Method of joining a porous silicon carbide body and a silicon carbide-silicon composite

Abstract

A method of joining a silicon carbide body and a silicon carbide-silicon composite, including a step of applying an adhesive paste 3 consisting of silicon carbide powder and a binder component to either or both of a porous silicon carbide body 1 and a silicon carbide-silicon composite 2 formed by impregnating a silicon carbide body with silicon such that said porous silicon carbide body and said silicon carbide-silicon composite are caused to adhere to each other, a step of causing a volatile constituent to evaporate from said adhesive paste 3 such that a porous silicon carbide adhesion layer 3 is formed between said porous silicon carbide body and said silicon carbide-silicon composite, and a step of causing the silicon in said silicon carbide-silicon composite to permeate said adhesion layer 3 through a heat treatment after the previous step such that said adhesion layer 3 is densified.

Description

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1A and FIG. 1B are conceptual diagrams illustrating the joining method of a porous SiC body and an SiC—Si composite in accordance with the present invention; and

FIG. 2 is a schematic configuration diagram illustrating the filter that is a joined body of a porous SiC body and an SiC—Si composite.

DESCRIPTION OF THE PREFFERED EMBODIMENTS

Hereinafter, the embodiments of the present invention will be described with reference to FIG. 1A and FIG. 1B.

A joining method in accordance with the present invention is the method for joining a porous SiC body 1 and an SiC—Si composite 2 as shown in FIG. 1A, and is characterized in that a porous SiC adhesion layer 3 is formed between the porous SiC body 1 and the SiC—Si composite 2, and molten Si in the SiC—Si composite 2 is caused to permeate the porous SiC adhesion layer 3 by a capillary phenomenon so as form a dense joining layer.

It is to be noted that in FIG. 1A, the black circles denote SiC particles, the'shaded area denotes Si, the squares denote SiC particles in the adhesion layer 3 and the blank areas denote pores schematically.

For the joining method of the present invention, in order to form a dense joining layer by causing molten Si in the SiC—Si composite 2 to permeate the porous SiC adhesion layer 3 by a capillary phenomenon as mentioned above, the average pore diameter of the porous SiC body, the average diameter of the Si portion in the SiC—Si composite and the average pore diameter of the porous SiC adhesion layer need to have the following relationship.

That is, the porous SiC body 1, the SiC—Si composite 2 and the porous SiC adhesion layer 3(adhesive paste consisting of SiC powder) to be used for this joining method need to have a relationship of the average pore diameter of the porous SiC adhesion layer<the average diameter of the Si portion in the SiC—Si composite<the average pore diameter of the porous SiC body.

Thus, the average pore diameter of porous SiC adhesion layer 3 is set to be the smallest in order to absorb the Si in the SiC—Si composite by a capillary phenomenon to make the adhesion layer 3 dense.

In addition, the average diameter of the silicon (Si) portion in the SiC—Si composite 2 is set to be smaller than the average pore diameter of the porous SiC body 1 in order not to cause the molten Si to permeate the porous SiC body 1 during a heat treatment.

It is to be noted that it is undesirable that the average pore diameter of the Si portion in the SiC—Si composite 2 is larger than the average pore diameter of the porous SiC body 1, because in such case, the molten Si will be caused to permeate the inside of the porous SiC body or the surface layer thereof via the joining layer 3 during the heat treatment to cause a loss of the function of the porous SiC body 1.

For carrying out the joining method of the present invention, the porous SiC body 1, the SiC—Si composite 2 and the porous SiC adhesion layer 3 (adhesive paste consisting of SiC powder) are prepared so as to maintain the above-mentioned relationship.

Then, the adhesive paste 3 consisting of SiC powder is applied to either or both of the porous SiC body 1 and the SiC—Si composite 2. The thin-porous SiC adhesion layer 3 is formed by causing a volatile consistent to evaporate from said adhesive paste 3 so as to cure the adhesive paste 3 consisting of SiC powder. In this manner, the porous SiC body 1 and the SiC—Si composite 2 become a temporarily-joined body (See FIG. 1A).

Thereafter, a heat treatment for the temporarily-joined body is performed at high temperature so that the Si in the SiC—Si composite 2 is melted and a small amount of the molten Si is caused to permeate the porous SiC adhesion layer 3 by a capillary phenomenon. In this manner, the dense joining layer is formed (FIG. 1B).

It is preferable that said heat treatment is performed under a condition of a temperature of 1450° C. or more, under a reduced pressure of a few Pa and a heat treatment time of 60 minutes or more. It is undesirable that said heat treatment is performed at a temperature of less than 1450° C. and a heat treatment time of less than 60 minutes, because in such case, silicon (Si) will not caused to permeate the adhesion layer and a porosity or the like is left with the result that a dense body will not be formed, and it can cause a leakage from the joining portion whereas the mechanical strength is reduced.

In the present invention, silicon (Si) is impregnated into the porous SiC adhesion layer and the mechanical strength of the joined body can be improved (See FIG. 1B).

Further, by using a body to be joined having the above mentioned predetermined relationship of pore diameters, a permeation of silicon (Si) into the porous SiC body to be joined can be restrained and exudation of surplus Si on the surface of the porous SiC body can be restrained.

It is to be noted that due to the outflow of Si from the SiC—Si composite, a small amount of microscopic pore 4 is formed in the area of a joined interface of the SiC—Si composite as shown in FIG. 1B. However, since those pores are discrete closed pores and they exist only in a narrow range of the joined interface area, a leakage of gas and liquid from the SiC—Si composite 2 will not occur. In addition, it does not affect a joining strength.

Next, particular examples and evaluation results of the present invention will be described.

EXAMPLE 1

Filter 10 shown in FIG. 2 was produced by joining the porous silicon carbide (SiC) body and the silicon carbide-silicon (SiC—Si) composite. In FIG. 2, the character 11 denotes a cap section made of the SiC—Si composite, the character 12 denotes a cylindrical filter section made of the porous SiC body to be joined with said cap section 11, and the character 13 denotes a filter body made of the SiC—Si composite to be joined with said filter section.

Firstly, the cap section 11 and the filter body 13 were produced out of the SiC—Si composite.

For said filter, said filter body was prepared by mixing 25% by weight of SiC raw powder of 100 μm, 25% by weight of SiC raw powder of 40 μm and 50% by weight of SiC raw powder of 4 μm, 3% by weight (outer percentage) of carbon powder, 13% by weight (outer percentage) of binder and 10% by weight (outer percentage) of water and granulating the mixture to be followed by extrusion molding.

Then, said molded filter body was cured at a temperature of about 200° C., calcined at 1500° C. to 1800° C. in a nitrogen atmosphere under a reduced pressure, processed into a cylindrical shape having predetermined dimensions (the outer diameter of 20 mm, the inner diameter of 16 mm, and the length of 100 mm).

Molten silicon (Si) was impregnated into said calcined filter body in an inert gas atmosphere of nitrogen, at a temperature of 1430° C. to 1500° C. At this time, the average diameter of the Si portion (SiC inter-particle distance) in the filter body (SiC—Si composite) was 0.4 μm.

Subsequently, said cap section was prepared by mixing SiC raw powder consisting of a weight ratio of SiC raw powder of 100 μm to SiC raw powder of 10 μm being 60:40 with 4% by weight (outer percentage) of carbon powder and 11% by weight (outer percentage) of binder, causing the mixture to be granulated and molding the granules by a cold isostatic pressing (CIP) method.

Then, the thus molded cap section was cured at a temperature of about 200° C., calcined at 1500° C. to 1800° C. and processed into a disc-shape form having predetermined dimensions (the diameter of 19 mm, the thickness of 3 mm).

Subsequently, molten silicon (Si) was impregnated into said calcined cap section in an inert gas atmosphere of nitrogen, at a temperature of 1430° C. to 1500° C. At this time, an average diameter of the Si portion (SiC inter-particle distance) in the cap section (SiC—Si composite) was 7 μm.

Secondly, the filter section was prepared out of the porous SiC body.

For the filter, a filter section was prepared by mixing 30% by weight of SiC raw powder of 100 μm and 70% by weight of SiC raw powder of 10 μm, 14% by weight (outer-percentage) of Si powder of 5 μm and 11% by weight (outer percentage) of binder, granulating the mixture, and molding the granules by a cold isostatic pressing (CIP) method.

The thus prepared filter section was temporally calcined at a temperature of 1500° C. to 1700° C. and processed and formed into a cylindrical shape having predetermined dimensions (the outer diameter of 19 mm, the inner diameter of 16 mm, and the length of 40 mm) . Then, said temporally-calcined filter section was further calcined fully at a temperature of 2200° C. so that it became a filter section made of porous SiC. At this time, an average pore diameter of the porous SiC body was 9 μm.

Next, a method of joining a cap section (SiC—Si composite) 11 and a filter body (SiC—Si composite) 13 with a filter section (porous SiC body) 12 will be explained.

Firstly, for only the surface layer of the joining surface of the cap section (SiC—Si composite) 11 and the filter body (SiC—Si composite) 13, the Si thereof was etched by hydrofluoric nitric acid. It is to make them hard to get peeled off when adhering mentioned below.

Further, an adhesive paste for joining was produced. This adhesive paste was produced by mixing 30% by weight of SiC powder of 100 μm and 70% by weight of SiC powder of 4 μm, 20% by weight (outer percentage) of binder and 7% by weight (outer percentage) of propylene glycol, degassing the mixture, adding 0.8% by weight (outer percentage) of hydrochloric acid, and then kneading the degassed mixture into an adhesive paste.

This adhesive paste was applied to the adhesion surfaces of the cap section (SiC—Si composite) 11 and the filter body (SiC—Si composite) 13.

Then, the filter section (porous SiC body) 12 was crimped to the cap section (SiC—Si composite) 11. Further, the filter section (porous SiC body) 12 was crimped to the filter body (SiC—Si composite) 13. The resultant joined body was cured in microwave oven by causing a volatile consistent to evaporate from said adhesive paste 3. It is to be noted that an average pore diameter of the adhesion layer (porous SiC) after the curing was 0.03 μm.

Thereafter, said joined body was heat treated at a temperature of 1470° C. under a reduced pressure of a few Pa for 3.5 hours, molten-silicon (Si) in the cap section (SiC—Si composite) and in the filter body (SiC—Si composite) was caused to permeate the adhesion layer (porous SiC) to be joined, thus completing the production of the filter (Example 1).

And, a same type of filter was produced by a conventional silicon (Si) impregnation-method. The procedure of this production method is as described below.

In the same manner as Example 1, a filter body, a cap section, a filter section and an adhesive paste were prepared. Then, a porous SiC body was overlaid on the top surface of the SiC body by way of a binder composed of thermosetting resin containing SiC micro-particles. Further, an Si sheet was overlaid on the top surface of the porous SiC body. Then, the entire body was heated up to a temperature at which said silicon (Si) is melted and the temperature was maintained for a predetermined period of time. And said silicon (Si) was infiltrated into pores of said porous SiC body and was caused to react with carbon (C) generated by carbonization of the thermosetting resin of said binder so that an SiC layer was formed at a joining portion, where joining was done.

For the Example 1 and the conventional example, the Si permeation into the adhesion layer, the permeation length of silicon (Si) into the porous SiC body, and the exudation (blow-off) of Si on the porous SiC body were verified. The result is shown in Table 1.

As can be observed from Table 1, the Example 1 was preferable since Si was caused to permeate the adhesion layer, and no permeation-free area was confirmed. In addition, Si was not caused to permeate the porous SiC body and silicon exudation (blow-off) was not confirmed.

On the other hand, for the conventional example, even though there was no permeation-free area of Si into the adhesion layer, Si was excessively caused to permeate the filter section (porous body) and the permeation length varied greatly in the range 4 to 40 mm. In addition, a large area and a large amount of Si exudation (blow-off) was observed.

TABLE 1
		Permeation
	Si permeation	length of Si
	into the	into the	Si
Joining method	adhesion layer	porous body	exudation	Judgment
Example 1	No	0	mm	Small	◯
	permeation-free			area,
	area			small
				amount
Conventional	No	4 to 40	mm	Large	X
Example	permeation-free			area,
	area			large
				amount
(◯: good, X: bad)

Next, in a same manner as the cap section in the Example 1, a column-shaped SiC—Si composite having a width of 4 mm, a thickness of 3 mm and a length of 40 mm was produced. And in the same manner as the filter section in the Example 1, a column-shaped porous SiC body having a width of 4 mm, a thickness of 3 mm and a length of 40 mm was produced.

Then, in a same manner as the Example 1, said column-shaped SiC—Si composite and said column-shaped porous SiC body were joined by using the adhesive paste shown in Example 1 (Example 2).

On the other hand, in a same manner as said Example 2, a column-shaped SiC—Si composite having a width of 4 mm, a thickness of 3 mm and a length of 40 mm and a column-shaped porous SiC body having a width of 4 mm, a thickness of 3 mm and a length of 40 mm were produced, and a joined body was obtained by a conventional silicon impregnation-method (Comparative Example 1).

Then, the strength (the three point flexural strength) of the joining portion was verified. The result is shown in Table 2. As can be observed from Table 2, the strength of the joining portion was significantly increased. It is to be noted in the Example 2 that this flexural strength test shows that breakage started from the substrate of the porous SiC body other than the joining portion thereof. It suggests that Si was caused to fully permeate the adhesion layer, and the strength of joining portion is more than that of substrate of the porous SiC body.

TABLE 2
		Strength		Strength ratio
		of the	Strength of	of the joining
		porous	the joining	portion to the
Joining method	Detail	body	portion	porous body
Example 2	Good	20.3 MPa	30.0 MPa	148%
	condition in
	the joining
	layer
Comparative	Permeation-	22.9 MPa	17.8 MPa	78%
Example 1	free area
	observed in
	the joining
	layer

Next, column-shaped SiC—Si composites (having a width of 20 mm, a thickness of 10 mm and a length of 40 mm) were produced in a same manner as the filter body and the cap section in the Example 1. Then, SiC—Si composites having the average diameter of a silicon (Si) portion (having an SiC inter-particle distance) D1 of 7 μm and 0.4 μm were obtained.

And, column-shaped porous SiC bodies (having a width of 20 mm, a thickness of 10 mm and a length of 10 mm) were produced in a same manner as the Example 1. By controlling the particle size of SiC raw powder, the compounding ratio and the calcinations temperature, porous SiC bodies having an average pore diameter D2 of 0.2 μm to 9 μm were obtained.

For an adhesive paste, the same paste as in the Example 1 (having a pore diameter of 0.03 μm) was used.

Then, by combining the results shown in Table 3, the permeation length of Si into the porous SiC body and the permeating condition were verified. It is to be noted that in the Example 3 to 5 and the Comparative Example 2 to 4, the heat treatment was performed under the same condition as the Example 1.

The result is shown in Table 3.

	TABLE 3
				Per-
				meation
				length into	Permeation
	D1	D2	D1/	the porous	into the
	(μm)	(μm)	D2	body	porous body	Judgment
Comparative	7	0.2	35	>2 mm	Permeated	X
Example 2					inside of the
					porous body
Comparative	7	0.6	12	>2 mm	Permeated	X
Example 3					inside of the
					porous body
Comparative	7	3	2.3	1 mm	Permeated	X
Example 4					surface layer
					of the porous
					body
Example 3	7	9	0.8	0 mm	No	⊚
					permeation
Example 4	0.4	0.6	0.7	<1 mm	Permeated	◯
					inside of the
					porous body
Example 5	0.4	3	0.13	0 mm	No	⊚
					permeation
(⊚: very good, ◯: good, X: bad)

As can be observed from Table 3, it is preferable to have a relationship such as the average diameter of the Si portion in the SiC—Si composite (SiC inter-particle distance)<the average pore diameter of the porous SiC body, since permeation into the inside of porous SiC body can be well restrained.

Then, the heat-treatment condition was verified. Tube-shaped SiC—Si composites (having an outer diameter of 20 mm, an inner diameter of 16 mm and a length of 100 mm) with the average diameter of the Si portion (SiC inter-particle distance) D1 being 7 μm were produced in the same manner as the cap section in the Example 1. Further, Tube-shaped porous SiC bodies (having an outer diameter of 20 mm, an inner diameter of 16 mm and a length of 100 mm) with the pore diameter being 9 μm were produced in the same manner as the filter section in the Example 1. The same paste as the Example 1 (having a pore diameter of 0.03 μm) was used as an adhesive paste, and heat treatments were performed under the conditions shown in Table 4 (Example 6, 7 and Comparative Example 5 and 6).

	TABLE 4
	Temperature	Time	Condition of the
	(° C.)	(minute)	adhesion layer	Judgment
Comparative	1430	15	Permeation-free	X
Example 5			area observed
Comparative	1430	45	Permeation-free	X
Example 6			area observed
Example 6	1450	60	No	◯
			permeation-free
			area
Example 7	1490	150	No	◯
			permeation-free
			area
(◯: good, X: bad)

It was confirmed that it is undesirable to have a heat-treatment condition such as a temperature of less than 1450° C. and a heat treatment time of less than 60 minutes because, in such case, a permeation-free area of silicon (Si) and a porosity or the like were left at the adhesion layer so no dense body was formed with the result that it can cause a leakage from the joining portion and a reduction in the mechanical strength.

The present invention can be widely used as a method of joining a porous SiC body and an SiC—Si composite. For example, it is widely used in the manufacturing industry of semiconductor-related components or the like such as a jig for production of semiconductors.

Claims

1. A method of joining a porous silicon carbide (SiC) body and a silicon carbide-silicon (SiC—Si) composite comprising the steps of: (a) applying an adhesive paste consisting of silicon carbide (SiC) powder and a binder component to either or both of a porous silicon carbide (SiC) body and a silicon carbide-silicon (SiC—Si) composite formed by impregnating a silicon carbide (SiC) body with silicon (Si) such that said porous silicon carbide (SiC) body and said silicon carbide-silicon (SiC—Si) composite are caused to adhere to each other;(b) causing a volatile constituent to evaporate from said adhesive paste such that a porous silicon carbide (SiC) adhesion layer is formed between said porous silicon carbide (SiC) body and said silicon carbide-silicon (SiC—Si) composite; and(c) causing the silicon in said silicon carbide-silicon (SiC—Si) composite to permeate said adhesion layer through a heat treatment after the step (b) such that said adhesion layer is densified.

2. The method of joining a porous silicon carbide (SiC) body and a silicon carbide-silicon (SiC—Si) composite according to claim 1, wherein there is a relationship that a silicon portion in said silicon carbide-silicon (SiC—Si) composite formed by impregnating the silicon carbide (SiC) body with silicon (Si) has an average diameter greater than an average pore diameter of said adhesion layer and smaller than an average pore diameter of said porous silicon carbide (SiC) body.

3. The method of joining a porous silicon carbide (SiC) body and a silicon carbide-silicon (SiC—Si) composite according to claim 1, wherein said heat treatment is performed under a condition of a temperature of 1450° C. or more, under a reduced pressure and a heat treatment time of 60 minutes or more.

4. The method of joining a porous silicon carbide (SiC) body and a silicon carbide-silicon (SiC—Si) composite according to claim 2, wherein said heat treatment is performed under a condition of a temperature of 1450° C. or more, under a reduced pressure and a heat treatment time of 60 minutes or more.