JPS60255669A - Manufacture of composite carbon material containing silicon carbide and titanium group element carbide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (a) Industrial Application Field The present invention relates to a composite carbon material containing silicon carbide and titanium group element carbide that can be used in various industrial fields as a high-temperature material, wear-resistant material, chemical-resistant material, etc. The present invention relates to a manufacturing method.

(b) Background explanation This type of composite carbon material containing silicon carbide and titanium group element carbides (titanium carbide, zirconium carbide, etc.) has excellent heat resistance and
Since it has excellent strength as well as abrasion resistance and chemical resistance, it can be used as a high-temperature material, wear-resistant material, or chemical-resistant material, provided that it can be made into any shape. There is a possibility that it will be widely used industrially as one of the strength reinforcing means. : By the way, it is difficult to make carbides in -F, especially titanium group element carbides, because titanium and zirconium are high melting point metals, but carbides in i are very hard and brittle. It is very difficult to process and mold it because it is a substance, and therefore, conventionally when trying to obtain materials containing this type of carbide, it was necessary to rely on a sintering method that molds the carbide powder etc. as a starting material. .

However, metal carbides are generally difficult to sinter, and their sintering requires the addition of an appropriate sintering aid, but since this aid has a negative effect on the properties of the carbide, the sintering method is difficult to sinter. This is causing the inconvenience of not being able to get it. Furthermore, baked crystals sometimes lack flexibility in shape and size, and it is of course difficult to process baked crystals into any desired shape.

(c) Purpose The present invention was made with attention to such circumstances,
As mentioned above, as a useful manufacturing method for obtaining a composite carbon material consisting of silicon carbide, titanium group element carbide, and carbon, whose utility value is expected to increase in the future,
The object is to provide a suitable alternative to known sintering methods.

(D) Structure As a result of extensive research to achieve the above object, the present invention has been developed to provide a carbon material, together with a silicon-containing material and a titanium-containing element material, in the presence of oxygen at a high temperature equal to or higher than the melting point of the silicon-containing material. Placed in an unaffected inert atmosphere, the silicon-containing material permeates and reacts with the carbon material to produce silicon carbide, and the heat of reaction of the silicon carbide formation is used to generate the titanium-containing element material. A method for producing this type of composite carbon material has been established, which is characterized in that a material made of silicon carbide, titanium group element carbide, and carbon is obtained by subjecting the carbon material to a permeation reaction.

That is, in the manufacturing method of the present invention, a silicon-containing material and a titanium-containing element material are attached to or in contact with a carbon material molded into a desired shape, and this is exposed to the influence of oxygen at a high temperature above the melting point of the silicon-containing material. Make sure to place it in a non-inert atmosphere.

Then, first, a silicon-containing material with a low melting point (silicon; approximately 141
0° C.), and this molten silicon-containing material penetrates into the voids of the carbon material, where it starts a reaction that produces carbon and silicon carbide.

However, the silicon carbide production reaction that occurs at this time is an exothermic reaction that releases a large amount of heat, and the humidity of the carbon material is increased at the same time as this reaction starts.

The temperature of the carbon material can be raised several hundred degrees above the ambient temperature due to the reaction of the silicon-containing material penetrating the carbon material, which varies depending on the amount of silicon reacted. When the titanium-containing element material having a high melting point on the surface (titanium: approximately 1,730°C, zirconium: approximately 1,860°C) is melted by increasing the temperature of this carbon material, this molten titanium-containing element material It also penetrates into the voids of the carbon material, where it reacts with carbon to produce titanium group element carbides. Note that this reaction for producing titanium group element carbides is also an exothermic reaction, and once this reaction starts, the temperature of the carbon material further increases, which lowers the viscosity of the molten silicon-containing material and the molten titanium group element material. , which further promotes the penetration reaction of these molten metals into the carbon material. Incidentally, the heat of reaction produced in each reaction equation of silicon, titanium, and zirconium with respect to carbon is shown as follows.

C+Si+SiCΔ)I”, = −73,2Kj/
■O1C Ti−+TiCΔH@= −184,I
Kj/ molC+ Zr+ ZrCΔH@5= −,
1[1.8Kj/mol] Thus, after the reaction is completed, the original carbon material is transformed into a composite carbon material containing reacted silicon carbide and titanium group element carbides and unreacted carbon in its voids. questioned.

In this method, the silicon-containing material and the titanium group element material permeate into the pores of the carbon material used as the base material and react to generate silicon carbide and titanium group element carbide, so there is no reaction with the original carbon material. The composite carbon material obtained by this method has the characteristic that it maintains approximately the same shape. Therefore, by forming the original carbon material into a desired shape in advance, a composite carbon material having an arbitrary shape can be easily obtained.

In addition, this method \ε reduces the porosity of the original carbon material to l
By adjusting the amount or blending ratio of the silicon-containing material and the titanium-containing element material to be reacted, the thickness of the material to be composited can be arbitrarily adjusted (to uniformly composite the entire material). (or only the surface layer) can be easily made, and it is also possible to control the composition of the composite part.

In the present invention, any general carbon material can be used as the carbon material. In addition, silicon-containing materials
・As the titanium-containing element material, pure metals or alloys thereof can be used. In order to infiltrate and react the silicon-containing material and the titanium-containing element material into the carbon material, for example, the powdered silicon-containing material and titanium-containing element material are dispersed in a suitable binder or solvent. Attach or apply to the surface. In addition, if the carbon material is relatively small, it is sufficient to simply place a small lump of silicon material and titanium group element material on the carbon material. The manner of initial contact with the carbon material is appropriately selected depending on the shape and size of the carbon material. on the other hand,
An ordinary high-temperature heating device may be used to create an atmosphere for carrying out the above-described osmosis reaction. In other words, such a heating device maintains the atmosphere in the furnace in an inert state unaffected by oxygen (e.g., argon, helium, etc.), and uniformly heats the carbon material to at least contain the carbon material. Any material that can maintain the silicon material in a molten state is sufficient.

(e) Examples Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 On the surface of a carbon material (C) having a rectangular parallelepiped shape of 10 x 40 x 51111, silicon (St) and titanium (Ti) in the form of small lumps were added at a weight ratio of Si/C=0.5 and Ti/C=0, respectively. .1 was loaded and placed under a temperature of 1800°C in an argon stream using a high-temperature heating device.
1 Under these conditions, silicon was observed to first melt and penetrate into the carbon material. , Also, in this case,
The brightness of the carbon material increased significantly, and at the same time, titanium also melted and gradually penetrated into the carbon material. When powder X-ray diffraction of the material thus obtained was measured, its composition was as follows:
They were silicon carbide, titanium carbide and carbon. In addition, when measuring the bending strength of this material (span 3 o) and crosshead speed 0.5 ram x in), the result was 5
31 Kgf / c l, which is about 20 kgf of the original carbon material.
When compared with that of 0 Kgf/cm', it is approximately 2.7
It turned out to be twice as valuable. An electron micrograph (35x magnification) of the fractured surface of this material and the respective distribution states of silicon and titanium in the same field of view are shown in Figures 1, 2, and 3. From these, it can be seen that molten silicon and titanium are It has been confirmed that silicon carbide and titanium carbide are produced by penetrating into the interior of the carbon material and reacting, respectively. Wake up,
Figures 4 and 5 show electron micrographs at a magnification of 2,000 times and the distribution of silicon in the same field of view.These images show that silicon carbide crystals are formed in the voids of the carbon material. This indicates that the carbon particles are crosslinked, and this is thought to be a major factor in increasing the bending strength.

Example 2 Carbon material (C
) on the surface of silicon (Si) and zirconium (Zr) in the form of small lumps with a weight ratio of Si/C=0°5 and Zr/
It was heated under the same conditions as in Example 1, except that an amount of C=0.1 was added. The composition of the material after reaction is silicon carbide, zirconium carbide and carbon, and its bending strength is 4t774
It was Kgf/c■2. An electron micrograph (35x magnification) of the fractured surface of this material and the respective distribution states of silicon and zirconium in the same field of view are shown in FIGS. 6, 7, and 8.

(f) Effects As described above, according to the production method of the present invention, a composite carbon material consisting of silicon carbide, a titanium group element carbide, and carbon can be produced relatively easily using a carbon material as a starting material. Furthermore, if the original carbon material is molded into the desired shape, any shape can be easily obtained, and the thickness and composition of the carbide layer can also be easily controlled. It has the characteristics of In addition, according to this method, the reaction heat accompanying the osmotic reaction of the silicon-containing material, etc. is used to cause the osmotic reaction of the titanium-containing element material with a high melting point to the carbon material, so the manufacturing conditions are high. It also has the advantage that it does not require

[Brief explanation of the drawing]

FIG. 1 is an electron micrograph (35x magnification) showing the fracture surface of a composite carbon-containing material made of silicon carbide, titanium carbide, and carbon according to an embodiment of the present invention, and FIG. Figure 3 is an X-ray elemental analysis photograph showing the distribution of silicon (the white part represents silicon), and Figure 3 is an X-ray elemental analysis photograph showing the distribution of titanium (the white part represents titanium). , is an enlarged electron micrograph (2000x magnification) of the one in Figure 1, and Figure 5 is an X-ray elemental analysis photograph showing the distribution of silicon in the same field of view. Fig. 7 is an electron micrograph (magnification: 35x) showing the fracture surface of a composite carbon material made of silicon carbide, zirconium carbide, and carbon according to Example 1, and Fig. 7 is an X-ray elemental analysis showing the distribution of silicon in the same field of view. The photograph, Figure 8, is an Xt1 elemental analysis photograph that also shows the distribution of zirconium (the white part represents zirconium). Agent Patent Attorney Hiroshi Akazawa Figure 5 Figure 7 Procedural Amendment (Method) % Formula % l Display of the case 1982 Patent Application No. 112390? Name of the invention Method for producing composite carbon material containing silicon carbide and titanium group element carbide 3 Person making the amendment Relationship to the case Patent applicant address Dojimahama, Kita-ku, Osaka-shi Item 4 No. 4 Name Osaka Cement Co., Ltd. Representative Kin Kitagawa - 4 Agent 606 Address 612 Tanihata Takano Building, 20 Takano Higashi Sekicho, Sakyo-ku, Kyoto City September 25, 1980 6 Drawings of the specification subject to amendment Brief explanation column 7 Amendment content 4, brief explanation of drawings Figure 1 shows a particle structure of a fractured surface of a composite carbon material made of silicon carbide, titanium carbide, and carbon according to an embodiment of the present invention. These are photographs (35x magnification). Figure 2 is an X-ray photograph showing the distribution of silicon in the same field of view (the white part represents silicon), and Figure 3 is an X-ray photograph showing the distribution of titanium (the white part (represents titanium). Figure 4 shows the first
A photo of the particle structure enlarged from the one in the figure (2000x magnification)
FIG. 5 is an X-ray photograph showing the distribution of silicon in the same field of view. FIG. 6 is a photograph (35x magnification) of the particle structure showing the fracture surface of a composite carbon material made of silicon carbide, zirconium carbide, and carbon according to another example of the present invention, and FIG. FIG. 8 is an X-ray photograph showing the distribution of silicon (the white part represents zirconium).

Claims (1)

[Claims] Carbon material together with silicon-containing material and titanium-containing element material,
The melting point of the silicon-containing material is placed in an inert atmosphere unaffected by oxygen at a high temperature, and the silicon-containing material permeates and reacts with the carbon material to produce silicon carbide. Silicon carbide, a titanium group element, characterized in that a material consisting of silicon carbide, a titanium group element carbide, and carbon is obtained by permeating and reacting the titanium group element material into the carbon material 1 using the heat of reaction generated. A method for producing a composite carbon material containing carbide.