JP2008223077A - Ceramic/metal composite material and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ceramic/metal composite material exhibiting small linear thermal expansion in a wide temperature range and also to provide its manufacturing method. <P>SOLUTION: The ceramic/metal composite material can be obtained by compositing a light metal or a light metal alloy, such as aluminum or magnesium alloy, with interstitial manganese nitride. A temperature region having a temperature width of at least ≥20 degrees where a variation δ in linear thermal expansion ΔL/L becomes ≤1×10<SP>-4</SP>is within a temperature range between -30°C and 90°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a metal-ceramic composite material and a method for producing the same.

  For example, in the field of semiconductor devices, the miniaturization of design rules has recently progressed rapidly, and the management of minute dimensions has become extremely important. For this reason, materials that are difficult to change in shape due to thermal expansion in the use environment, and ultimately, zero-expansion materials are required for the components of semiconductor manufacturing apparatuses, particularly members that hold and transport silicon wafers.

  As is well known, a low thermal expansion material generally refers to a material having a small absolute value of linear expansion coefficient. As such a low thermal expansion material, a 32Ni-5Co-Fe alloy (so-called Super Invar) is known, and a material to which about 2% of C and Si are added for the purpose of imparting castability to this alloy is known. It has been. However, since such an alloy material has a specific gravity of about 8, it is easily bent due to its own weight, and it is difficult to use from the viewpoint when the fine dimension management is emphasized. In addition, the use of such a material having a high specific gravity causes a problem in that a large mechanical strength is required for a related member for holding the material.

  Thus, a composite material comprising a metal matrix and a ceramic reinforced phase has attracted attention as a substitute for such an alloy material. This composite material has both the rigidity and wear resistance of the reinforcing phase and the ductility and toughness of the metal matrix, and has been used for various precision machine parts (for example, see Patent Document 1). ).

However, the value of the linear expansion coefficient in the temperature range of about −50 ° C. to 100 ° C. of the conventional metal-ceramic composite material is about 4 × 10 ⁻⁶ / ° C., and its absolute value is not sufficiently small. Therefore, there exists a problem that the temperature range which shows the linear thermal expansion permitted from a viewpoint of minute dimension management is narrow. Further, the temperature range where the linear thermal expansion is small does not always coincide with the temperature range of the usage environment, and there is a problem that the range of material selection is narrow.
Japanese Patent Laid-Open No. 10-8164 (paragraphs [0021], [0022], [0037], etc.)

  This invention is made | formed in view of this situation, and it aims at providing the metal-ceramics composite material which shows small linear thermal expansion in a wide temperature range, and its manufacturing method.

  In order to solve the above problems, the inventors examined a metal-ceramic composite material in which the linear thermal expansion was suppressed because the absolute value of the linear expansion coefficient was small, and a material in which the linear thermal expansion was suppressed small. Note that is not necessarily limited to a material whose linear expansion coefficient does not change in temperature and exhibits a constant small value. That is, by changing the linear expansion coefficient from a positive value to a negative value, or vice versa, from a negative value to a positive value, the linear thermal expansion can be kept within a certain range over a wide temperature range. Attention was paid to the completion of the present invention.

According to the first aspect of the present invention, a metal-ceramic composite material obtained by combining a light metal or a light metal alloy and interstitial manganese nitride, the amount of change in linear thermal expansion is within 1 × 10 ^−4. A metal-ceramic composite material is provided in which a temperature range of at least 20 ° C. or more is in a temperature range of −30 ° C. or more and 90 ° C. or less.

According to a second aspect of the present invention, there is provided a metal-ceramic composite material obtained by combining a light metal or light metal alloy and interstitial manganese nitride, and having a temperature range of 20 ° C. or more within a temperature range of 0 ° C. to 40 ° C. The metal-ceramic composite material is characterized in that the absolute value of the linear expansion coefficient in the region is always 1.5 × 10 ⁻⁶ / ° C. or less.

  According to a third aspect of the present invention, there is provided a method for producing such a metal-ceramic composite material, that is, a method for producing a metal-ceramic composite material obtained by combining a light metal or light metal alloy and interstitial manganese nitride. Then, a melted light metal or light metal alloy is pressed and infiltrated into the filler or molded body containing the interstitial manganese nitride, and the processing temperature at that time is set to 600 ° C. to 1000 ° C. A method of manufacturing a composite material is provided.

  International publication WO 2006/011590 shows that interstitial manganese nitride has a negative coefficient of linear expansion in a predetermined temperature range depending on the composition, and that such interstitial manganese nitride is used. It is suggested that it is possible to produce a material with suppressed thermal expansion.

  However, this publication does not describe any examples of the composite material that actually suppresses thermal expansion. In addition, since interstitial manganese nitride has a large change in linear thermal expansion, for example, it is not easy to keep linear thermal expansion within an allowable range in the vicinity of room temperature. Furthermore, in order to obtain a composite material in which the thermal expansion is actually suppressed to be small within a certain temperature range, there are various problems such as the structural uniformity of the composite material and the maintenance of material properties during the manufacturing process. The present invention also solves such problems that have not been solved by the prior art.

  Since the metal-ceramic composite material according to the present invention has a low linear thermal expansion in a desired temperature range, particularly in the vicinity of room temperature, extremely strict management is required for dimensional accuracy used in such a temperature environment. Excellent properties as a part to be used. In addition, the temperature range with low linear thermal expansion can be adjusted by adjusting the constituent elements and composition ratio of interstitial manganese nitride and the ratio of interstitial manganese nitride and metal matrix. Can do. By using such a metal-ceramic composite material as a part of a manufacturing apparatus, particularly a part that requires strict dimensional control at the time of use, the quality and yield of the manufactured product can be improved.

The metal-ceramic composite material (hereinafter referred to as “composite material”) according to the present invention includes a light metal or light metal alloy (hereinafter referred to as “light metal”) as a base material, and an interstitial ceramic as a reinforcing material and a thermal expansion control material. A temperature region of at least a temperature range of 20 degrees or more where the variation δ of the linear thermal expansion ΔL / L is within 1 × 10 ⁻⁴ (δ ≦ 1 × 10 ⁻⁴ ) is made of manganese nitride, and is −30 ° C. or more It has the characteristic that it exists in the temperature range below 90 degreeC.

  Note that “L” is the length of the composite material at the reference temperature, and the reference temperature can be, for example, room temperature or the use environment temperature of the composite material. “ΔL” is the difference (length change) between the length of the composite material at a predetermined temperature and the length at the reference temperature. The change amount δ of the linear thermal expansion ΔL / L is a difference between the maximum value and the minimum value of the linear thermal expansion ΔL / L in a certain temperature range, and is not necessarily limited to the linear thermal expansion ΔL / L at the minimum temperature in the temperature range. It is not the difference in linear thermal expansion ΔL / L at the highest temperature. Also, δ is always defined as a value greater than or equal to zero. The temperature differential (slope) of linear thermal expansion ΔL / L, that is, d (ΔL / L) / dT is defined as the linear expansion coefficient, and is usually expressed as α.

More preferably, this composite material has a temperature range of at least 10 ° C. in which the variation δ of the linear thermal expansion ΔL / L is within 5 × 10 ⁻⁵ (δ ≦ 1 × 10 ⁻⁵ ). It has the characteristic that it exists in the temperature range of 70 degreeC or more. For example, when a composite material in which the linear thermal expansion ΔL / L is kept small is used as a manufacturing apparatus member in such a temperature range as a use environment, dimensional accuracy can be managed extremely strictly, so that the quality of the product is improved, Can be maintained.

  As the light metal, metal aluminum, aluminum alloy, metal magnesium, magnesium alloy is preferably used. The linear expansion coefficient α of these light metals or the like always shows a positive value in a general use environment of various manufacturing apparatuses, specifically, −100 ° C. or higher.

  Therefore, the interstitial manganese nitride has a temperature increase in the temperature region so that the change amount δ of the linear thermal expansion ΔL / L of the composite material is within the predetermined range as described above in the predetermined temperature region. Accordingly, those having a characteristic that the linear thermal expansion ΔL / L becomes smaller, that is, those having a region where the value of the linear expansion coefficient α is negative are preferably used.

  Interstitial manganese nitride is the same as what is called reverse perovskite manganese nitride, which is cubic or slightly distorted cubic (eg hexagonal, monoclinic, orthorhombic) Crystal system, tetragonal system, trigonal system, etc.), but cubic system is preferable.

  The negative thermal expansibility of interstitial manganese nitride is derived from the magnetovolume effect of manganese nitride. The magnetic volume effect refers to a phenomenon in which the volume changes as the magnetic moment changes. In the interstitial manganese nitride, the magnetic moment increases in the low-temperature magnetic ordered phase, and the volume increases as the temperature decreases accordingly. The effect derived from this magnetism overcomes the normal positive thermal expansion, thereby realizing the net negative thermal expansion of interstitial manganese nitride. Therefore, when interstitial manganese nitride is used for thermal expansion control in a composite material, the temperature range in which the linear expansion coefficient α can be kept small is about the magnetic transition temperature of interstitial manganese nitride and lower.

The general chemical formula of interstitial manganese nitride is represented by “Mn _4-x A _x N”. The element A is one element selected from Co, Ni, Cu, Zn, Ga, Rh, Pd, Ag, Cd, and In, and 0 <x <4 (where x is not an integer). is there. Alternatively, the element A is Mg, Al, Si, Sc and any two or more elements of Group 4 to 15 atoms in the 4th to 6th periods of the periodic table, at least one of which is Co, Ni, Cu, Any of Zn, Ga, Rh, Pd, Ag, Cd, and In, and 0 <x <4. Furthermore, a part of nitrogen N may be substituted with any of hydrogen H, boron B, carbon C, and oxygen O, preferably boron B and carbon C, more preferably carbon C.

The general chemical formula “Mn _4-x A _x N” of interstitial manganese nitride is a formula based on the assumption that there are no atomic defects or excess, but interstitial manganese nitride is a defect that can normally occur in the crystal lattice. Even if there is an excess, as described above, as long as there is a temperature range exhibiting a negative linear expansion coefficient α, the composite material can be used without any problem.

As a specific composition of the interstitial manganese nitride, Mn ₃ Cu _0.5 Sn _0.5 N, Mn _3.1 Cu _0.4 Sn _0.5 N, Mn ₃ Cu _0.5 Sn _0.5 N _{0 .9} C _0.1 , Mn _3.1 Cu _0.4 Sn _0.5 N _0.9 C _0.1 , Mn _2.88 Fe _0.12 Cu _0.4 Sn _0.6 N, Mn ₃ Zn _{0 .5} Sn _0.5 N, Mn _3.1 Zn _0.4 Sn _0.5 N, Mn ₃ Zn _0.5 Sn _0.5 N _0.9 C _0.1 , Mn _3.1 Zn _0.4 Sn _0.5 N _0.9 C _0.1 , Mn _2.88 Fe _0.12 Zn _0.4 Sn _0.6 N and the like can be mentioned.

FIG. 1 shows the relationship between the linear thermal expansion ΔL / L of Mn ₃ Cu _0.5 Sn _0.5 N and the linear expansion coefficient α corresponding to the temperature differentiation (gradient). The linear thermal expansion ΔL / L was measured at a temperature increase rate of 2 ° C./min from room temperature using [ThermoPlus2 TMA8310] manufactured by Rigaku Corporation. Mn ₃ Cu _0.5 Sn _0.5 N used for this measurement has a rectangular parallelepiped shape of 3 mm × 3 mm × 10 mm. In this sample, a predetermined amount of Mn ₃ N, Sn, and Cu are weighed and uniformly mixed, uniaxially molded at 1 t / cm ² (= 98 MPa), and then heated in a nitrogen atmosphere. It was cut out from a sintered body obtained by maintaining at the same temperature for 5 hours as ° C.

  As shown in FIG. 1, between room temperature and about 50 ° C., the linear thermal expansion ΔL / L increases as the temperature increases. At this time, the linear expansion coefficient α decreases as the temperature rises, but in this temperature range, the linear expansion coefficient α shows a positive value. In other words, although the linear expansion coefficient α decreases as the temperature rises, the absolute value thereof is a positive value. Therefore, the sample expands as the temperature rises, and as a result, the linear thermal expansion ΔL / L gradually increases. Is getting bigger.

However, it can be seen that the linear thermal expansion ΔL / L of the sample gradually decreases as the temperature rises in the temperature range of about 50 ° C. to 90 ° C., and the sample starts to shrink as the temperature rises. That is, the linear expansion coefficient α of the sample becomes 0 / ° C. at about 50 ° C., and is about −5 × 10 ⁻⁶ / ° C., which is the smallest value (= a negative value indicating a large absolute value) at about 75 ° C. And then increased to about 90 ° C. and again to show 0 / ° C., and in the temperature range of about 50 ° C. to about 90 ° C., the linear expansion coefficient α always shows a negative value. Therefore, in this temperature region, the sample shrinks as the temperature rises. Thus, a phenomenon called negative thermal expansion in which the linear thermal expansion ΔL / L of the sample gradually decreases (that is, a phenomenon in which the gradient of the linear thermal expansion ΔL / L with respect to the temperature becomes negative) appears.

  It can be seen that when the temperature exceeds about 90 ° C., the linear thermal expansion ΔL / L of the sample starts to increase, and the sample expands as the temperature increases. That is, when the linear expansion coefficient α of the sample exceeds about 90 ° C., it shows a positive value again, so that the linear thermal expansion ΔL / L increases as the temperature rises.

Thus, Mn ₃ Cu _0.5 Sn _0.5 N exhibits a characteristic behavior of shrinking with increasing temperature between about 50 ° C. and about 90 ° C. On the other hand, the linear expansion coefficient α in this temperature region of the light metal or the like constituting the composite material always shows a positive value, that is, shows a behavior of expanding as the temperature rises.

Therefore, in the composite material composed of Mn ₃ Cu _0.5 Sn _0.5 N and light metal or the like, in this temperature region, when the temperature rises, the volume decrease of Mn ₃ Cu _0.5 Sn _0.5 N and the volume of light metal or the like The increase can be offset, and the volume increase of Mn ₃ Cu _0.5 Sn _0.5 N and the volume decrease of light metal or the like can be offset when the temperature drops.

That is, the amount of change δ of the linear thermal expansion ΔL / L as a composite material can be kept small in a certain temperature range by combining Mn ₃ Cu _0.5 Sn _0.5 N and light metal etc. at a predetermined ratio. Can do. In addition, the absolute value of the linear expansion coefficient α can be kept at a very small value within a predetermined temperature range. As shown in Example 3 to be described later, a temperature range 20 within a temperature range of 0 ° C. to 40 ° C. Thus, it is possible to obtain a composite material in which the absolute value of the linear expansion coefficient α is always 1.5 × 10 ⁻⁶ / ° C. or less in a region of more than 1 degree.

Mn ₃ Cu _0.5 Sn _0.5 N exhibits the thermal characteristics as described above, but by adjusting the constituent elements and composition ratio of interstitial manganese nitride, the ratio of interstitial manganese nitride and light metal, etc. The temperature range where the linear expansion coefficient α is negative can be shifted to the low temperature side or the high temperature side, the width of the temperature range can be narrowed or expanded, and the absolute value of the linear expansion coefficient α can be increased. Can be changed.

  Therefore, by adjusting the negative expansion property of interstitial manganese nitride to the thermal expansion characteristics of light metals and the like, or adjusting the composite ratio thereof, a composite material suitable for the application and use conditions, that is, linear thermal expansion ΔL It is possible to obtain a composite material in which the temperature range in which such characteristics can be obtained is adjusted to a desired temperature while suppressing the change amount δ of / L.

  Next, the manufacturing method of a composite material is demonstrated. For the production of composite materials, a method in which light metal or the like is melted and infiltrated into a filler or molded body of interstitial manganese nitride powder is suitably used, but interstitial manganese nitride is easily altered, oxidized and decomposed at high temperatures. Therefore, it is important to prevent such alteration or the like from occurring in the filling body or the molded body during the molten metal infiltration process. In addition, a filling body means the thing in the state with which the container was filled. The simple “molded body” includes, in addition to the press molding method, a molded body produced by a method generally used as a ceramic powder molding method, a calcined body and a sintered body of the molded body.

  Therefore, in the manufacture of composite materials, first, interstitial manganese nitride powder is filled into a container such as iron or carbon, and pressure is applied to the interstitial manganese nitride powder, or vibration is applied to the container, so Manganese powder filler is prepared. Alternatively, the interstitial manganese nitride powder may be pressed by adding an inorganic binder or an organic binder to the interstitial manganese nitride powder, or by mixing the interstitial manganese nitride powder, a solvent and an inorganic binder, and using a method such as filter press. The press-molded body can be produced.

In addition, the calcined body can be produced by continuously performing the synthesis of interstitial manganese nitride and preliminary sintering. For example, when the interstitial manganese nitride is Mn ₃ Cu _0.5 Sn _0.5 N, a predetermined amount of Mn ₃ N, Sn and Cu are weighed and uniformly mixed, and the powder is obtained by uniaxial molding. By heating the press-molded body to a predetermined temperature in a nitrogen atmosphere, a calcined body can be obtained by advancing the synthesis reaction and partly sintering.

Also, a predetermined amount of Mn ₃ N and Sn are weighed and mixed, and then heated in a nitrogen atmosphere to synthesize Mn ₃ SnN, while a predetermined amount of Mn ₃ N and Cu are weighed and mixed, and then nitrogen is added. Mn ₃ CuN is synthesized by heating in an atmosphere, the two types of synthetic powders thus obtained are weighed in predetermined amounts, the mixed powder is uniaxially molded, and the resulting press-molded body is heated to a predetermined temperature in a nitrogen atmosphere. It is also possible to use a method of obtaining a calcined body or a sintered body by synthesizing Mn ₃ Cu _0.5 Sn _0.5 N and partially advancing sintering.

The filling body or the molded body thus produced is combined with both by combining light metal and the like under pressure. That is, the filler or molded body is preheated (heated) to 500 ° C. to 1000 ° C., and this is set in a casting mold. On the other hand, by melting a light metal or the like at a temperature equal to or higher than its melting point, injecting the molten metal into the casting mold and applying a predetermined pressure, the molten metal can be infiltrated into the filler or molded body. . In this case, the molten metal temperature is preferably 600 to 1000 ° C. If the temperature is lower than 600 ° C., poor penetration tends to occur, and if the temperature is 1000 ° C. or higher, the molten metal is easily oxidized and oxides are mixed therein. When the light metal is magnesium or a magnesium alloy, in order to prevent ignition, gas such as CO ₂ , nitrogen gas, argon gas, mixed gas of argon gas and nitrogen gas, reduced pressure (1 atm or less) nitrogen gas, etc. Is preferably introduced into the melting furnace and the casting mold.

  When such a permeation process is completed, the solid matter is taken out from the casting mold. Since a layer made only of a light metal or the like is formed around the solid material, this portion can be removed by machining, and thus a composite material can be obtained.

[Example 1]
A predetermined amount of Mn ₃ N, Sn and Cu were weighed and uniformly mixed, uniaxially molded at 1 t / cm ² (= 98 MPa), and then heated in a nitrogen atmosphere. The maximum heating temperature at this time was set to 800 ° C., held at the same temperature for 5 hours, and then cooled to room temperature. The calcined body thus obtained was crushed to obtain Mn ₃ Cu _0.5 Sn _0.5 N powder.

To the obtained Mn ₃ Cu _0.5 Sn _0.5 N powder, 5 parts by weight of colloidal silica and 5 parts by weight of polyvinyl butyral (PVB) as a binder are uniformly added to 100 parts by weight of the powder. And a press-molded body of 150 mm × 100 mm × 50 mm was produced by a press molding method. The ceramic content of this compact was 40% by volume.

This compact was preheated at 400 ° C. using an electric furnace and set in an aluminum casting mold. An aluminum alloy (JIS AC8A) was heated to 750 ° C. and melted, and this molten alloy was poured into the previous casting mold and pressurized at 60 MPa for 10 minutes to allow the molten alloy to penetrate into the compact. After lowering the temperature of the casting mold to room temperature, the solid in the casting mold is taken out, and the alloy layer on the surface of the solid is removed to obtain Mn ₃ Cu _0.5 Sn _0.5 N and A composite material composed of an aluminum alloy was obtained.

  A test piece of 4 mm × 4 mm × 15 mm was cut out from this composite material, and a linear thermal expansion ΔL / L of 20 ° C. to 300 ° C. with a thermal dilatometer (manufactured by ULVAC-RIKO: LIX-I) was increased at a rate of temperature increase of 2 ° C./min Measured with

The result is shown in FIG. Here, the reference temperature of the linear thermal expansion ΔL / L is set to 27 ° C. In Example 1, the change amount δ of the linear thermal expansion ΔL / L is always δ ≦ 1 × 10 ⁻⁴ within a temperature range of about 25 ° C. to 57 ° C. About is always a δ ≦ 5 × ^{10 -5} at a temperature region of the temperature range 10 ° within the temperature range of 25 ° C. to 52 ° C., the broadest temperature range becomes δ ≦ 5 × ^{10 -5} is about 25 ° C. It was -42 degreeC and about 36 to 53 degreeC. The linear expansion coefficient α in the range of 35 ° C. to 45 ° C. showed a value of −7.4 × 10 ⁻⁶ / ° C.

[Example 2]
Except that the heating temperature of Mn ₃ N, Sn, and Cu was set to 900 ° C. and the ceramic content of the formed body was changed to 64% by volume, the composite was produced according to the method for producing and evaluating the composite material according to Example 1 described above. Materials were prepared and their properties were evaluated. The composition of manganese nitride was Mn ₃ Cu _0.5 Sn _0.5 N as in Example 1. The result is shown in FIG. Here, the reference temperature of the linear thermal expansion ΔL / L is set to 65 ° C.

In Example 2, the change amount δ of the linear thermal expansion ΔL / L is always δ ≦ 1 × 10 ⁻⁴ in a temperature range of 20 degrees in a temperature range of about 45 ° C. to 80 ° C., The widest temperature range where δ ≦ 1 × 10 ⁻⁴ was about 53 ° C. to 77 ° C. Δ ≦ 5 × 10 ⁻⁵ is always established in the temperature range of 10 ° C. within the temperature range of about 52 ° C. to 78 ° C., and the widest temperature range satisfying δ ≦ 5 × 10 ⁻⁵ is about 58 ° C. It became 72 degreeC. The linear expansion coefficient α at 65 ° C. to 80 ° C. was 3.5 × 10 ⁻⁶ / ° C.

[Example 3]
Example 1 described above except that the composition of manganese nitride was Mn _3.226 Sn _0.387 Cu _0.387 N, the heating temperature was 900 ° C., and the ceramic content of the compact was changed to 51% by volume. According to the composite material manufacturing method and evaluation method according to the present invention, composite materials were produced and their characteristics were evaluated. The result is shown in FIG. Here, the reference temperature of the linear thermal expansion ΔL / L is 23 ° C.

In Example 3, the change amount δ of the linear thermal expansion ΔL / L is always δ ≦ 1 × 10 ⁻⁴ in the temperature range of 20 degrees in the temperature range of about −22 ° C. to 40 ° C. The widest temperature range where δ ≦ 1 × 10 ⁻⁴ is about −15 ° C. to 33 ° C. In the temperature range of about −15 ° C. to 33 ° C. within the temperature range of 10 ° C., δ ≦ 5 × 10 ⁻⁵ is always ^satisfied, and the widest temperature range where δ ≦ 5 × 10 ⁻⁵ is about −10 C. to 31.degree. Further, Example 3 shows a characteristic that δ ≦ 2 × 10 ⁻⁵ in a temperature range of about −8 ° C. to 28 ° C. As described above, Example 3 exhibited excellent characteristics that the temperature range in which the linear thermal expansion ΔL / L is small is extremely wide.

Further, the linear expansion coefficient α at 0 ° C. to 20 ° C. of Example 3 is −1.4 × 10 ⁻⁶ / ° C., and its absolute value is extremely small over a wide temperature range, and exhibits excellent low thermal expansion. Was confirmed.

[Example 4]
Example 1 described above except that the composition of manganese nitride is Mn _3.209 Sn _0.396 Cu _0.396 N, the heating temperature is 900 ° C., and the ceramic content of the compact is changed to 54% by volume. According to the composite material manufacturing method and evaluation method according to the present invention, composite materials were produced and their characteristics were evaluated. The result is shown in FIG. Here, the reference temperature of the linear thermal expansion ΔL / L is 23 ° C.

In Example 4, the change amount δ of the linear thermal expansion ΔL / L is always δ ≦ 1 × 10 ⁻⁴ in the temperature range of 20 degrees in the temperature range of about −14 ° C. to 48 ° C. The widest temperature range where δ ≦ 1 × 10 ⁻⁴ is about −10 ° C. to 46 ° C. Δ ≦ 5 × 10 ⁻⁵ is always satisfied in the temperature range of 10 ° C. within the temperature range of about −8 ° C. to 44 ° C., and the widest temperature range where δ ≦ 5 × 10 ⁻⁵ is about −5. It became 45 degreeC-43 degreeC, and also this Example 4 showed the value with small linear thermal expansion (DELTA) L / L in the wide temperature range. In addition, the linear expansion coefficient α in the range of 10 ° C. to 30 ° C. of Example 4 showed a value of −2.5 × 10 ⁻⁶ / ° C.

[Example 5]
Example 1 described above except that the composition of manganese nitride was Mn _3.191 Sn _0.404 Cu _0.404 N, the heating temperature was 900 ° C., and the ceramic content of the compact was changed to 59% by volume. According to the composite material manufacturing method and evaluation method according to the present invention, composite materials were produced and their characteristics were evaluated. The result is shown in FIG. Here, the reference temperature of the linear thermal expansion ΔL / L is 23 ° C.

In Example 5, the change amount δ of the linear thermal expansion ΔL / L is always δ ≦ 1 × 10 ⁻⁴ in a temperature range of 20 ° C. within a temperature range of about −12 ° C. to 55 ° C. The widest temperature range where δ ≦ 1 × 10 ⁻⁴ is about −10 ° C. to 53 ° C. Δ ≦ 5 × 10 ⁻⁵ is always established in the temperature range of 10 ° C. within the temperature range of about −8 ° C. to 54 ° C., and the widest temperature range where δ ≦ 5 × 10 ⁻⁵ is about −5. The linear thermal expansion ΔL / L was small over a wide temperature range. The linear expansion coefficient α in the range of 15 ° C. to 35 ° C. showed a value of −3.8 × 10 ⁻⁶ / ° C.

Mn ₃ Cu _0.5 Sn _0.5 N graph showing the linear thermal expansion [Delta] L / L and the linear expansion coefficient α of. 2 is a graph showing the linear thermal expansion ΔL / L and the linear expansion coefficient α of Example 1. The graph which shows linear thermal expansion (DELTA) L / L and linear expansion coefficient (alpha) of Example 2. FIG. 6 is a graph showing the linear thermal expansion ΔL / L and the linear expansion coefficient α of Example 3. The graph which shows linear thermal expansion (DELTA) L / L and the linear expansion coefficient (alpha) of Example 4. FIG. 10 is a graph showing the linear thermal expansion ΔL / L and the linear expansion coefficient α of Example 5.

Claims (7)

A metal-ceramic composite material obtained by combining light metal or light metal alloy and interstitial manganese nitride,
A metal-ceramic composite material, characterized in that a temperature range of at least a temperature range of 20 ° C. or more within which a change in linear thermal expansion is within 1 × 10 ^{−4 is} within a temperature range of −30 ° C. to 90 ° C. 2. The temperature range of at least a temperature range of 10 degrees or more where the change amount of linear thermal expansion is within 5 × 10 ^{−5 is} within a temperature range of −20 ° C. or more and 70 ° C. or less. Metal-ceramic composite material. A metal-ceramic composite material obtained by combining light metal or light metal alloy and interstitial manganese nitride,
Metal-ceramic composite material, characterized in that the absolute value of the linear expansion coefficient in a temperature range of 20 ° C. or more within a temperature range of 0 ° C. to 40 ° C. is always 1.5 × 10 ⁻⁶ / ° C. or less. .   4. The metal-ceramic composite material according to claim 3, wherein the interstitial manganese nitride has a negative linear expansion coefficient in the temperature range of 20 degrees or more. 5.   5. The metal-ceramic composite material according to claim 1, wherein a linear expansion coefficient of the interstitial manganese nitride has a negative value in the temperature region.   The metal-ceramic composite material according to any one of claims 1 to 5, wherein the base material is any one of metallic aluminum, an aluminum alloy, metallic magnesium, and a magnesium alloy. A method for producing a metal-ceramic composite material comprising a composite of light metal or light metal alloy and interstitial manganese nitride,
A metal-ceramic composite material, characterized in that a melted light metal or light metal alloy is pressed and infiltrated into the filler or molded body containing the interstitial manganese nitride, and the treatment temperature at that time is 600 ° C. to 1000 ° C. Manufacturing method.

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