JPS62120447A - Manufacture of metallic matrix-fiber composite material - Google Patents

Abstract

PURPOSE:To strengthen the interface between matrix-forming metal and fibers and to improve heat resistance by allowing trace amounts of additive elements which enter into solid solution in a metal for forming matrix and react with fibers to enter into solid solution uniformly with the metal for forming matrix. CONSTITUTION:A coating layer 2 of the metal for forming matrix is formed on a fiber 1, and plural pieces of the fibers are bundled,and then a fine wire 3 of the metal containing the additive elements which enter into solid solution in the metal for forming matrix and react with the fiber 1 is wound round the above bundle. This bundle of fibers is woven into prescribed fiber blending, and the resulting woven fabrics are alternately laminated so that they are perpendicular to each other. When the above is subjected to hot pressing, the additive elements contained in the metallic fine wire 3 are diffused into the base metal in the coating layer 2 of the fiber 1 to form a solid solution.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a method for producing a metal matrix-fiber composite material.
Fiber composite materials are used, for example, to adjust the coefficient of thermal expansion between members, and are installed and bonded between semiconductor substrates, which are ceramics and gold MC, and are insulated with heat sink metal during brazing or cooling/heating cycles. It is possible to prevent the ceramic from peeling off from the metal, or from warping or cracking of the ceramic due to the difference in thermal expansion with the plate ceramic.

[Conventional technology]

Metal matrix-fiber composites (hereinafter referred to as rFRMJ), which have metal as a matrix and metal or ceramic fibers embedded in this matrix, have the characteristics of both fibers and matrix, and furthermore, the fibers are oriented in one direction. By forming it into a net shape, a spiral shape, or a non-directional shape, it is possible to adjust the characteristics depending on the direction, so it is used as a structural or functional member of various devices. One such F''RM is carbon [C] fiber and copper (Cu).
) FRM is available. Carbon fiber is also called graphite &11# or carbon fiber, but below, these are collectively referred to as carbon fiber. This C fiber and C1,1 l"RM are the negative thermal expansion coefficient of carbon and the negative thermal expansion coefficient of Cu. It has an expansion coefficient between the positive expansion coefficients and can adjust the thermal expansion coefficient among the nine members.

There are two methods for manufacturing these FRMs: an impregnation method and a hot press method. In the impregnation method, a matrix-constituting metal is made into a molten metal, and fibers are impregnated with the molten metal to form a composite. In the hot press method, fibers are coated with a metal for forming a matrix in advance, and then the fibers are pressed at high temperature to form a composite. The matrix coating in this hot press method is electroplated and chemical vapor deposition.

By ion brating, thermal spraying, etc. In addition, there are various manufacturing methods, and the Vi
The manufacturing method is selected as appropriate depending on category i. For example, CJ14 in Cu matrix! Cu-C&l with embedded fibers
The fiber composite is sli-formed by hot pressing method and impregnating method is not applied because C and Cu are not wettable at all and essentially cannot be impregnated.

On the other hand, C11-W fiber composite material in which W fibers are embedded in Cu can also be made into a composite material by hot pressing method;
Since U and W have excellent wettability and do not generate compounds, impregnation is generally used.

As shown in H-H, any manufacturing method suitable for the composite system is selected. In particular, in composite systems where the fibers and the matrix do not have wettability or where a compound is formed between the fibers and the matrix, the matrix is formed into a solid phase. The hot press method is used. This hot press method has favorable points such as being able to reliably composite fibers and matrix.

The difference in the FRM manufacturing method described above is also reflected in the difference in heat resistance. For example, Cu-CA4I has no wettability between Cu and cm fibers.
Fiber composite materials do not have sufficient heat resistance, as when heated, the Cu matrix softens, the C fibers and the Cu matrix separate, and a swelling phenomenon occurs in the composite material itself.
c u -CMRJI; m In order to improve the heat resistance of the composite material, Ti, Zr, Cr, and Nb are added to the Cu matrix.
There are Cu-C fiber composites to which Cu-C is added. By adding Ti etc. to the above C11, Cu-CJl
The heat resistance of fiber FRM is improved because an intermetallic compound is formed between C and Ti, and a solid solution is formed between Cu and Ti, which strengthens the Cu-C interface. It is.

As a conventional example of manufacturing FRM with such a reinforced interface, as described in Japanese Patent Publication No. 52-53720,
A method is known in which an additive element (such as Ti) is powdered, methyl cellulose or the like is added thereto to form a slurry, the slurry is made to be a medium between fibers, and the slurry is hot-pressed. This conventional example has the advantage that arbitrary elements can be added regardless of the wettability of the cm fibers and the reaction can be controlled by controlling the temperature for 2 hours.

[Problems to be Solved by the Invention] However, in the conventional example described above, it is difficult to uniformly disperse the additive elements due to factors such as the particle size of the powder and the fluidity of the methylcellulose and additive element powder. In particular, it is difficult to homogenize trace elements, and if the powder particle size is large, there is a risk that a homogeneous matrix may not be obtained. If there is non-uniform dispersion of additive elements, If'R
There may be a portion of M that has poor heat resistance, and as a result, a swelling phenomenon may occur due to a rise in heat.

In addition, as in the conventional example above, additional elements can be added using slurry.
In order to uniformly disperse it in the u matrix, a large amount of additive elements is required. As a result, the thermal conductivity and conductivity of the FRM are significantly reduced.

Therefore, it is possible to hot press the fiber by coating it with an alloy of Cu and other additive elements such as Ti, but in the case of an alloy, the components that can be coated are limited, and it is difficult to control the content of the additive element. There are some manufacturing difficulties.

In order to solve such problems, the present invention aims to provide an FRM with excellent heat resistance by strengthening the interface between the fibers and the metal matrix without reducing conductivity and thermal conductivity. .

[Technical means for solving the problem] The present invention provides that the fiber coated with the matrix-forming metal contains an additive element that is dissolved in the matrix-forming base Jti≦ and that reacts with the fiber. Wrapping thin metal wire,
This is a method for producing a metal matrix-fiber composite material, which is characterized in that a composite material of matrix-constituting metal and fibers is made by subjecting the material to high temperature and high pressure.

[Effect]

In the configuration of the present invention described above, the additive element is dissolved in solid solution in the matrix-constituting metal, and can react with the fibers to form an intermetallic compound. Therefore, the interface between the matrix-constituting metal and the fibers is strengthened, and heat resistance is improved. Since the additive element is obtained from the thin metal wire, the amount of the additive element solid-dissolved in the matrix-constituting metal is only *f, and it is homogeneously diffused in the matrix-constituting metal.

Therefore, a decrease in thermal conductivity and conductivity can be avoided.

〔Example〕

Next, an example of the method for manufacturing a metal matrix-fiber composite material according to the present invention will be described.

First, as shown in FIG. 1, a fiber 1 is coated with a matrix metal in advance by electroplating or the like to form a coating layer 2. On the other hand, in consideration of the amount of the matrix-constituting metal coated on the fibers, a metal thin wire containing an additional element that is solid-dissolved in the matrix-constituting metal and reacts with the fibers is manufactured separately. Fine metal wires are made by alloying additive elements and matrix-constituting metals as necessary.
Alternatively, a four-metal thin wire containing only an additive element is thinned by hot or cold heating.

As shown in FIG. 2, a thin metal wire 3 is wound around a fiber bundle coated with a metal for forming a matrix. The number of fiber bundles around which the metal thin wire 2 is wound is selected in consideration of the element content of the thin wire and the mechanical properties of the thin wire.
-CJljl In the absolute complex, there are usually 500 to 6000. The thin alloy wire is preferably about 0.1 m, which is easy to draw, and the winding density is 15 to 20 tan/m from the viewpoint of workability.
The following conditions are desirable.

A fiber bundle around which thin metal wires are wound is woven in a predetermined fiber orientation. For example, the scallions are made into a net shape or layered in alternating orthogonal layers and placed under high temperature and pressure (hot press). The additive element contained in the thin metal wire diffuses into the main component metal coated on the fiber at high temperature during hot pressing, and forms a solid solution with the main component metal.

It also reacts with the fibers, forming intermetallic compounds between the added metal and the fibers. As a result, the interface between the woven edge and the metal matrix is strengthened, and a composite as shown in FIG. 3 is formed. In FIG. 4: 3 indicates a thin metal wire, and 4 indicates a fiber. The fibers wrapped around the thin metal wires are woven into a net-like structure. Figure: In the composite shown in Figure 3, the amount of added elements dissolved in solid solution from the thin metal wire is minute;
and uniformly enough to diffuse into the matrix-constituting metal.

Deterioration of thermal conductivity and conductivity of the composite can be prevented.

1- The amount of added elements in the thin metal wire is determined as follows. In other words, since the additive element in the thin metal wire is a solid solution that dissolves in the matrix-constituting metal, that is, the main component metal, the amount of the additive element in the metal wire is such that it dissolves in solid solution up to the maximum solid solubility limit in the main component metal. It is preferable to This is because if an amount of the added element exceeding the maximum solid solubility limit is dissolved in the main component metal, a crystallized phase will precipitate in the matrix, making it impossible to obtain essential uniformity of the matrix. If the amount of the added element is within the maximum solid solubility limit, the added element will easily diffuse into the component metal coated on the fiber depending on the temperature and time during hot pressing, forming a composite of the fiber and the metal matrix. However, even if the partially precipitated phase in the matrix that occurs when the additive element is included in the metal wire beyond the maximum solid solubility limit is present in the composite, the properties of the composite will not deteriorate significantly. In some cases, there may be no particular problem even if the amount of added elements exceeds the maximum solid solubility limit, or other properties may be exhibited due to the presence of a partially crystallized phase. In addition, the dispersion of the crystallized phase that actually occurs is
It can be adjusted by $+1 depending on the diameter of the fiber bundle and thin wire.

It is better to have a smaller number of fiber bundles around which the thin metal wire is wound in order to prevent partial precipitation of crystallized phases or to uniformly disperse the additive element in the matrix. Further, the smaller the diameter of the thin metal wire, the easier it is to wind around the fiber bundle, and the more uniform the dispersion of the additive element in the thin metal wire into the matrix, which is preferable.

Next, specific examples will be described.

(Example 1) In order to improve the heat resistance of the reticulated Cu-CJI fiber composite material, a reticulated Cu-Cr-C delicate composite material containing Cr as an additive element was prepared.

As shown in FIG. 1, C fiber 1 with a diameter of 7 μm has a thickness of 1.
A 7μ C112 coating was applied by electroplating.

On the other hand, a Cu-0.7 wt % Cr alloy was melted by high frequency heating to produce an ingot with a diameter of 30 mm. This is hot- and cold-rolled to form a straight fine wire, and as shown in Figure 2, one of the alloy fine wires 3 is CM for one Cu-plated C fiber bundle consisting of 3000 pieces! The fibers were wound at a frequency of 15 per meter of fibers, and then hand-woven at a weaving density (10 pieces per inch) to form a woven fabric. Two sheets of this woven fabric were stacked and charged into a graphite mold, and a temperature of 1000°C and a pressure of 250 kgf/cs were applied to
I spent a lot of time hot pressing it. As a result, as shown in FIG. 3, the Cu matrix contains about 0.16% by weight of Cr, and C#! Reticulated Cu-C with 35% volume
An r-C complex was successfully produced.

('A Example 2) The FRM produced in Example 1 above was
A heat resistance test was conducted in comparison with -C&1ml;'RM. The results are shown in Figure 4. - The thermal test was approximately 0.
FRM containing 16% Cr and FRM containing no Cr
This was done by heating the FRM to 800°C and observing the state of swelling on the FRM surface. In the Cr-containing FRM(t) of Example 1, the surface did not swell even when heated to 800°C.

On the other hand, in the conventional case that does not include Crt &T< M, it is 60
At 0''C, swelling on the surface of the material to be bonded w4 was observed.

Furthermore, - F T < M containing Cr in Example 1 above has a conductivity of 48% and an average coefficient of thermal expansion at RT-200°C of 8.8.
It exhibits characteristics of high conductivity and low thermal expansion at X 10-@/'C.

Furthermore, according to the results of the study using FPMA, it is clear that Cr diffuses uniformly in Cu plating, and that Cr is a solid solution Cu matrix in which Cu is dissolved in solid solution1? d According to Example 1, by interposing a thin alloy wire containing Cr in the cm fiber bundle, Cr can be uniformly diffused into Cu, and an intermetallic compound is formed between Cr and the fiber. etc., the interface between metal and fiber is strengthened and heat resistance is improved. At this time, since the amount of the additive element Cu is flexible, there is no risk of deterioration of the conductivity and thermal conductivity of the FRM.

(Example: 3) Next, the Cu-Cr-cm fiber F R manufactured in Example 1
The differences in conductivity and thermal conductivity between M and FRM obtained by the conventional methyl cellulose + Cu powder slurry method were investigated.

The Cu powder in the methyl cellulose + Cu powder slurry method is
A 200 mesh one was used. Cr in the FRM formed by the methyl cellulose + Cu powder slurry method in this way
The content is 25% by weight based on the Cu matrix. On the other hand, the Cu-Cr-C fiber 1'' produced in Example 1 above
The Cr content in the RM is 0.16%.As seen from Table 1 above, the conductivity of the FRM manufactured according to Example 1 was 48% compared to that of the conventional methyl cellulose. +F R manufactured by Cu powder slurry method
It can be seen that this value is quite good compared to the conductivity of M, which is 27%. This can be achieved by diffusing Cr into Cu using a thin alloy wire, so that Cr is *i and Cu is sufficiently
This is due to diffusion into the matrix. What?
? , the thermal conductivity is Cr in the matrix (l addition Am)
It is related to If, and as with conductivity, as Cr bt (amount of added elements) increases, thermal conductivity also deteriorates.In this example, the heat resistance standard for both FRMs was set to 800°C, and the The content of 0% fiber wax was 35% wax.

(Example 4) (Similar to Example 1, CU plated C fiber and Cυ~
A thin wire of Cr alloy was prepared, a reticular c: u -Cr Cmm composite material containing 45% C fiber was fabricated, and its heat resistance was examined. As a result, the heat resistance is 800
C, that is, no swelling of the surface was observed even when heated to 800°C. Further, the conductivity was 36%, the thermal expansion coefficient was 6.2 x 10-'/'C, and a structure in which Cr was solidly dissolved in the Cu matrix was observed. According to this example, even when the C fiber content is large relative to the Cu matrix amount, heat resistance can be improved without reducing conductivity and thermal conductivity, as in Example 1.

〔Effect of the invention〕

As explained below, the metal matrix according to the present invention
According to the 12-layer method for producing fiber composite materials, it is possible to uniformly dissolve the additive elements that are solid-dissolved in the matrix component and react with the fibers into the 71-trix component. Therefore, the interface between the matrix-forming base J and the fibers is strengthened, and heat resistance can be improved without reducing conductivity and thermal conductivity.

Further, by winding the additive element around the matrix-forming metal fiber, the additive element can be solid-dissolved in the matrix inside the tube.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of a fiber coated with a matrix-constituting metal, FIG. 2 is a side view showing a state in which a thin metal wire containing an additive element is wound around a fiber coated with a matrix-constituting metal, and FIG. FIG. 3 is a configuration diagram of a composite material showing a state in which fibers are woven into a net shape, and FIG. 4 is a graph showing the relationship between heating temperature and plate pressure increase rate of the composite material.

Claims (1)

[Claims] 1. A matrix is formed by wrapping a fiber coated with a matrix-constituting metal with a thin metal wire containing an additive element that is dissolved in the matrix-constituting metal and reacting with the fiber, and subjecting it to high temperature and high pressure. 1. A method for producing a metal matrix-fiber composite material, comprising forming a composite material of a constituent metal and fibers.