JP2000203973A - Carbon-base metal composite material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve defects of a carbon material such as brittleness, insufficient strength, easy oxidizability, inferior scuffing resistance and low surface workability and to obtain a carbon material having an enhanced heat conductivity and a coefficient of thermal expansion adjusted according to the purpose of use. SOLUTION: A molten metal is pressurized and impregnated into a carbon molding with the pressing member of a pressure device to produce the objective carbon-base metal composite material. The temperature of the molten metal is higher than the melting point of the metal by 50-250 deg.C and pressure applied to the molten metal is >=200 kg/cm2 per unit cross-sectional area of the pressing member. The carbon-base metal composite material consists of a carbonaceous matrix and the metal dispersed in the matrix, >=90 vol.% of the pores in the matrix have been substituted by the metal and the metal content of the composite material is <=35% of the total volume.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon-based metal composite material and a method for producing the same, and more particularly, to a substrate having a high thermal conductivity and a low thermal expansion coefficient for a semiconductor package, and a substrate having a specific strength and a specific rigidity. High structural materials for aerospace equipment,
Structural materials for general industry, heat-resistant materials such as gas turbines, or electrical contact materials with good sliding properties, especially carbonaceous metal composite materials useful for providing substrate-like molded products for electronic equipment and metals for carbon molded products The present invention relates to a method for producing a carbon-based metal composite material by pressure impregnation of components.

[0002]

2. Description of the Related Art Conventionally, a metal composite material containing a carbon material has been
It is manufactured by dispersing and arranging carbon particles or carbon fibers as a reinforcing material in a metal component matrix.
In addition, a production method by a powder metallurgy method from graphite powder and metal powder is also employed. All of these are called metal-based carbon composite materials that are manufactured for the purpose of improving the properties of the metal component serving as the base material with the carbon material, and the volume ratio of the carbon material greatly exceeds that of the metal component. Has not been realized, so its performance was naturally limited.

On the other hand, carbon materials are widely used because they have excellent heat resistance and are easy to process, but are brittle, have low strength,
There are many points that need to be improved, such as being easily damaged, not having oxidation resistance, being difficult to plate, and having low thermal conductivity.One of the reasons is that, except for special carbon materials, carbon materials have pores, The point is that the electrical, thermal and chemical functions inherent to carbon materials cannot be fully exhibited.

[0004] Therefore, attempts have been made to improve the characteristics of the carbon material by filling the pores of the carbon material with a metal material to form a composite of the carbon material and the metal material. For example, it has been proposed to replace some of the pores with molten copper, copper alloy, or silver in order to improve the electrical characteristics of carbon materials. However, a material in which most of the pores could be replaced with these metals was not obtained, and the performance was insufficient.

In general, the wettability between a carbon material and a molten metal is poor, and it has been almost impossible to impregnate pores of the carbon material with a molten metal component in conventional studies. In particular, in the case of aluminum impregnation, the wettability is improved at high temperatures, but when cast and impregnated under high temperature conditions, the carbon component and the metal component react with each other, and as a result, the carbon material deteriorates and a metal-based carbon composite material cannot be obtained. There was a problem.

[0006] That is, in a composite method of impregnating a carbon material with a metal component, a reaction is generated at the interface between the carbon component and the metal component by the conventionally proposed manufacturing method under conditions and operations, and carbonization with deliquescent occurs. Due to the formation of aluminum, carbon-based aluminum composite materials have not been actually developed.

[0007] Under the circumstances of the technical development of such a metal / carbon composite material, the generation of heat is increasing as the functions and the capacity of the electronic device are increased, and the high heat conductivity effective for heat removal is obtained. As a material having a small coefficient of thermal expansion, attention has been paid to a carbon-based metal composite material having a high carbon component content and excellent strength, and its development has been eagerly desired.

[0008]

Accordingly, an object of the present invention is to provide a carbon material having improved functionality by impregnating the pores of the carbon material with a molten metal at a low temperature while suppressing the reaction between the carbon material and the metal. Is to provide. Here, the improvement of the functionality means that the coefficient of thermal expansion of the carbon material can be controlled according to the application, that the thermal conductivity is improved, that the strength is improved and the brittleness is improved, and that oxidation resistance at high temperatures is improved. Another object of the present invention is to make it possible to control the thermal expansion coefficient and to improve the thermal conductivity, for example, to improve the heat resistance, to facilitate the surface treatment by plating or the like.

[0009]

Means for Solving the Problems Accordingly, the present inventors have:
In view of the conventional development situation as described above, as a result of intensive studies to solve the problems of the present invention, a mixture of a filler such as coke and a binder such as coal tar pitch,
Plate-like, block-like general carbon materials produced by molding and firing, plate-like and block-like molded products of carbon fiber reinforced carbon composite material, artificial graphite powder or carbon fiber pressed in a container, etc. From 50 to 250 ° C. from the melting point
Immerse in the molten metal at high temperature and apply 20
By applying a pressure of 0 kg / cm ² or more, the metal is forcibly injected and impregnated into the pores existing in the carbon material, and then cooled to obtain a carbon-based metal composite material in which the carbon material is a skeleton. The present invention has been completed based on these findings.

That is, a first aspect of the present invention is a carbon-based metal composite material comprising a carbonaceous matrix and a metal component dispersed in the carbonaceous matrix, and (1) 90 volumes of pores of the carbonaceous matrix. % Or more of the carbon-based metal composite material, wherein (2) the content of the metal component is 35% or less based on the total volume of the carbon-based metal composite material. .

[0011] A second aspect of the present invention is a method for producing a carbon-based metal composite material, comprising impregnating a carbon compact with a molten metal by a presser of a pressurizing device. Is 50 ° C. to 250 ° C. higher than the melting point, and the pressure of the molten metal is 200 kg /
The present invention relates to a method for producing a carbon-based metal composite material, which has a size of at least ² cm ² .

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Carbonaceous matrix The carbonaceous material used as the carbonaceous matrix constituting the carbon-based metal composite material of the present invention includes (a) a general carbon material and (b) a carbon composite reinforced with carbon fibers. A press-formed body containing the material and (c) at least one carbon material of carbon powder, artificial graphite powder and carbon fiber can be used. In the present specification, these carbon materials are collectively referred to as “carbon molded body” as necessary. The shape of the carbon molded body can be appropriately selected according to the use of the carbon-based metal composite material.

(A) General carbon material As the carbon molded body used as the carbonaceous matrix of the carbon-based metal composite material of the present invention, amorphous carbon, graphite-based crystalline carbon or a mixture thereof is used.
In particular, those containing graphite-based crystals are preferable from the viewpoint of uniformity of the pore characteristics and suppression of reaction with a metal component. It is important to select a graphite-based crystal having an average spacing d of 0.340 nm or less as measured by X-ray diffraction. Further, the carbon material structure preferably has fine pores uniformly present, but may have a pore diameter distributed over a wide range from submicron to several hundred microns. The average pore diameter is 0.1 μm to 10 μm as a diameter, preferably 0.1 μm to 3 μm. When the pore diameter is in the specific range as described above, the impregnation of the metal component is facilitated by specifying the production conditions, and the metal filling rate is 90% by volume or more, and moreover 95% by volume.
It is possible to increase the volume percentage to substantially achieve a filling rate of 100%. Here, the filling rate is a volume ratio of the metal impregnated in the pores to the total pore volume.

The porosity of the carbon molded body is less than 40% by volume, preferably 5% by volume to 35% by volume, and more preferably 5% by volume to 25% by volume. That is, a carbonaceous portion having a volume ratio of 60% by volume or more, particularly exceeding 75% by volume is realized. This makes it possible to make full use of the inherent properties of carbon materials, which have been difficult in the past, and in particular makes it possible to sufficiently provide the thermal conductivity and coefficient of thermal expansion required for electronic device substrates.

[0015] The density of the carbon molded body is 1.4 g / c.
m^Three ~ 2g / cm^Three , Preferably 1.6 g / cm^Three ~ 2
g / cm^Three And especially 1.7 g / cm^Three ~ 1.9g /
cm ^Three Is preferred. The density is 1.4 g / cm^Three Less than
And the ratio of metal increases, and the coefficient of thermal expansion becomes excessive
Adverse effects, while 2 g / cm^Three Exceeds the metal impregnation rate
Is reduced. Also, almost completely filled
Substrate for electronic equipment because the metal ratio is small
Coefficient of thermal expansion 4 × 10 useful as^-6/ ° C or higher cannot be obtained
There is a problem.

Specific examples of the carbon molded body applicable to the carbonaceous matrix include electric steelmaking, aluminum refining, an electrode for an electrolytic furnace, an electrode for electric discharge machining, and a jig for producing a silicon semiconductor or an optical fiber. Alternatively, a carbon molded body for a heat-resistant structural material can be used.

Such a carbon molded article can be produced by using a filler and a binder as raw materials, and mainly through steps such as mixing, molding, firing and graphitization. Calcined petroleum coke, calcined pitch coke,
Natural graphite, calcined unleaded coal, carbon black, etc.
As the binder, coal tar pitch, coal tar, synthetic resin and the like can be used arbitrarily. mixture,
The operations and conditions of each of the steps of molding, firing and graphitization may be the same as those conventionally employed, and may be appropriately determined so as to obtain the desired properties described above. As described above, in particular, it can be obtained by a baking treatment at a temperature of 2800 ° C. or more. The average spacing d ₀₀₂ = 0.340 n by the firing treatment under this temperature condition
m or less can be prepared. Examples of the method for forming the carbon molded body include an extrusion method, a molding method, and a CIP method, and the extrusion method and the molding method are preferred.

(B) Carbon fiber reinforced carbon composite material The carbon fiber reinforced carbon composite material is a carbon / carbon composite material (hereinafter referred to as “c / c composite material” as required) composed of carbon fiber and a compound containing carbon. It is.) Carbon fibers are used as fillers, including composite materials using fibers (1D) aligned in one direction by a fiber arrangement method, as well as one-dimensional, two-dimensional, and composite materials using 3D woven from plain woven (2D) fibers. Various three-dimensional forms are provided,
It can be arbitrarily selected depending on the application.

The c / c composite material used as the carbonaceous matrix of the carbon-based metal composite material of the present invention may be composed of amorphous carbon. Are preferred. The density is 1.6 g / cm ^{3 to} 2 g.
/ Cm ³ , preferably 1.7 g / cm ^{3 to} 1.9 g / c
m ³ can be adopted.

The pore structure of the c / c composite material may be the same as that of the general carbon material, but the average pore diameter is 0.5 μm to 5 μm.
m, preferably in the range of 1 μm to 3 μm. Further, the porosity is preferably controlled to 10% to 30%.

The c / c composite material as described above may be produced by any method.
After impregnated with a carbon matrix precursor such as petroleum pitch and molded, it can be manufactured by baking at a temperature of usually 1000 ° C. or higher in an inert gas.
By controlling the firing temperature to 2500 ° C. or higher, particularly 2800 ° C. or higher, a graphitized crystal-containing carbon material can be obtained.

As a method for avoiding the re-impregnation of the matrix precursor required in the conventional production method, a dispersion in which a carbon powder containing 50% by weight or more of raw coke powder is dispersed is heated at a heat treatment temperature of 500 ° C. or more. A method in which carbon fibers are impregnated, then the solvent is volatilized, and the carbon fibers containing the carbonaceous matrix precursor are molded and fired under pressure (Japanese Unexamined Patent Application Publication No.
See -247563. ), It is possible to provide a carbon material having properties suitable as a carbonaceous matrix of the carbon-based metal composite material of the present invention.

(C) The press-formed body made of carbon powder, artificial graphite powder or carbon fiber is, for example, a carbon composite obtained by filling an iron container with graphite powder, carbon fiber, and the like and pressing. The porosity is controlled to 10% by volume to 30% by volume, and is useful as a raw material for a carbonaceous matrix of the present invention. Specifically, graphite particles having a major axis of 1.0 mm to 3 mm are 10% or more on a volume basis, or pitch-based carbon fibers having a fiber length of 0.02 mm to 5 mm are 10% or more on a volume basis, or a major axis is 0 as a carbon molded body. .1mm
Examples thereof include those containing 10% or more by volume of graphite particles of up to 3 mm and pitch-based carbon fibers having a fiber length of 0.02 mm to 5 mm. This carbon molded product is particularly useful as a carbonaceous matrix of a substrate-like molded product for electronic equipment described later.

Metal Component The metal component constituting the carbonaceous metal composite material of the present invention can be arbitrarily selected according to its use.
Magnesium, aluminum, titanium, iron, cobalt,
Examples thereof include nickel, copper, zinc, silver, tin, and alloys of the respective metals.

Preferred metal components are aluminum, copper,
It is an alloy of silver and the metal, etc., and a pure metal component of aluminum or copper is particularly preferable. These metal components are
The carbonaceous metal composite material of the present invention is suitable for satisfying specific thermal conductivity and thermal expansion coefficient, which are considered to be one of the specificities.

Carbon-based metal composite material The carbon-based metal composite material of the present invention comprises a carbonaceous matrix and a metal component dispersed in the carbonaceous matrix as described above. 9 of the pores of the carbonaceous matrix
0% by volume or more; 2) The content is 35% or less based on the total volume of the carbonaceous metal composite material.

As described above, the metal component is filled in the pores of the carbonaceous matrix, and at least 90% by volume of the fully open pores
Above, those which account for at least 95% by volume are preferred. More preferably, it is substantially 100% by volume filled. When the filling rate reaches 90% by volume, required performance such as thermal conductivity can be easily satisfied. Heretofore, the proposed impregnation method of molten metal has a volume of at most 70% by volume, and no high filling rate is disclosed. Further, the carbonaceous matrix is amorphous carbon or graphite-based crystalline carbon and a mixture thereof, and graphite-based carbon is particularly preferable. The form of the metal component in the carbonaceous matrix can be observed using a scanning electron microscope.

Next, in the carbon-based metal composite material of the present invention, the content of the metal component is 35% by volume or less, preferably 3% by volume.
0% by volume or less, more preferably 5% by volume to 25% by volume
It is. When the content exceeds 35% by volume, it becomes difficult to satisfy the performance of high thermal conductivity and low thermal expansion coefficient.

As described above, the carbon-based metal composite material of the present invention varies depending on the type of the metal component, but when impregnated with aluminum, has a density of 2 g / cm ^{3 to} 2.4 g / c.
m ³ , preferably 2.1 g / cm ^{3 to} 2.2 g / cm ³
And a thermal conductivity of 200 W / (m · K) or more,
Thermal expansion coefficient of 12 × 10 ⁻⁶ / ° C. or less, especially 4 × 10 ⁻⁶ / ° C
C. to 12 * 10 < ^-6 > / [deg.] C. can be provided.

The shape of the carbon-based metal composite material of the present invention is not particularly limited, and can be arbitrarily selected depending on various uses. For example, a plate, a block, a sheet,
Molded articles such as films, granules, powders, fibers, woven fabrics, non-woven fabrics, machined parts and the like can be mentioned.

The carbon-based metal composite material of the present invention has a thermal conductivity and a thermal expansion coefficient as described above, and thus is useful as a substrate-like molded article for electronic equipment. Semiconductor elements, resistors,
In electronic equipment that encloses a circuit instruction board for an electronic circuit composed of a transformer, a capacitor, or wiring and a base substrate that is a support for the circuit instruction board, most of the heat generated from the electronic circuit is generated from the circuit support board and the base substrate. The heat is transferred to the cooling device and finally released to the atmosphere or a cooling liquid. Conventionally, a metal made of aluminum, copper, or an alloy thereof is used as a base substrate material, but there is a difference in thermal expansion between the electronic circuit and an electronic circuit, and there is a problem of warpage or peeling.

The carbon-based metal composite material of the present invention has a thermal conductivity of 150 W / (m · K) or more and a thermal expansion coefficient of 12 × 1.
0 ^-6 / ° C. are those having the following, the metal base substrate excellent substrate properties than can solve the above problems by using it.

Next, a method for producing the carbon-based metal composite material of the present invention will be described. According to the present invention, there is provided a method for producing a carbon-based metal composite material comprising sealing a molten metal in a carbon molded body with a pusher, and impregnating the molded body with a pressurizing device, wherein the temperature of the molten metal is the melting point of the molten metal. The temperature is 50 ° C. to 250 ° C. higher, and the pressure of the molten metal is 200 kg /
The present invention relates to a method for producing a carbon-based metal composite material, which has a size of at least ² cm ² .

As the carbon molded body, any of the above-mentioned carbon materials which can be converted into a carbonaceous matrix can be used. Specific Preferred carbon molded body the density is ^{1.4g / cm 3 ~2g / cm 3} , less than a porosity of 40 vol%, preferably 35 vol% or less, more preferably, is generally a carbon material 5 Those having a volume percentage of 25% by volume, those having a carbon fiber reinforced composite material or those having a volume of 10% by volume to 30% by volume can be used as the pressed body.

In the impregnation of the metal component, specifically, the carbon molded body is placed in a mold, and the metal component is supplied into the mold in the form of granules and the like, heated, sealed with a pusher, and pressed. For example, a method of pressurizing with a press machine or a method of placing a preheated carbon molded body in a mold, injecting a molten metal, enclosing the molten metal with a presser, and pressurizing can be employed. The carbon compact is preferably preheated, and the temperature is preferably 100 ° C or more, more preferably 100 ° C to 250 ° C, from the melting point of the molten metal.
Further, in the case of a metal having a high melting point, a metal component can be impregnated by making a hole in the carbon molded body and injecting a molten metal into the hole.

The pressure impregnation of the molten metal is preferably performed at a temperature of 50 ° C. or more, more preferably 50 ° C. to 250 ° C., than the melting point of the metal. If the temperature does not reach 50 ° C., the metal filling rate is low, so that it is impossible to obtain a composite material having a low metal content and the required performance, whereas if the temperature exceeds a high temperature, for example, 250 ° C., the reaction between carbon and the metal is suppressed. It becomes difficult. For example, in the case of aluminum, if it exceeds 250 ° C., deliquescent aluminum carbide is easily generated, and a practical composite material cannot be obtained.

In the pressure impregnation of the molten metal, when the carbon compact is brought into contact with the molten metal, the pressure is not less than 200 kg / cm ² , preferably 500 k / cm ² , per sectional area of the pusher.
g / cm ² or more, particularly preferably 1000 kg / cm ²
The molten metal is pressurized with the above pressure to impregnate the carbon compact. If the impregnation pressure does not reach 200 kg / cm ² , the metal filling rate is low and a composite material having desired performance cannot be obtained. The pressure impregnation of the molten metal into the carbon compact is unique in that the molten metal is injected into the carbon compact and pressed directly with a pusher. Is different from

The pressurization method proposed for impregnation of molten metal is a gas pressurization method using a high-pressure gas, and it is necessary to increase the size of the impregnation-related apparatus. For this reason, it was impossible to produce a composite material having a practical size at a pressure necessary for sufficient impregnation of a metal due to equipment problems. On the other hand, the peculiarity of the pressure impregnation of the present invention is to inject a molten metal by using a normal press machine, enclose with a presser and pressurize, and all the conventional problems can be solved.
As a result, a high metal filling rate is obtained, and a high-performance composite material can be realized.

Since the pore diameter of the carbon molded body is distributed from submicron to several hundred microns, the melting temperature is higher by about 100 ° C. than the melting point in order to inject and fill the molten metal into pores of 1 micron or less. It is calculated that a high pressure of about 1 ton / cm ² is required for aluminum. Average pore size is 5μ
In the case of an impregnated body larger than m, if the pressure is set to 200 kg / cm ² or more per presser cross-sectional area, it is possible to impregnate almost 90% or more of the pores depending on the state of the molten metal. The pressure is desirably 1000 kg / cm ² or more,
The upper limit is determined by the ram pressing pressure and the economical pressure resistance of the mold. It is important that the carbon molded article of the present invention contains many open pores whose pores communicate with the outside from the viewpoint of press-in of the molten metal.

After completion of the pressure impregnation, a carbon-based metal composite material can be obtained through steps such as cutting. Conventionally,
In a metal-based carbon composite material using carbon fiber as a reinforcing material, there has been a problem that the metal and the carbon fiber react and become brittle, so that strength cannot be obtained. In the metal composite material, since carbon is the main component and the metal is a filling material of pores, the effect of the reaction between the carbon material and the metal on the composite material function is extremely small as compared with the metal-based carbon composite material. Within the above temperature range, the reaction occurring between the carbon material and the molten metal can be sufficiently suppressed, and a desired composite material can be obtained.

The method for producing a carbon-based metal composite material of the present invention will be specifically described with reference to the drawings. In FIG. 1, reference numeral 1 denotes a hot press heating unit or a sample chamber. Reference numeral 2 denotes a steel or carbon mold. 3 indicates a ram.

A hot press is used because of the need to melt the metal and to apply pressure to the molten metal. A metal or carbon mold with pressure resistance is placed in the sample chamber of the hot press. The carbon material and the mold particles are placed in the mold and a presser is placed. The atmosphere is raised to a predetermined temperature with a vacuum or an inert gas, and the presser is pressed by a hot press ram to pressurize the molten metal inside the mold. In the case of a high-temperature metal, a sample is obtained by making a hole in the carbon to be impregnated itself, putting a molten metal therein, and directly impregnating the sample. In addition, the presser part is cooled by gas at the time of pressurization.
After maintaining this condition for 30 minutes, the mold is taken out after cooling to about 200 ° C. Cut out a carbon-based metal composite from a metal sample.

[0043]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited by the examples and the like. In addition, the measurement method and the test method were used for quality / performance evaluation of the carbon-based metal composite materials prepared in the examples and the comparative examples.

1) Impregnation of Metal Components The distribution of metal components was observed at a magnification of 500 times using a scanning electron microscope S2300 manufactured by Hitachi, Ltd.

2) Porosity The porosity of the carbon compact before impregnation with the metal component is a calculated value calculated from its apparent density assuming that the density of carbon is 2.1 g / cm ³ .

3) Metal filling rate [(porosity before metal filling−porosity after metal filling) / porosity before metal filling] × 100

4) Specific heat DSC method using Perkin Elmer DSC-2 (DSC:
(Differential scanning calorimeter) at a heating temperature of 10 ° C./min and in a dry nitrogen stream at room temperature. Sapphire was used for comparative calibration.

5) Density The density was measured at room temperature (25 ° C.) by Archimedes method using an electronic analytical balance AEL-200 manufactured by Shimadzu Corporation.

6) Bending strength Using a precision universal tester AG-500 manufactured by Shimadzu Corporation, a distance between spans of 60 mm and a crosshead descent speed of 0.4 mm for a 4 mm × 4 mm × 80 mm strength test piece.
The bending strength was measured under the condition of 5 mm / min.

7) Thermal conductivity The thermal conductivity was determined as the product of the thermal diffusivity, specific heat and density. The thermal diffusivity was measured at 25 ° C. by using TC-7000 manufactured by Vacuum Riko Co., Ltd. by a laser flash method. Ruby laser light (excitation voltage 2.5 k
v, uniform filter and one extinction filter).

8) Thermal expansion coefficient Thermal analyzer 001, TD-50 manufactured by Max Science
20 was used to measure the coefficient of thermal expansion from room temperature to 300 ° C.

Example 1 Commercially available artificial graphite material I (density: 1.85 g / cm ³ , porosity: 12% by volume, bending strength: 3.5 kg / cm ² , thermal conductivity: 100 W / (m · K), Thermal expansion coefficient: 3.8 × 10
^-6 / ° C) to length 30mm, width 30mm, thickness 10mm
Was cut out in an iron mold together with pure aluminum granules, and heated to 750 ° C. in argon gas. 500kg / cm pressure per ram cross section
^By pressurizing at ² and maintaining the state for 30 minutes, aluminum was impregnated into the pores of the artificial graphite material I to form a composite.
After cooling, the aluminum mass was taken out and cut to obtain a carbon-based aluminum composite material.

The impregnation of aluminum in the obtained carbon-based aluminum composite material was observed by the above-mentioned method. It was confirmed that the pores were 100% replaced by aluminum and aluminum was uniformly dispersed in the carbonaceous matrix. The aluminum content in the carbon-based aluminum composite material was 12% by volume.

When a strength test piece was prepared and subjected to a bending test, a result of a bending strength of 8 kg / mm ² was obtained. The results are shown in Table 1. According to this, it can be seen that the bending strength has been improved to twice the 4 kg / mm ² of the artificial graphite material I not impregnated with aluminum.

Further, the thermal conductivity and the coefficient of thermal expansion were measured by the methods described above. The results are shown in Table 1. The thermal conductivity is improved to 200 W / (m · K) which is twice the 100 W / (m · K) of the artificial graphite material I, and the coefficient of thermal expansion is increased from 3.8 × 10 ⁻⁶ / ° C. to 11 × 10 ^-6 / ° C.

Example 2 A block having a length of 30 mm, a width of 30 mm, and a thickness of 10 mm was cut out from a commercially available artificial graphite material I, placed in a carbon mold together with pure copper granules, and placed in an argon gas atmosphere.
Heated to 0 ° C. Pressure 1000 per ram cross section
By pressurizing at kg / cm ² and maintaining the state for 30 minutes, copper was impregnated into the pores of the artificial graphite material I to form a composite.
After cooling, the copper lump was taken out and cut to obtain a carbon-copper composite material.

The carbon impregnation in the carbon-based copper composite material thus obtained was observed by the above-mentioned method. It was confirmed that the pores were 100% replaced by copper, and that copper was uniformly dispersed in the carbonaceous matrix. The copper content in the carbon-based copper composite material was 12% by volume.

A strength test piece was prepared and subjected to a bending test.
The test results are shown in Table 1. According to this, the bending strength is
4 kg / mm ² of artificial graphite material I not impregnated with copper
It can be seen that it was improved to 8 kg / mm ² , which is twice as large.

The thermal conductivity and the coefficient of thermal expansion were measured by the above-described methods, respectively, and the results are shown in Table 1.
The coefficient of thermal expansion is 3.8 at 220 W / (m · K), whose thermal conductivity is at least twice the 100 W / (m · K) of the artificial graphite material I.
It increased from × 10 ⁻⁶ / ° C. to 9.9 × 10 ⁻⁶ / ° C.

Example 3 A block of commercially available artificial graphite material I having a diameter of 5 mm and a depth of 10
A hole of 0 mm was made, and granules of pure nickel were put in the hole. The pusher was inserted into the hole, and after degassing under vacuum, heated to 1550 ° C. in argon gas. The pressure was applied at a pressure of 1000 kg / cm ² per sectional area of the presser, and the pressure was maintained for 30 minutes to impregnate the pores of the artificial graphite material I with nickel. After cooling, the nickel-impregnated portion of the block was taken out and cut to obtain a carbon-based nickel composite material.

The impregnation of nickel of the carbon-based nickel composite material thus obtained was observed. Further, the bending strength, the thermal conductivity, and the thermal expansion coefficient were measured. As a result of observation of the impregnation of nickel, the pores were
It was confirmed that 0% was substituted and nickel was uniformly dispersed in the carbonaceous matrix. The nickel content of the carbon-based nickel composite material was 12% by volume.

The bending strength of the artificial graphite material I was 4 kg / mm.
^{2 to} 11 kg / mm ² , the thermal conductivity is from 100 W / (m · K) of the artificial graphite material I to 170 W / (m ·
K), and the coefficient of thermal expansion is 3.8 for the artificial graphite material I.
× became 7.5 × 10 ^-6 / ° C. to 10 ^-6 / ° C.. Table 1 shows the results.

Example 4 JP-A-3-247563 and JP-A-8-15727
No. 3, the fiber direction is oriented at 0 ° and 90 °, and the length is obtained from the laminated pitch-based carbon fiber reinforced carbon composite material (hereinafter referred to as “2D carbon composite material” (see FIG. 2)). (Xy direction) 100mm, width 100m
m, a block having a thickness (z direction) of 250 mm was produced.
The porosity of the 2D carbon composite material is 25% by volume, and the bending strength, thermal conductivity, and thermal expansion coefficient are shown in Table 1 in the xy direction and the z direction.

The block of 2D carbon composite material has a diameter of 5 m.
m, 100mm deep hole, pure nickel inside
Add the granules. Insert the pusher into the hole, remove
After heating to 1550 ° C in a gas, the cross-sectional area of the pusher
Pressure per unit 500kg / cm ^Two And pressurized in that state
By maintaining for 30 minutes, the energy of the 2D carbon composite block
The holes were impregnated with nickel. Nickel in block after cooling
Take out the part impregnated with
A mixture was obtained.

When the impregnation of nickel was observed, it was confirmed that the pores were replaced by 100% with nickel, and that nickel was uniformly dispersed in the carbonaceous matrix. The nickel content was 25% by volume.

A strength test piece was prepared and subjected to a bending test.
The results are shown in Table 1. According to this, the bending strength is 20 kg / mm ² before impregnation on the xy plane, which is 2.5 times 50 kg / mm ² , and 1 kg / mm ² on the z plane.
What was less than ² was improved to 5 kg / mm ^2.

The measurement results of the thermal conductivity are shown in the vertical direction of the xy plane,
That is, in the z-axis direction, 8 W / (m · K)
5W / (m · K), and the vertical direction of the z plane, ie, x
Alternatively, in the y-axis direction, the power was increased from 200 W / (m · K) before impregnation to 250 W / (m · K).

A test piece impregnated with nickel was 3 mm in length and width.
The sheet was cut into a length of 10 mm, and its surface was coated with nickel having a total thickness of about 10 μm by electrolytic plating and electroless plating. Place this sample in an atmospheric furnace at 1000 ° C, 1
It was left for a while, taken out after cooling, and visually observed. There was no change other than the darkening of nickel. On the other hand, the sample of the 2D carbon composite without impregnation lost weight to 38% of its original weight.

Comparative Example 1 A carbon-based aluminum composite material having an aluminum content of 2% by volume was obtained in the same manner as in Example 1 except that the temperature of the molten aluminum was 700 ° C. Observation of the impregnation property of aluminum revealed that there were voids not filled in the open pores, and only 17% by volume of the pores of the artificial graphite material was replaced by aluminum. In addition, thermal conductivity 113
W / (m · K) and a coefficient of thermal expansion of 3.9 × 10 ⁻⁶ / ° C. were obtained. Table 1 shows the results of the performance evaluation.

Comparative Example 2 Aluminum impregnation was carried out in the same manner as in Example 1 except that the pressure per sectional area of the pusher was 150 kg / cm ² , but the aluminum filling rate was 47% by volume.
However, almost no molten aluminum could be impregnated, and a carbon-based aluminum composite material having sufficient performance could not be obtained. Table 1 shows the results of the performance evaluation.

Comparative Example 3 A carbon-based aluminum composite material impregnated with aluminum was prepared in the same manner as in Example 1 except that an artificial graphite material having an aluminum content of 40% by volume was used. When the bending strength, the thermal conductivity and the coefficient of thermal expansion were measured, the results shown in Table 1 were obtained. The aluminum filling rate was 100%, but the coefficient of thermal expansion was 13.2 × 10 ⁻⁶ /
° C, which was too high to meet the required performance.

Comparative Example 4 Instead of the commercial artificial graphite material I, a carbon molded product (average interplanar spacing d ₀₀₂ = 0.343 nm) obtained by finally firing acicular coke, pitch and a phenol resin at 2000 ° C. was used. Except for the above, a carbon-based aluminum composite material was prepared in the same manner as in Example 1. Table 1 shows properties and the like. Although the aluminum filling rate, the thermal conductivity, and the coefficient of thermal expansion obtained relatively good results, when this molded product (30 mm cube) was immersed in water, it foamed and collapsed. Further, when left in the air, the powder gradually turned into a powder which did not lose its original shape in about 2 weeks, and a powder having practical value was not obtained. This is presumed to be due to the reaction between aluminum and carbon to produce aluminum carbide.

[0073]

[Table 1]

[0074]

Industrial Applicability The carbon-based metal composite material of the present invention is a composite obtained by impregnating a carbon compact with a molten metal under pressure under conditions in which the reaction between carbon and metal is suppressed. The metal filling rate is substantially 100% by volume and the metal content is 35% by volume or less. The component composition of carbon and metal is specified, the strength is high, and the thermal conductivity and thermal expansion coefficient are 150 W / (m · K) and 4 to 12 × 1, respectively, the required quality of electronic device substrates, for example, semiconductor package materials.
0 ⁻⁶ / ° C. can be easily satisfied. In particular, thermal conductivity can be higher than would be calculated assuming that all of the pores were simply impregnated with metal.

Filling the pores of the carbon material with metal facilitates plating with airtightness. In addition, the diffusion of oxygen is prevented by the reduction of the pores, so that a carbon material having improved oxidation resistance can be obtained. It also makes it possible to produce high-strength materials, for example turbine components.

Furthermore, the brittleness of the carbon material can be improved, and the material is less likely to be cracked or chipped, particularly in mechanical working, and the working operation is easy and the accuracy can be improved.

In addition, the presence of the metal on the surface of the composite material can enhance the adhesion between the composite material and the ceramic or glassy coating. For example, in the case of a metal containing silicon, the carbon material surface has been converted to silicon carbide, and is easily wetted by vitreous material such as silicic acid.
A coating with good adhesion can be obtained.

As described above, by filling the metal into the mesh-like pores of the carbon material, the mechanical strength of the carbon material, for example, tensile strength, bending strength, elastic modulus, toughness, surface hardness, etc., is doubled. The above can be improved. In the carbon fiber composite material, since the interlayer strength is greatly enhanced, the strength in the Z direction is improved more than 5 times, and the effect is remarkable.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a basic structure of a carbon-based metal composite material manufacturing apparatus of the present invention.

FIG. 2 is a conceptual diagram of a 2D carbon fiber reinforced carbon composite material used in Example 4.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Hot press heating part 2 Die and presser 3 Ram 4 Fiber orientation 90 degree orientation sheet 5 Fiber orientation 0 degree orientation sheet

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Eiki Tsushima 747-1 Onukijima, Fuji City, Shizuoka Prefecture Inside Advanced Materials (72) Inventor Nobuyuki Suzuki 140-15 Shimotsukari, Nagaizumi-cho, Sunto-gun, Shizuoka Prefecture

Claims (12)

[Claims] 1. A carbon-based metal composite material comprising a carbonaceous matrix and a metal component dispersed in the carbonaceous matrix, wherein (1) 90% by volume or more of pores of the carbonaceous matrix are:
(2) The carbon-based metal composite material, wherein the content of the metal component is 35% or less based on the total volume of the carbon-based metal composite material. 2. The method according to claim 1, wherein the metal component is at least one metal selected from the group consisting of aluminum, magnesium, tin, zinc, copper, silver, iron and nickel, or an alloy containing at least one metal. A carbon-based metal composite material as described in the above. 3. The carbon-based metal composite material according to claim 2, wherein the metal component is a pure metal component selected from the group consisting of aluminum, copper and silver. 4. The method according to claim 1, wherein the carbonaceous matrix comprises:
It is selected from the group consisting of a graphite crystalline carbon material, (b) a carbon composite material reinforced with carbon fibers, and (c) a carbon powder, artificial graphite powder, and a press-formed body containing at least one carbon material. The carbon-based metal composite material according to claim 1, which is at least one carbon material. 5. The carbon-based metal composite material according to claim 4, wherein an average interplanar spacing d ₀₀₂ of graphite crystals of the graphite crystal-based carbon material is 0.340 nm or less. 6. The carbonaceous matrix having pores 9
The carbon-based metal composite material according to claim 1, wherein 5% by volume or more is substituted with the metal component. 7. The content of the metal component is 5% to 30% based on the total volume of the carbon-based metal composite material.
4. The carbon-based metal composite material according to any one of items 3 to 3. 8. The carbon-based metal composite material has a thermal conductivity of 150 W / (m · K) or more and a thermal expansion coefficient of 1
The carbon-based metal composite material according to claim 1, wherein the temperature is 2 × 10 ⁻⁶ / ° C. or less. 9. A method for producing a carbon-based metal composite material, comprising impregnating a carbon compact with a molten metal by a presser of a pressing device, wherein the temperature of the molten metal is 50 ° C. or less of its melting point. 250 ° C. higher temperature, and the pressure of the molten metal is 200 kg /
cm ² or more, a method for producing a carbon-based metal composite material. 10. An average plane distance d ₀₀₂ obtained by firing the carbon compact at a temperature of 2500 ° C. or more is 0.340 nm.
The method for producing a carbon-based metal composite material according to claim 9, which is a graphite crystalline carbon material that is as follows. 11. The method for producing a carbon-based metal composite material according to claim 9, wherein the porosity of the carbon molded body is less than 40% by volume. 12. The method for producing a carbon-based metal composite material according to claim 9, wherein the porosity of the carbon molded body is 5% by volume to 30% by volume.