JPH10158776A - Compound material of intermetallic compound, and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To inexpensively obtain a material using an intermetallic compound excellent in strength, toughness, and wear resistance at high temp. and also having oxidation resistance. SOLUTION: A powder of the oxide of a metal selected from Ti, Zr, and Hf and a powder of a metal selected from Cu, Co, Sn, Ni, and Zn are mixed, compacted, and heated by using microwaves, by which a compound material, where an oxide 2 of the metal selected from Cu, Co, Sn, Ni, and Zn is compounded with a matrix containing an intermetallic compound 1 constituted of the metal selected from Ti, Zr, and Hf and the metal selected from Cu, Co, Sn, Ni, and Zn, is obtained. When the heating atmosphere is formed into oxidizing atmosphere, a surface layer containing the oxide of the metal selected from Cu, Co, Sn, Ni, and Zn is further formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material using an intermetallic compound which is useful for high-temperature heat-resistant members such as gas turbines, jet engines, and high-temperature valves.

[0002]

2. Description of the Related Art Among AB binary intermetallic compounds, fc
A ₃ B-type intermetallic compounds and AB-type intermetallic compounds having a structure belonging to c, hcp or bcc can be plastically deformed and have high toughness, and thus are widely used as heat-resistant structural members.

However, since the intermetallic compound is obtained by once melting the metal and then cooling it, there is a disadvantage in terms of cost that a considerable high temperature and time are required. Therefore, Japanese Patent Application Laid-Open No. 5-117716 discloses a simpler and cheaper method for producing an intermetallic compound.
A method has been proposed in which a raw metal powder is finely pulverized by a mechanical alloying method and then sintered by a plasma sintering method. However, in this method, there are two steps of a fine powder generation step and a sintering step, so that it does not contribute much to cost reduction.

Further, when used under high temperature conditions such as gas turbine members, there is a disadvantage that the intermetallic compound is inferior in oxidation resistance and corrosion resistance. To overcome this,
Although it is conceivable that only the surface is oxidized to form a protective film by heat treatment in an oxygen-containing atmosphere, the thickness of the film obtained by the heat treatment is about several tens of μm, which is not sufficient as a protective film. Further, there is a disadvantage that the intermetallic compound itself is easily worn.

[0005]

As described above, the conventional intermetallic compounds have problems that the production cost is high, oxidation resistance and corrosion resistance are inferior, and that they are easily worn. The present invention has been made in order to solve such problems of the prior art, and provides a metal material having high strength at high temperatures, high toughness and high frictional properties, and having oxidation resistance at low cost. The purpose is to do so.

[0006]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies, and as a result, a compact formed of a metal powder and an oxide powder is microwave-heated to obtain a low-temperature, short-form product. In time, a material containing an intermetallic compound is obtained,
This was found to be an intermetallic compound composite and an intermetallic compound composite having an oxidation-resistant film formed on the surface, and the inventors have invented an intermetallic compound composite of the present invention and a method for producing the same.

[0007] The intermetallic compound composite of the present invention comprises Ti, Z
r, Hf and a metal selected from Cu, Co, Sn, Ni,
Cu, Co, Sn, Ni, Zn are added to a matrix containing an intermetallic compound containing a metal selected from Zn as an element.
An oxide containing a metal selected from the elements as a component is compounded.

Further, another intermetallic compound composite of the present invention comprises:
Metal selected from Ti, Zr, Hf and Cu, Co, S
In a matrix containing an intermetallic compound containing a metal selected from n, Ni, and Zn as elements, Cu, Co, Sn,
An oxide containing a metal selected from Ni and Zn as an element is compounded and has a surface layer containing an oxide containing a metal selected from Ti, Zr and Hf as an element.

The method for producing an intermetallic compound composite according to the present invention is characterized in that an oxide powder containing a metal selected from Ti, Zr and Hf as an element and a metal powder selected from Cu, Co, Sn, Ni and Zn are used. Are mixed and molded to obtain a molded body, and the molded body is heated using a microwave in a non-oxidizing atmosphere or under vacuum.

Further, another method for producing an intermetallic compound composite according to the present invention is directed to an oxide powder containing a metal selected from Ti, Zr, and Hf as an element and Cu, Co, Sn, Ni, Zn.
A molded body is obtained by mixing with a powder of a metal selected from the above and molding, and the molded body is heated using microwaves in an oxidizing atmosphere.

The surface layer further contains an oxide containing a metal selected from Ti, Zr and Hf as an element.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION An oxide of a metal element such as Ti, Zr, Hf (hereinafter referred to as a first metal) has a feature that its microwave absorptivity rapidly increases between 400 and 1000 ° C. . Since microwaves have the property of selectively heating materials having high absorptivity, when a molded body in which these oxides and metal powder coexist is heated by microwaves, the above oxides are selectively heated and formed. Even when the body temperature is about 500 ° C., the temperature may locally become higher than 1000 ° C. In addition, oxygen is easily dissociated at a high temperature in these oxides, and when the metal powder is a metal such as Cu, Co, Sn, Ni, and Zn (hereinafter, referred to as a second metal), the first powder is used.
The oxygen dissociated from the metal oxide and the surrounding second metal react to form an oxide, and the dissociated first metal also reacts with the surrounding second metal to become an intermetallic compound. . As a result, a composite of the intermetallic compound and the oxide of the second metal is obtained. This intermetallic compound composite has a structure in which ceramic particles are dispersed in an intermetallic compound matrix, and has improved strength and wear resistance as compared with a material containing only an intermetallic compound.

When microwave heating of the molded body is performed in a vacuum or in an inert gas atmosphere, a uniform intermetallic compound composite is obtained. The body surface is oxidized. As a result,
A surface layer of a composite of the first metal oxide and the second metal oxide, which is the same as the raw material, is obtained. The thickness of this surface layer can be controlled by the oxygen content in the atmosphere, and it is also possible to use an oxide entirely.

Hereinafter, the present invention will be described in detail.

First, the first selected from Ti, Zr and Hf
Powder of an oxide containing a metal of Cu, Co, Sn,
A powder of a metal selected from Ni and Zn is mixed, and a compact is obtained by compression molding. Preparation of the mixed powder is, as a specific example, mixing with a ball mill for about 3 to 10 hours using a liquid medium such as acetone, removing the liquid medium using a rotary evaporator or the like, and adjusting the particle size through a sieve. Can be done by The composition of the intermetallic compound formed varies depending on the mixing ratio of the metal oxide powder and the metal powder used, and the second metal is mixed with the oxide 1 of the first metal in a molar ratio of 3 to 5. Is preferred. Second
If the metal is less than this range, no intermetallic compound will be generated, and if it is too large, the amount of the intermetallic compound in the matrix will be small and the second metal will be contained in large amounts. The raw material powder to be used may be appropriately adjusted to a desired particle size as needed,
Those having a thickness of about 0.1 to 10 μm are preferable because the formation of the intermetallic compound is good and the handling of the powder is easy. The obtained mixed powder is filled into a mold in a predetermined amount, and is subjected to pressure molding to obtain a molded body. Pressure molding is performed by, for example, 1
After uniaxially pressing at a pressure of about 00 to 1000 kg / cm ² and then applying cold isostatic isostatic pressing at a pressure of about 1 to 10 t / cm ² , the desired shape can be appropriately obtained.

It is preferable that the obtained molded body is placed in an applicator of a microwave heating device and heated by covering the periphery with a heat insulating material. The frequency of the microwave used when producing the above-mentioned intermetallic compound composite from the molded product is 0.3
The range is preferably 30 to 30 GHz, and more preferably 20 to 30 GHz. The microwave has a heating temperature of 1200
Irradiation is performed at a temperature of at least 1 ° C, preferably at least 1400 ° C. If the heating temperature is too high, there is a possibility that the heat insulating material covering the molded body may melt, which is not preferable. For this reason, the heating temperature is preferably set to 1200 to 1700 ° C, more preferably 1400 to 1600 ° C. The heating time is 5
Minutes or more, preferably 30 minutes or more.

When the above-mentioned microwave heating is performed in a non-oxidizing atmosphere such as nitrogen, the above-described first heating as schematically shown in FIG.
A complex of an intermetallic compound (reference numeral 1 in the drawing) and an oxide of the second metal (reference numeral 2 in the drawing) is formed in the oxidizing atmosphere such as air. When heated in the atmosphere, oxidation proceeds on the surface of the composite, the intermetallic compound is oxidized, and an oxide of the first metal and an oxide of the second metal are generated. As a result, as shown in FIG. 2, the surface of the complex formed by the intermetallic compound composed of the first metal and the second metal (reference numeral 1 in the figure) and the oxide of the second metal (reference numeral 2) Then, an oxide film (reference numeral 4) including an oxide of the second metal (reference numeral 2) and an oxide of the first metal (reference numeral 3) is formed. The thickness of such an oxide film depends on the partial pressure of the oxidizing gas in the atmosphere. For example, after reducing the pressure to about 10 ^-3 to 10 ^-4 torr according to ordinary gas replacement, an inert gas such as nitrogen or argon is removed. When introduced, the remaining oxidizing gas is negligible and an oxide film is not substantially formed.

[0018]

The present invention will be described in more detail with reference to the following examples.

(Example 1) TiO ₂ powder and Cu powder were weighed so that the molar ratio became 1: 3, and ball mill mixing with nylon balls was performed using acetone as a dispersion medium. After mixing, drying was performed using a rotary evaporator, and the particle size was adjusted through a 500 μm sieve. The obtained mixed powder was filled in a mold, uniaxially pressed at a pressure of 200 kg / cm ² , and then subjected to cold isostatic pressing at a pressure of ² t / cm ² . The periphery of the obtained molded body is covered with a heat insulating material, and placed in an applicator of a microwave heating device.
30 Hz under N ₂ atmosphere by microwave of 15 kW
Heated to 800 ° C. for minutes. As a result of identifying the obtained sintered body by X-ray diffraction, CuTi and CuO were generated.
FIG. 1 shows a micrograph of the cross section of the obtained sintered body.
Was similar to

Example 2 Example 1 was repeated except that the TiO ₂ powder and the Cu powder were weighed so that the molar ratio was 1: 5.
Under the same conditions as described above, mixing, drying, molding, and microwave heating were performed. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, Cu ₃ Ti and CuO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 3 Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 1 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, CuTi and CuO were generated inside, and TiO ₂ and CuO were generated in the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 4 Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 2 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Cu ₃ Ti and CuO were contained therein,
TiO ₂ and CuO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 5 ZrO was used instead of TiO ₂ powder.
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 1 except that _two powders were used. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, CuZr
And CuO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 6 Instead of TiO ₂ powder, ZrO
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 2 except that _two powders were used. The product phase of the obtained sintered body was identified by X-ray diffraction, and as a result, Cu ₃ Z
r and CuO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 7 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 5 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, CuZr and CuO were generated inside, and ZrO ₂ and CuO were generated in the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 8 Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 6 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, Cu ₃ Zr and CuO were contained therein,
ZrO ₂ and CuO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 9 HfO was used instead of TiO ₂ powder.
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 1 except that _two powders were used. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, CuHf
And CuO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 10 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 2 except that HfO ₂ powder was used as the TiO ₂ powder. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Cu ₃ Hf and C
uO had been produced. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

(Example 11) Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 9 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, CuHf and CuO were
HfO ₂ and CuO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

(Example 12) Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 10 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, Cu ₃ Hf and CuO
However, HfO ₂ and CuO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 13 Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 1 except that a Co powder was used instead of the Cu powder. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, CoTi and Co
O had formed. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 14 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 2 except that Co powder was used instead of Cu powder. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, Co ₃ Ti and C
oO had been generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 15 Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 13 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, CoTi and CoO
However, TiO ₂ and CoO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 16 Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 14 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, Co ₃ Ti and CoO
However, TiO ₂ and CoO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

(Example 17) Zr was used instead of TiO ₂ powder.
Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 13 except that O ₂ powder was used. The product phase of the obtained sintered body was identified by X-ray diffraction.
r and CoO had been produced. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 18 Instead of TiO ₂ powder, Zr
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 14 except that the O ₂ powder was used. Results generated phase of the obtained sintered body was identified by X-ray diffraction, Co ₃
Zr and CoO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 19 Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 17 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, CoZr and CoO
However, ZrO ₂ and CoO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 20 Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 18 except that the heating atmosphere was air. The product phase of the obtained sintered body was identified by X-ray diffraction. As a result, Co ₃ Zr and CoO
However, ZrO ₂ and CoO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

(Example 21) Hf instead of TiO ₂ powder
Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 13 except that O ₂ powder was used. The product phase of the obtained sintered body was identified by X-ray diffraction.
f and CoO had been produced. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 22 Hf was used instead of TiO ₂ powder.
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 14 except that the O ₂ powder was used. Results generated phase of the obtained sintered body was identified by X-ray diffraction, Co ₃
Hf and CoO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 23 Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 21 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, CoHf and CoO
However, HfO ₂ and CoO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 24 Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 22 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, Co ₃ Hf and CoO
However, HfO ₂ and CoO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 25 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 1 except that Ni powder was used instead of Cu powder. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, NiTi and Ni
O had formed. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 26 Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 2 except that Ni powder was used instead of Cu powder. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Ni ₃ Ti and N
iO had been generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 27 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 25 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, NiTi and NiO
However, TiO ₂ and NiO were formed on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 28 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 26 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Ni ₃ Ti and NiO
However, TiO ₂ and NiO were formed on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

(Example 29) Zr instead of TiO ₂ powder
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 25 except that O ₂ powder was used. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, it was found that NiZ
r and NiO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

(Example 30) Instead of TiO2 powder, Zr
Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 26 except that O2 powder was used. Results generated phase of the obtained sintered body was identified by X-ray diffraction, Ni ₃
Zr and NiO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 31 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 29 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, NiZr and NiO
However, ZrO ₂ and NiO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 32 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 30 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Ni ₃ Zr and NiO
However, ZrO ₂ and NiO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 33 Instead of TiO ₂ powder, Hf
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 25 except that O ₂ powder was used. The product phase of the obtained sintered body was identified by X-ray diffraction.
f and NiO had been produced. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

(Example 34) Hf was used instead of TiO ₂ powder.
Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 26 except that O ₂ powder was used. Results generated phase of the obtained sintered body was identified by X-ray diffraction, Ni ₃
Hf and NiO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 35 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 33 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, NiHf and NiO
However, HfO ₂ and NiO were formed on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 36 Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 34 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, Ni ₃ Hf and NiO
However, HfO ₂ and NiO were formed on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 37 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 1 except that Sn powder was used instead of Cu powder. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, SnTi and Sn
O had formed. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 38 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 2 except that Sn powder was used instead of Cu powder. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, Sn ₃ Ti and S
nO was generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 39 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 37 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, SnTi and SnO
However, TiO ₂ and SnO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 40 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 38 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Sn ₃ Ti and SnO
However, TiO ₂ and SnO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 41 Zr was used instead of TiO ₂ powder.
Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 37 except that O ₂ powder was used. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, SnZ
r and SnO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

(Example 42) Zr was used instead of TiO ₂ powder.
Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 38 except that O ₂ powder was used. Results generated phase of the obtained sintered body was identified by X-ray diffraction, Sn ₃
Zr and SnO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 43 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 41 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, SnZr and SnO
However, ZrO ₂ and SnO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 44 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 42 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Sn ₃ Zr and SnO
However, ZrO ₂ and SnO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

(Example 45) Hf was used instead of TiO ₂ powder.
Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 37 except that O ₂ powder was used. The product phase of the obtained sintered body was identified by X-ray diffraction.
f and SnO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

(Example 46) Hf was used instead of TiO ₂ powder.
Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 38 except that O ₂ powder was used. Results generated phase of the obtained sintered body was identified by X-ray diffraction, Sn ₃
Hf and SnO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 47 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 45 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, SnHf and SnO
However, HfO ₂ and SnO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 48 Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 46 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Sn ₃ Hf and SnO
However, HfO ₂ and SnO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 49 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 1 except that Zn powder was used instead of Cu powder. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, ZnTi and Zn
O had formed. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 50 Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 2 except that Zn powder was used instead of Cu powder. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, Zn ₃ Ti and Z
nO was generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 51 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 49 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, ZnTi and ZnO
However, TiO ₂ and ZnO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 52 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 50 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, Zn ₃ Ti and ZnO
However, TiO ₂ and ZnO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

(Example 53) Zr was used instead of TiO ₂ powder.
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 49 except that O ₂ powder was used. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, ZnZ
r and ZnO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

(Example 54) Zr was used instead of TiO ₂ powder.
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 50 except that O ₂ powder was used. Results generated phase of the obtained sintered body was identified by X-ray diffraction, Zn ₃
Zr and ZnO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 55 Mixing, drying, molding and microwave heating were carried out under the same conditions as in Example 53 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, ZnZr and ZnO
However, ZrO ₂ and ZnO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 56 Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 54 except that the heating atmosphere was air. As a result of identifying the formed phase of the obtained sintered body by X-ray diffraction, Zn ₃ Zr and ZnO
However, ZrO ₂ and ZnO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

(Example 57) Hf was used instead of TiO ₂ powder.
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 49 except that O ₂ powder was used. The product phase of the obtained sintered body was identified by X-ray diffraction.
f and ZnO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

(Example 58) Hf was used instead of TiO ₂ powder.
Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 50 except that O ₂ powder was used. Results generated phase of the obtained sintered body was identified by X-ray diffraction, Zn ₃
Hf and ZnO were generated. An image of a cross section of the obtained sintered body taken with a micrograph was the same as that in FIG.

Example 59 Mixing, drying, molding and microwave heating were performed under the same conditions as in Example 57 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, ZnHf and ZnO
However, HfO ₂ and ZnO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

Example 60 Mixing, drying, molding, and microwave heating were performed under the same conditions as in Example 58 except that the heating atmosphere was air. As a result of identifying the generated phase of the obtained sintered body by X-ray diffraction, Zn ₃ Hf and ZnO
However, HfO ₂ and ZnO were generated on the surface layer. An image of a cross section of the obtained sintered body taken by a micrograph was the same as that in FIG.

(Evaluation) The obtained test pieces of the sintered bodies of Examples 1 to 60 were subjected to a three-point bending test based on JIS-1601R, and the strength at room temperature was measured. Further, a friction test was performed on each test piece by a disk-on-disk method using an iron-based material as a mating material. Further, each test piece was left in the air at 1500 ° C. for 1000 hours to perform an oxidation resistance test.

The above three tests were also performed on test pieces of only intermetallic compounds prepared by a conventional method, and the ratios of the values obtained in Examples 1 to 60 to the values obtained therefrom were defined as specific strength, specific wear amount and specific ratio. It was determined as a change in weight. Table 1 shows the results.

[0081]

Table 1------------------------------------------------------Specific strength ---------------------------------------------------------------------------------------------------------- Example 1 1.17 0.28 0.78 Example 2 1.14 0.33 0.69 Example 3 1.53 0.18 0.12 Example 4 1.52 0.16 0.10 Example 5 1.16 0.26 0.80 Example 6 1.17 0. 23 0.68 Example 7 1.51 0.14 0.10 Example 8 1.47 0.12 0.09 Example 9 1.25 0.31 0.77 Example 10 1.30 0.29 0 0.74 Example 11 1.42 0.13 0.11 Example 12 1.44 0.15 0.13 Example 13 1.16 0.26 0.74 Example 14 1.12 0.30 67 Example 15 1.58 0.20 0.10 Example 16 1.55 0.17 0.10 Example 17 1.12 0.22 0.81 Example 18 1.17 0.23 0.69 Operation Example 19 1.53 0.15 0.13 Example 20 1.58 0.15 0.07 Example 21 1.23 0.29 0.76 Example 22 1.27 0.27 0.72 Example 23 1.40 0.15 0.10 Example 24 1.44 0.15 0.12 Example 25 1.12 0.21 0.79 Example 26 1.14 0.23 0.76 Example 27 1. 63 0.12 0.08 Example 28 1.59 0.13 0.10 Example 29 1.10 0.20 0.61 Example 30 1.15 0.23 0.64 Example 31 1.56 0 .12 0.15 Example 32 1.57 0.12 0.14 Example 33 1.22 0.23 0.75 Example 34 1.26 0.21 0.72 Example 35 1.52 0.11 0.11 Example 36 1.54 0.13 0.13 Example 37 1.19 0.23 0.74 Example 38 1.16 0.26 0.69 Example 39 1.52 0.18 0.12 Example 40 1.52 0.17 0.10 Example 41 1 .13 0.20 0.78 Example 42 1.17 0.23 0.79 Example 43 1.67 0.13 0.11 Example 44 1.58 0.12 0.09 Example 45 1.23 0.28 0.69 Example 46 1.30 0.29 0.74 Example 47 1.52 0.13 0.11 Example 48 1.54 0.17 0.13 Example 49 1.17 0. 28 0.70 Example 50 1.14 0.31 0.69 Example 5 1.53 0.18 0.12 Example 52 1.51 0.14 0.11 Example 53 1.13 0.23 0.82 Example 54 1.19 0.21 0.80 Example 55 1. 54 0.14 0.10 Example 56 1.57 0.12 0.09 Example 57 1.22 0.25 0.77 Example 58 1.26 0.29 0.73 Example 59 1.62 0 .13 0.11 Example 60 1.52 0.15 0.13 ------------------------------------------------------------------------------------ --- As is clear from the above results, the intermetallic compound composite according to the present invention has high strength, and has a small amount of wear and a small weight change due to oxidation. This tendency becomes more remarkable when an oxide surface layer is formed.

[0082]

As described above, according to the present invention,
Maintains high strength, high toughness and high friction characteristics at high temperatures,
In addition, an intermetallic compound composite having oxidation resistance can be provided, and this material can be manufactured at low cost, which is extremely useful in industry.

[Brief description of the drawings]

FIG. 1 is a diagram schematically showing an image obtained by photographing a cross section of a sintered body according to the present invention with a micrograph.

FIG. 2 is a diagram schematically showing an image of a cross section of another sintered body according to the present invention taken by a micrograph.

[Explanation of symbols]

 Reference Signs List 1 intermetallic compound 2 oxide of second metal 3 oxide of first metal 4 oxide film

Claims (4)

[Claims] 1. A metal selected from Ti, Zr, Hf and C
A matrix containing an intermetallic compound containing a metal selected from u, Co, Sn, Ni, and Zn as elements
An intermetallic compound composite, wherein an oxide containing a metal selected from Co, Sn, Ni, and Zn as an element is composited. 2. A metal selected from Ti, Zr, Hf and C
A matrix containing an intermetallic compound containing a metal selected from u, Co, Sn, Ni, and Zn as elements
A metal characterized in that an oxide containing a metal selected from Co, Sn, Ni, and Zn is compounded, and a surface layer containing an oxide containing a metal selected from Ti, Zr, and Hf is provided. Compound complex. 3. An oxide powder containing a metal selected from Ti, Zr, and Hf as an element and Cu, Co, Sn, Ni, Zn
2. The metal according to claim 1, wherein a molded body is obtained by mixing and molding with a powder of a metal selected from the group, and the molded body is heated using microwaves in a non-oxidizing atmosphere or under vacuum. Method for producing intermetallic compound complex. 4. An oxide powder containing a metal selected from Ti, Zr and Hf as an element and Cu, Co, Sn, Ni, Zn
3. An intermetallic compound composite according to claim 2, wherein a molded body is obtained by mixing and molding with a powder of a metal selected from the group, and the molded body is heated using a microwave in an oxidizing atmosphere. Manufacturing method.