JPH01306533A - Production of composite material of intermetallic compound - Google Patents

Abstract

PURPOSE:To efficiently produce the good composite material which is an intermetallic compd. by bringing a molding contg. an inorg. reinforcing material, metal forming the intermetallic compd. with Al, and the fine pieces of metal fluoride into contact with molten Al, thereby penetrating the molten Al therein. CONSTITUTION:Ni-plated carbon fibers 10 and Ni fibers 12 are oriented unidirectionally in the state of mixing the same substantially uniformly with each other into a stainless steel case 14 in such a manner that the respective volume ratios attain about 38% and about 43% and a columnar molding 16 is formed. This molding 16 is immersed together with the case 14 into an aq. K2ZrF6 soln. 18 of about 13g/100cc concn. and about 90 deg.C; thereafter, the molding is heated together with the case 14 to about 150 deg.C and is sufficiently dried to deposit the crystals of K2ZrF6 finely on the surfaces of the individual fibers. This molding 16 is then preheated by heating the same for 10 minutes at about 200 deg.C and is immersed together with the case 14 for about 2 minutes in the pure molten Al 20 kept at about 750 deg.C. The molding is taken out of the molten metal and the molten metal 20 is allowed to solidify as it is. The good composite material is thereby obtd. at a low cost without pressurizing the molten metal 20 and without preheating the reinforcing material 10.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to composite materials, and more particularly to composite materials that use inorganic fibers such as ceramic fibers as reinforcing materials, and mainly contain intermetallic compounds of Al and other metals. This invention relates to a method for manufacturing a composite material used as a matrix.

Conventional technology For example, "Industrial Materials" (■o1.
31), page 21 of Metal, published in 1986.
Progress page 27, Waku 1'i in 1985
“Research Report of the 123rd Committee on Heat-Resistant Metallic Materials” (V
As described on p. 69 of OL, 26, No. 1), as a method for producing composite materials whose matrix is mainly an intermetallic compound,
), (1) deposition method (thermal spraying, plating, CVD), (2) powder metallurgy method, etc. are conventionally known.

Problems to be Solved by the Invention However, the above-mentioned method (1) has a problem in that it is limited to cases where the reinforcing fibers have a large diameter and the matrix metal can easily penetrate between the fibers due to plastic flow. In addition, although this method is suitable for manufacturing plate-shaped composite materials, it is difficult to manufacture composite materials of other shapes.
In addition, since the manufacturing equipment and apparatus are complicated, there is a problem that the manufacturing cost of the composite material tends to be high.

In addition, in the method (2) described above, it is difficult to densify the matrix, and the matrix does not necessarily fill sufficiently between the individual fibers, making it difficult to produce a good corrugated abrasive material.

In the method (2) mentioned above, if the reinforcing material is a relatively long fiber, it is difficult to uniformly disperse the fibers, and if HIP or hot pressing is not used, it is difficult to form a composite. There is a problem that it is difficult to achieve, and therefore the manufacturing cost of composite materials is high, and furthermore, 113
There is a problem in that it is difficult to manufacture complex-shaped composite materials or large-sized composite materials.

In view of the various problems mentioned above in the conventional methods of manufacturing composite materials in which the matrix is mainly an intermetallic compound, the present invention provides an efficient and inexpensive way to produce a good composite material in which the matrix is mainly an intermetallic compound. The first objective is to provide a method for manufacturing.

Means for Solving the Problems According to the present invention, the above-mentioned target contains an inorganic reinforcing material, a metal that reacts with Al to form an intermetallic compound, and fine particles of metal fluoride. A porous molded body is formed, and at least a portion of the molded body is made of Al or Al.
An intermetallic compound 132 that is brought into contact with molten gold and infiltrated into the molded body without substantially pressurizing the molten metal.
This is accomplished by the H-method of manufacturing composite materials.

Effects and Effects of the Invention According to the method of the present invention, a porous molded body containing an inorganic reinforcing material, a metal that reacts with Al to form an intermetallic compound, and fine pieces of metal fluoride is formed. , at least a portion of the molded body is brought into contact with meltable Al or Al alloy.

In general, metals that react with Al to form intermetallic compounds (hereinafter referred to as specific metals) have excellent wettability against the elution of Al or Al alloys, so the elution penetrates into the compact through the specific metal. . Also, metal fluoride removes the oxide film on the surface of the molten metal and certain metals, thereby eliminating the wetting of the molten metal against reinforcement +1. In addition, the molten metal and specific metals react with each other to form intermetallic compounds and generate heat, which heats the molten metal and the reinforcing material, which improves the permeability of elution into the compact and the wettability of the reinforcing material. As a result, the molten metal penetrates into the molded body well, and intermetallic compounds are successively formed between the individual reinforcing materials.

Therefore, according to the method of the present invention, there is no need to pressurize the molten metal or preheat the reinforcing material to a high temperature, and therefore, there is no need for Okawa Rina equipment for pressurizing the molten metal or preheating the reinforcing material to a high temperature. Therefore, a composite material in which intermetallic compounds are well filled between individual reinforcing materials can be produced more efficiently and at lower cost than conventional methods such as hot pressing.

Furthermore, the processing temperature when manufacturing composite materials is 1000°C or higher in conventional methods, whereas it is approximately 750°C or lower in the method of the present invention, which is superior to conventional methods. Therefore, deterioration of the reinforcing material can be reduced, and a good composite material can also be manufactured by this.

Furthermore, according to the method of the present invention, as described above, the molten metal penetrates into the molded body well, so that the molded body containing the reinforcing material, the metal, and fine pieces of metal fluoride can be formed into a predetermined shape and size. If a part of the molten metal is brought into contact with the elution of the metal, the molten metal will quickly permeate the entire body, and an intermetallic compound will be formed, which will substantially form a predetermined amount. A composite material of shape and dimensions is formed. Therefore, it is possible to efficiently and inexpensively produce a composite material 1 having a substantially predetermined shape and dimensions at a very high yield, and by forming a continuous molded product in the shape of a rod or plate, it is possible to It is possible to continuously manufacture composite materials, and in history, secondary processing such as rolling and forging can be continuously performed on the manufactured composite materials as they are.

According to one particular feature of the invention, the metal is used in fine pieces such as short fibers, whiskers, powder, and thus by mixing the reinforcing material with the metal fine pieces and the metal fluoride@stripes. Alternatively, by attaching fine pieces of metal and fine pieces of metal fluoride to the surface of the reinforcing material, a molded body made of these is formed.

According to another detailed feature of the invention, the metal is coated on the surface of the reinforcement. Therefore, in this case, by mixing a metal-coated reinforcement material with a metal fluoride, or by attaching a metal fluoride to the surface of a metal-coated reinforcement material, A molded body is formed.

According to another detailed feature of the invention, the surface of the reinforcing material is coated with metal, fine particles of metal fluoride are dispersed in the coating layer, and the reinforcing material with such a composite coating layer is used. A molded body is formed.

Further, in the method of the present invention, the metal fluoride may be a fluoride of any metal element, but for example, 2 ZrF6
, K2TiF6 , KAlF4 , K2AlF3
, K2 AlF3-H20, CS AIF 4, C
s A I F 5 ・H20 is a fluoride containing transition metals such as Ti5Zr, Hf, V, Nb5Ta, or AI combined with electrically positive elements such as alkali metals, alkaline earth metals, and rare earth metals. It is preferable. According to another detailed feature of the invention, therefore, the metal fluoride is a fluoride containing a transition metal or AI in combination with an electrically positive metal element.

Further, in the method of the present invention, the metal contained in the molded body is A
Force 1 may be any metal as long as it reacts with I to form an intermetallic compound, especially Ni, Fe.

Co, Cr, M n, Cu, Ag5S i, Mg, Z
, Zn, Sn, Pb, Ti5Nb, or an alloy containing any of these as a main component. Therefore, according to another detailed feature of the invention, the metal is Ni, Fe.
,, Co, CrSMn, CusAg, St, Mg, Z
The metal flakes are selected from the group consisting of r, Zn, Sn%Pb%TtSNb, and alloys containing any of these as main components.

According to yet another detailed feature of the invention, the molded body has a predetermined shape and dimensions, and only a portion thereof is immersed in the molten metal. According to this method, n pieces of composite material of a predetermined shape and size can be efficiently produced at a very high yield without pressurizing molten metal or using a mold to define a predetermined product shape. Can be manufactured cheaply.

In the method of the present invention, it is not necessary to preheat the molded body, but when preheating the molded body in order to improve the abrasiveness of the reinforcing material and the metal against molten metal, the temperature is lower than that of the conventional method. Preferably, the temperature is lower than that employed. In addition, the form of the fine pieces of metal fluoride in the present invention is short fibers,
It may be in any form such as whiskers or powder.

In addition, in the method of the present invention, the reinforcing material may have any form and material, for example, silicon carbide fibers, ceramic fibers such as alumina fibers, iron fibers, metal fibers such as tungsten fibers, carbon fibers, etc. The particles may be inorganic fibers other than ceramics and metals such as ceramics and metals, whiskers such as silicon carbide whiskers, silicon carbide particles, and titanium carbide particles.

The invention will now be described in detail by way of example embodiments with reference to the accompanying drawings.

Practical Example 1 As shown in Fig. 1, carbon fiber 10 plated with Ni to a thickness of 0.2 μm (fiber diameter 7 μm 1 rT300J manufactured by Toshi Co., Ltd.) and Ni fiber with a fiber diameter of 4 μm were used. 12(
"Suzlon" manufactured by Suzuki Metal Industry Co., Ltd.) was cut into 10 cm long pieces, each with a volume ratio of 38 cm.
96.4396 in a stainless steel case (length 12en, outer diameter 12+am, inner diameter 10mm), the Ni Carbon fiber and Ni plated with
A cylindrical molded body 16 made of fibers was formed.

Next, as shown in FIG.
3g/100cc, 2ZrF6 aqueous solution 1 at a temperature of 90°C
8, and then the molded body was immersed in case 1.
The fibers were sufficiently dried by heating to 50° C., thereby finely depositing 2ZrF6 crystals on the surface of each fiber.

Next, the molded body 16 is preheated by heating to 200° C. for 10 minutes, and then the preheated molded body 16 is heated to a temperature of 200° C. as shown in FIG.
It was immersed in a molten metal 20 of pure Al at 0° C. for 2 minutes, taken out from the molten metal, and left to solidify the molten metal. In this case, the molten metal remained attached to the molded body due to surface tension until it solidified, and substantially did not drip from the molded body.

After the molten metal was completely solidified, the solidified body was cut and the metallographic structure of the cross section was examined using an optical microscope. As a result, there was no defective impregnation of the matrix metal. Furthermore, when the structure of the cut surface of the solidified body was analyzed using EPMA, it was found that Ni on the surface of the carbon fiber and Ni fibers formed by reacting with pure Al molten metal accounted for most of the cross section of the Ni3Al or 7 trix portion. Therefore, it was confirmed that a composite material mainly composed of the intermetallic compound Ni3Al as a matrix and carbon fibers oriented in one direction and having a volume fraction of about 3096 as a reinforcing material was well formed.

Example 2 SiC fibers with a fiber diameter of 15 μm (11 “Nicalon” manufactured by Carbon Co., Ltd.) and a cone diameter of 1. Ott m Ti fibers were cut into lengths of 10 cm, and each was placed in a stainless steel case (length: 12 cm, outer diameter: 12 mm) so that the volume ratio of each fiber was 40% and 30~6.

S i CG
A cylindrical molded body consisting of an R-shaped cone and Ti fibers was formed.

The molded body was then treated in the same manner and under the same conditions as in Example 1, whereby 2ZrFδ was applied to the surface of each fiber.
Fine crystals were precipitated. The molded body is then heated to about 200°C.
After that, the preheated molded body was immersed in a pure Al molten metal at 750° C. for 2 minutes and taken out from the eluent, and the molten metal was allowed to solidify in that state. In this case as well, the eluate remains attached to the molded body due to surface tension until it solidifies.
There was virtually no dripping from the molded article.

After the molten metal had completely solidified, the solidified body was cut and the metallographic structure of the cross section was examined using an optical microscope, and no defective matrix metal impregnation was found. In addition, when the structure of the cut surface of the coagulated body was analyzed using EPMA,
TiAl formed by the reaction of Ti fibers with pure Al molten metal occupies most of the cross section of the matrix portion, and therefore, the intermetallic compound TiAl is used as a 7 trix and the volume fraction oriented in one direction is approximately 40%. It was observed that IM and &+J materials using SiC fibers as reinforcing materials were well formed.

Example 3 SiC whiskers (manufactured by Tokai Carbon Co., Ltd. i!, “1.-
Ni was electrolessly plated to a thickness of 0.2 μm on the surface of the “Kamasokusu”). The thus plated SiC whiskers were then mixed with Ni alloy powder (N i O,
SiC whiskers and Ni The volume fraction of alloy powder is 1
096.63%, and a disc-shaped molded body having dimensions of 30 mm in diameter and 5+ am in thickness was formed.

The compact is then preheated to about 300°C, and then -r
The heated molded body was immersed in pure Al eluate at 750° C. for 2 minutes and taken out from the melt, and the molten metal was allowed to solidify in that state. In this case as well, the molten metal remained in a state where it was attached to the molded body due to surface tension until it solidified, and substantially did not drip from the molded body.

After the molten metal had completely solidified, the solidified body was cut and the metallographic structure of the cross section was examined using an optical microscope, and no defective matrix metal impregnation was found. In addition, when the structure of the cut surface of the coagulated body was analyzed by EPM A, it was found that
Ni3Al formed by reacting Ni on the surface of the SiC whisker and Ni alloy powder with pure Al molten metal occupies most of the cross section of the matrix portion, and therefore the intermetallic compound Ni3A+ is mainly used as a matrix and the volume fraction is approximately 1096. It was observed that a composite material using SiC whiskers as a reinforcing material was well formed.

Example 4 Si3 with average fiber diameter 0.3 μm 1 average fiber length 100 μl
N4 whisker and average fiber diameter 20μI5 average fiber length 1-9
S
The volume fractions of i3N4 whiskers and Ti fibers are each 20
%, 4096, and a disk-shaped molded body having the same dimensions and shape as the molded body of Example 3 was formed.

Next, a composite material was formed using the molded body thus formed in the same manner and under the same conditions as in Example 3, and the composite material was cut and the metal structure of the cross section was investigated using an optical microscope. There were no areas with poor matrix metal impregnation. In addition, the structure of the cut surface of the coagulated body was examined using EPMA.
According to the analysis, TiAl formed by the reaction of Ti fibers with pure Al molten metal occupies most of the cross section of the matrix part.
It was observed that the composite material with N4 whiskers as a reinforcement material was well formed.

Example 5 W fiber with an average fiber diameter of 12 μm and an average fiber length of 1 ゛1ξ
By uniformly mixing Cu powder with an average particle size of 40 μm at a volume ratio of 15:28, uniformly mixing 2ZrF6 powder into the mixture, and compression molding the mixture in a mold, W fibers were produced. and the volume percentage of Cu powder is 15% and 28%, respectively.
%, and a disk-shaped molded body was formed using the same XJ method and shape H as the molded body of Example 3.

Next, a composite material was formed in the same manner as in Example 3, except that the p-thermal temperature was set to about 200°C and an Al alloy (JIS standard AC8A) was used as the molten metal. When the material was cut and the metallographic structure of the cross section was examined using an optical microscope, no defective matrix metal impregnation areas were found. Furthermore, when the structure of the cut surface of the solidified body was analyzed using EPMA, it was found that CuA was formed by the reaction of Cu fibers with AI in the molten Al alloy.
12 occupies most of the cross section of the matrix portion, and it is therefore recognized that a composite material mainly composed of the intermetallic compound CuAl2 as a matrix and Wm fibers with a volume fraction of about 15% as a reinforcement material is well formed. It was done.

Although the present invention has been described in detail with respect to specific embodiments above, the present invention is not limited to these embodiments, and various other embodiments are possible within the scope of the present invention. This will be obvious to those skilled in the art.

[Brief explanation of the drawing]

1 to 3 are process diagrams showing one embodiment of the method for manufacturing a composite material according to the present invention. 10... Carbon fiber, 12... Ni fiber, 14...
Stainless steel case, 16... Molded object, 18...
・K2ZrF6 aqueous solution, 20... when molten pure Al
Applicant: Toyota Autotun Co., Ltd. Representative: Patent Attorney: Akashi
Takeshi Masa Figure 1 Figure 2 20-Ml's ;f”i

Claims (1)

[Claims] A porous molded body containing an inorganic reinforcing material, a metal that reacts with Al to form an intermetallic compound, and fine pieces of metal fluoride is formed, and at least a portion of the molded body is made of Al or A.
1. A method for producing an intermetallic compound composite material, which comprises contacting a molten metal of an I-alloy and causing the molten metal to permeate into the molded body without substantially applying pressure.