufacturing a reinforced composite material characterized by combining with.