JPH08259330A - Material containing boron nitride and its production - Google Patents

Abstract

PURPOSE: To obtain a material containing boron nitride extremely excellent in corrosion resistance against a molten metal or a molten slag by not using expensive BN and AlN powders but using inexpensive B4 C and Al as starting materials. CONSTITUTION: This material containing boron nitride is obtained by heating a mixed powder containing 10-70wt.% B4 C, 30-90wt.% Al and 10-60wt.% Si or SiO2 up to 1300-2300 deg.C in a nitrogenizing atmosphere, and contains 22-90wt.% BN, 4-48wt.% AlN and 6-30wt.% SiC, or 22-90wt.% BN, 4-48wt.% AlN and/or AlON, 6-30wt.% SiC and 4-30wt.% Al2 O3 .

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a boron nitride-containing material containing AlN and / or AlON in addition to BN and a method for producing the same, and particularly to a boron nitride-containing material excellent in corrosion resistance against molten metal and molten slag and its production. Regarding the method.

[0002]

BACKGROUND OF THE INVENTION Hexagonal boron nitride has high thermal conductivity, excellent electrical insulation, and excellent lubricity, and is suitable for iron, copper,
It is known as a chemically stable material that does not react with a melt such as nickel, zinc, gallium, arsenic, glass and cryolite. It is stable up to 950 ° C. in air and up to 2200 ° C. in an inert gas or nitrogen gas atmosphere, and is resistant to thermal shock. Further, like metal, it has a feature that machining such as cutting and grinding can be easily performed. Utilizing these features, it is used in various applications as a simple substance of boron nitride or a composite material containing boron nitride.

Applications as sintered bodies include insulating parts, heat resistant parts, crucibles for molten metal, break rings for horizontal continuous casting, heat radiating parts, setters for sintering powder compacts of metal or ceramics, and mold materials. Further, it is also attempted to be applied to a refractory for casting such as an upper nozzle and a dipping nozzle.

JP-A-63-84750 discloses a material suitable for continuous casting of deoxidized steel, 20 to 70 parts by weight of boron nitride, 10 to 40 parts by weight of aluminum nitride and graphite 10.
Disclosed is a continuous casting nozzle containing -30 parts by weight. The nozzle in which boron nitride, aluminum nitride and graphite are blended at a predetermined ratio has low wettability with molten steel, and therefore has an effect of preventing inclusions from adhering to the inner surface of the nozzle. In addition, Interceram, Special Issue (1987) page 70, 52.6 wt% B as a boron nitride-based continuous casting nozzle.
N, 27.0 wt% AlN, 2.0 wt% SiO ₂ , C
And SiC in total of 17.5 wt% are disclosed. These materials usually use a powder corresponding to the components constituting the product as a starting material.

On the other hand, a method of producing hexagonal boron nitride in a sintered body by a reaction is known, and for example, in JP-A-4-325461, silicon and B ₄ are contained.
By molding a mixed powder with C and heating it in a nitrogen atmosphere, BN and C produced by nitriding B ₄ C, SiC produced by carbonizing silicon, and Si ₃ N ₄ produced by nitriding silicon are contained. The sintered body is disclosed.

[0006]

The hexagonal boron nitride material has been expected to expand in the market due to the above-mentioned unique properties, but it has not grown as much as expected. The main reason for this is that the starting hexagonal boron nitride powder is expensive. For materials containing BN and AlN, see Al
Since N is also expensive, it becomes more expensive.

On the other hand, hexagonal boron nitride is a soft ceramic and is weak against wear. Therefore, the boron nitride-containing material has a drawback that it is easily worn by mechanical friction such as flow of molten metal or molten slag.
Even if AlON is contained, the abrasion resistance may not be sufficient.

The present invention has been made in view of the above circumstances, and a boron nitride-containing material which can be obtained without using expensive BN and AlN powders and which has excellent corrosion resistance to molten metal and molten slag, and It is an object to provide a manufacturing method thereof. Another object of the present invention is to provide a boron nitride-containing material having excellent corrosion resistance against molten metal and molten slag, and a method for producing the same.

[0009]

In order to solve the above-mentioned problems, the present invention firstly requires 10 to 70 wt% of B.
₄ C, 30-90 wt% Al, 10-60 wt% S
a mixed powder containing i in a nitriding atmosphere at 1300 to 230
A material obtained by heating to 0 ° C., which is 22 to 90
wt% BN, 4-48 wt% AlN, 6-30 wt%
Provided is a boron nitride-containing material, characterized in that it comprises% SiC.

Second, 10 to 70 wt% B ₄ C, 30
A mixed powder containing ˜90 wt% Al and 10-60 wt% Si is heated to 1300 to 2300 ° C. in a nitriding atmosphere, and BN is 22 to 90 wt% and A is 4 to 48 wt%.
Provided is a method for producing a boron nitride-containing material, which comprises obtaining a boron nitride-containing material containing 1N and 6 to 30 wt% SiC.

Third, 22-90 wt% BN, 4-4
8 wt% AlN and / or AlON, 6-30w
Provided is a boron nitride-containing material, characterized in that it contains t% SiC and 4 to 30 wt% Al ₂ O ₃ .

Fourth, 10 to 70 wt% B ₄ C, 30
A material obtained by heating a mixed powder containing ˜90 wt% Al and 10 to 60 wt% SiO ₂ to 1300 to 2300 ° C. in a nitriding atmosphere.
BN, 4-48 wt% AlN and / or AlO
N, 6 to 30 wt% SiC, 4 to 30 wt% Al ₂
Provided is a boron nitride-containing material characterized by containing O ₃ .

Fifth, 10 to 70 wt% B ₄ C, 30
~ 90wt% Al, mixed powder containing 10 ~ 60wt% SiO ₂ was heated to 1300 ~ 2300 ° C in a nitriding atmosphere, 22 ~ 90wt% BN, 4 ~ 48wt%
AlN and / or AlON, 6-30 wt% S
Provided is a method for producing a boron nitride-containing material, which comprises obtaining a boron nitride-containing material containing iC and 4 to 30 wt% of Al ₂ O ₃ .

Sixth, 22-90 wt% BN, 4-4
Provided is a boron nitride-containing material characterized by containing 8 wt% AlON and 6 to 30 wt% SiC. Seventh
10 to 70 wt% of B ₄ C and 30 to 90 wt% of A
1, a material obtained by heating a mixed powder containing ₁₀ to 60 wt% of SiO ₂ to 1700 to 2300 ° C. in a nitriding atmosphere, and 22 to 90 wt% of BN, 4 to 48
Provided is a boron nitride-containing material characterized by containing wt% AlON and 6 to 30 wt% SiC.

Eighth, 10 to 70 wt% B ₄ C, 30
~ 90wt% Al, mixed powder containing 10 ~ 60wt% SiO ₂ was heated to 1700 ~ 2300 ° C in a nitriding atmosphere, 22 ~ 90wt% BN, 4 ~ 48wt%
The present invention provides a method for producing a boron nitride-containing material, characterized in that the boron nitride-containing material containing AlON and 6 to 30 wt% SiC is obtained.

Ninth, 22-90 wt% BN, 4-4
8 wt% AlN and / or AlON, 6-30w
A material containing t% SiC and having a thickness of 2 to 10 on the surface.
Provided is a boron nitride-containing material characterized by having a concentrated layer of AlN and / or AlON of mm.

Tenth, 70% by weight of B ₄ C, 3
A mixed powder containing 0 to 90 wt% of Al and 10 to 60 wt% of Si or SiO ₂ in a nitriding atmosphere at 1300 to
A material obtained by heating to 2300 ° C.
˜90 wt% BN, 4-48 wt% AlN and /
Alternatively, there is provided a boron nitride-containing material comprising AlON and 6 to 30 wt% of SiC, and having a concentrated layer of 2 to 10 mm thick AlN and / or AlON on the surface.

Eleventh, 10 to 70 wt% of B ₄ C, 3
A mixed powder containing 0 to 90 wt% of Al and 10 to 60 wt% of Si or SiO ₂ in a nitriding atmosphere at 1300 to
Heated up to 2300 ° C., 22-90 wt% BN, 4
~ 48 wt% AlN and / or AlON, 6-3
A containing 0 wt% SiC and having a thickness of 2-10 mm on the surface
Provided is a method for producing a boron nitride-containing material, which comprises obtaining a boron nitride-containing material having a concentrated layer of 1N and / or AlON.

The present invention will be specifically described below.
In the present invention, basically, B ₄ C, Al, Si or / and SiO ₂ is used as a starting material and heated to a predetermined temperature in a nitriding atmosphere to obtain BN, SiC and AlN, Al ₂ O ₃ And a boron nitride-containing material containing at least one of AlON.

In the present invention, AlN, Al ₂ O ₃ , A
The production ratio of each crystal phase of 1ON depends on the ambient temperature, the holding time at that temperature, the nitrogen partial pressure of the atmosphere, the density, size, shape, and packing of the filling body or shape-retaining shaped body used for nitriding Alternatively, the temperature is controlled by the particle size of the powder forming the compact, and the most influential factor among these is the ambient temperature. For example, when a molded body having a wall thickness of 30 mm or less and a holding time of 3 hours or more, AlN and Al ₂ O ₃ are the main production phases at 1300 to 1500 ° C. Also, 14
At 00 to 1900 ° C., solid solution of AlN and Al ₂ O ₃ progresses, and AlN, AlON, and Al ₂ O ₃ coexist. Further, at 1700 to 2100 ° C., AlN and AlON are the main components. Then, at 2000 to 2300 ° C., AlON becomes the main component. When the wall thickness becomes larger, the solid solution inside is delayed compared to the surface, and the characteristics of the generated phase due to the above temperature division become unclear as a whole, and there is a tendency that multiple phases coexist in the high temperature region. For example, even at 2000 to 2300 ° C, A
In addition to 1N, AlN and Al ₂ O ₃ may be detected by X-ray diffraction.

Although there are various factors as described above, the raw materials are selected at least as in each of the embodiments described below, and the materials are heated to a temperature range selected from 1300 to 2300 ° C. in each of the embodiments to be described later. The above reaction can be effectively caused, and the boron nitride-containing material of each aspect can be obtained.

B used as a raw material in the present invention
_If the particle size of the powder of ₄ C, Al, Si or / and SiO ₂ is too large, these reactants remain unreacted, which is not preferable. The particle size of the powder is preferably fine in order to complete the reaction of the present invention, and a 150-mesh sieve mesh powder is preferable. More preferred is a 200 mesh sieve mesh powder. Among them, Al is nitrided in the liquid phase after melting, so that the reaction is relatively easy. On the other hand, B ₄ C, Si, S
Since iO ₂ reacts in the solid phase, diffusion of nitrogen into the grains has a significant effect on the reaction rate. Therefore, it is more preferable that these raw materials have an average particle size of 10 μm or less in addition to defining the mesh screen.

Next, each aspect of the present invention will be described individually. First, the first aspect of the present invention is 10 to 70 wt%.
A mixed powder containing B ₄ C, 30 to 90 wt% of Al, and 10 to 60 wt% of Si was added to a nitrogen-containing atmosphere at 1300 to 23
By heating up to 00 ° C., 22-90 wt% BN, 4-48 wt% AlN, 6-30 wt% Si
A boron nitride-containing material containing C is obtained.

Here, the nitriding atmosphere at the time of heating is not particularly limited, but nitrogen, ammonia, ammonia decomposition gas,
A gas containing these can be applied. The following reactions occur in such an atmosphere.

Al + (1/2) N ₂ → AlN B ₄ C + 2N ₂ + Si → 4BN + SiC First, Al, which is a starting material, is nitrided. For nitriding Al, the ambient temperature is preferably 650 ° C. or higher. This is because if the temperature is lower than 650 ° C., the reaction is slow and the nitriding time becomes too long. On the other hand, the nitriding of Al is preferably completed at 2300 ° C. or lower. This is because the nitridation of Al is accompanied by a large amount of heat generation, so that the temperature of the processed material becomes higher than the atmospheric temperature, and the volatilization loss becomes large when the atmospheric temperature exceeds 2300 ° C. In the temperature cycle in which these reactions occur, the highest temperature reached needs to be 1300 ° C or higher, preferably 1400 ° C or higher.
When this temperature is lower than 1300 ° C, a part of Al is B
_Since it only reacts with ₄ C to form AlB ₂ and C or Al ₄ C _3, and a part of Si becomes Si ₃ N ₄ , resulting in insufficient formation of the target BN, AlN, and SiC. Is.

The materials produced are AlN which has excellent corrosion resistance to molten metal, especially molten steel, and S which has excellent slag resistance.
It is a material that combines iC and BN having excellent corrosion resistance and machinability, and has 22 to 90 wt% BN and 4 to 48
It is necessary to include at least wt% AlN and 6 to 30 wt% SiC. Because when it comes out of this composition,
This is because the various material properties described above are not sufficiently exhibited.

Next, a second aspect of the present invention is 10 to 70.
wt% B ₄ C, 30-90 wt% Al, 10-60w
13% of mixed powder containing t% of SiO ₂ in a nitriding atmosphere
Heated to 00 to 2300 ° C., 22 to 90 wt% B
N, 4-48 wt% AlN or AlON, 6-30
A boron nitride-containing material containing wt% SiC and 4 to 30 wt% Al ₂ O ₃ is obtained.

Here, Si may be contained in addition to SiO ₂ as a raw material Si source as long as the composition of the boron nitride-containing material of the present embodiment is satisfied. The nitriding atmosphere during heating is not particularly limited, but nitrogen, ammonia, ammonia decomposition gas, gas containing these, or the like can be applied. The following reactions occur in such an atmosphere.

Al + (1/2) N ₂ → AlN B ₄ C + 2N ₂ + SiO ₂ → 4BN + SiC + (2
/ 3) Al ₂ O ₃ First, the starting material, Al, is nitrided. For nitriding Al, the ambient temperature is preferably 650 ° C. or higher. This is because if the temperature is lower than 650 ° C., the reaction is slow and the nitriding time becomes too long. On the other hand, the nitriding of Al is preferably completed at 2300 ° C. or lower. This is because the nitridation of Al is accompanied by a large amount of heat generation, so that the temperature of the processed material becomes higher than the atmospheric temperature, and the volatilization loss becomes large when the atmospheric temperature exceeds 2300 ° C. In the temperature cycle in which these reactions occur, the highest temperature reached needs to be 1300 ° C or higher, preferably 1400 ° C or higher.
When this temperature is lower than 1300 ° C, a part of Al is B
It reacts with ₄ C to produce AlB ₂ and C or Al ₄ C ₃ , and also reduces SiO ₂ to produce Al ₂ O ₃ and Si, and a part of Si becomes Si ₃ N _4. BN, A
This is because the production of 1N and SiC becomes insufficient. AlN
And a part of Al ₂ O ₃ may form a solid solution and be converted into AlON. Here, AlON is a general term for a solid solution of Al, O, and N, but the composition is not particularly limited,
It may have any composition.

The materials produced were AlN or AlON having excellent corrosion resistance to molten metal, particularly molten steel, SiC having excellent slag resistance, BN having excellent corrosion resistance and machinability, and excellent oxidation resistance. A material that combines Al ₂ O ₃ and has 22 to 90 wt% BN and 4 to 48 wt%
AlN or AlON of 6 to 30 wt% SiC must be included. This is because, if the composition is out of this range, the various material properties as described above are not sufficiently exhibited.

Further, the third aspect of the present invention is 10 to 7
0 wt% B ₄ C, 30 to 90 wt% Al, 10 to 60
Mixed powder containing 1 wt% SiO ₂ in nitriding atmosphere
Heated to 700-2300 ° C., 22-90 wt% BN, 4-48 wt% AlON, 6-30 wt% S
A boron nitride-containing material containing iC is obtained.

BN, AlN or AlON, SiC
The material containing Al is kept at a high temperature of 1700 to 2300 ° C. for preferably 2 hours or more, more preferably 3 hours or more, so that AlN and Al ₂ O ₃ are sufficiently dissolved to form A.
The conversion rate to ON increases. AlON has both the corrosion resistance of AlN against molten metal and the oxidation resistance of Al ₂ O ₃ , and improves the corrosion resistance and oxidation resistance of the material against molten metal.

Here, also in this embodiment, Si may be contained in addition to SiO ₂ as the source Si source as long as the composition of the boron nitride-containing material of this embodiment is satisfied. The produced material is a material in which AlON having excellent corrosion resistance to molten metal, particularly molten steel, SiC having excellent slag resistance, and BN having excellent corrosion resistance and machinability are combined, and the content is 22 to 90 wt%. BN, 4-48 wt% AlO
It is necessary to contain at least N and SiC of 6 to 30 wt%. This is because, if the composition is out of this range, the various material properties as described above are not sufficiently exhibited.

Still further, according to the fourth aspect of the present invention,
To 70 wt% of B ₄ C, 30~90wt% of Al, 10
By heating a mixed powder containing ˜60 wt% Si or SiO ₂ to 1300 to 2300 ° C. in a nitriding atmosphere, 22 to 90 wt% BN, 4 to 48 wt% AlN and / or AlON, 6 to 30 wt % Si
A boron nitride-containing material containing C and having a concentrated layer of AlN and / or AlON having a thickness of 2 to 10 mm on the surface thereof.

This material is made of AlN and / or AlON having excellent corrosion resistance to molten metal, especially molten steel, SiC having excellent slag resistance, and B having excellent corrosion resistance and machinability.
It is a material that combines N and is 22 to 90 wt% of B
N, 4-48 wt% AlN and / or AlON,
It is necessary to contain at least 6 to 30 wt% of SiC.
This is because, if the composition is out of this range, the various material properties as described above are not sufficiently exhibited.

Further, as a result of the study by the present inventors, the total composition is within the range of the above composition and the surface has a thickness of 2 to 10.
It has been found that by forming a concentrated layer of AlN and / or AlON of mm, the wear resistance of the material is significantly improved.

Therefore, in this embodiment, the surface has a thickness of 2 to 10 m.
It is required to have a concentrated layer of mN AlN and / or AlON. Specifically, the ratio of the sum of the diffraction intensities of the maximum peaks of X-ray diffraction of AlN and AlON to the maximum intensity of the X-ray diffraction of BN in the range of 2 mm from the surface (AlN + AlON) / BN value, It is preferable that the ratio of (AlN + AlON) / BN within 10 mm or more from the surface is 1.3 or more. By forming the concentrated layer in this way, in addition to the corrosion resistance to the molten metal and the molten slag that the surface portion of the boron nitride-containing material of the present invention essentially has, it also has wear resistance to them. It will be.

This concentrated layer is made of AlN and / or AlO.
Since N is concentrated, it is harder than the inside and thus improves wear resistance, but the thickness of this concentrated layer is 2 m.
If it is smaller than m or exceeds 10 mm, the following inconvenience occurs. That is, if the thickness is less than 2 mm, the concentrated layer is likely to crack when a load is applied to the surface of the material, resulting in insufficient wear resistance. On the other hand, the thermal shock resistance of the material forming the concentrated layer is inferior to that of the material forming the inside, so if the thickness is less than 10 mm, the thermal stress generated in the concentrated layer due to thermal shock may be caused by the deformation inside the material. Although it is relaxed, if it exceeds 10 mm, it becomes difficult to relax and cracks easily occur. Therefore, from the viewpoint of wear resistance and thermal shock resistance, the thickness of this concentrated layer is defined as 2 to 10 mm.

The material of this embodiment is not particularly limited in the thickness and shape of the molded body as long as the thickness of the concentrated layer of AlN and / or AlON is in the range of 2 to 10 mm.
As the thickness becomes thinner, the amount of gas that is dissipated from the inside of the molded body relatively when heating the molded body to be described later decreases, so Al diffusion becomes insufficient, and 2-10 mm on the surface.
It becomes difficult to form a concentrated layer. Therefore, the thickness of the molded body is preferably 8 mm or more.

Next, a method for producing the material of this embodiment will be described. As described above, in this aspect, 1
0-70 wt% B ₄ C, 30-90 wt% Al, 1
The above-mentioned boron nitride-containing material is obtained by heating a mixed powder containing 0 to 60 wt% of Si or SiO ₂ to 1300 to 2300 ° C. in a nitriding atmosphere.

Here, the nitriding atmosphere at the time of heating is not particularly limited, but nitrogen, ammonia, ammonia decomposition gas,
A gas containing these can be applied. The following reactions occur in such an atmosphere.

Al + (1/2) N ₂ → AlN B ₄ C + 2N ₂ + Si → 4BN + SiC and /
Or B ₄ C + 2N ₂ + SiO ₂ → 4BN + SiC + (2
/ 3) Al ₂ O ₃ First, the starting material, Al, is nitrided. For nitriding Al, the ambient temperature is preferably 650 ° C. or higher. This is because if the temperature is lower than 650 ° C., the reaction is slow and the nitriding time becomes too long. On the other hand, the nitriding of Al is preferably completed at 2300 ° C. or lower. This is because the nitridation of Al is accompanied by a large amount of heat generation, so that the temperature of the processed material becomes higher than the atmospheric temperature, and the volatilization loss becomes large when the atmospheric temperature exceeds 2300 ° C. In the temperature cycle in which these reactions occur, the highest temperature reached needs to be 1300 ° C or higher, preferably 1400 ° C or higher.
When this temperature is lower than 1300 ° C, a part of Al is B
It reacts with ₄ C to form AlB ₂ and C or Al ₄ C _3, and a part of Si becomes Si ₃ N ₄ .
This is because the generation of AlN and SiC becomes insufficient. Al
A part of N and Al ₂ O ₃ may form a solid solution and be converted into AlON. The composition of AlON is not particularly limited and may be any composition. In addition, AlO
A part of Al of N may be replaced by Si. However, the Si / Al molar ratio is preferably 1.0 or less from the viewpoint of corrosion resistance. This is because if it exceeds 1.0, the corrosion resistance to the melt, particularly the molten steel and the molten slag, is lowered. An example of such AlON is Al ₁₁ O
₁₅ N, AlON, Al ₁₉₈ O ₂₈₈ N ₄ , Al ₂₇ O ₃₉ N,
Al ₁₀ N ₈ O ₃ , Al ₉ O ₃ N ₇ , SiAl ₇ O ₂ N
₇ , Si ₃ Al ₃ O ₄₅ N _{5 and the} like.

When the molded body is heated, the moisture adsorbed on the surface of the powder forming the molded body is evaporated or 600 ° C.
When it exceeds, the gas is generated due to the increase of the partial pressure of B ₂ O ₃ , etc., diffuses to the surface of the molded body, and is diffused to the outside. For this reason, Al melts at 650 ° C. or higher and becomes a liquid phase, and thus moves to the surface as the gas moves. Utilizing this phenomenon of movement of Al to the surface, Al is concentrated on the surface. Then, by nitriding the concentrated Al on the surface, Al
N, and Al and SiO ₂ are reacted to form Al ₂ O ₃
And Depending on the conditions, these are converted to AlON. In this way, a concentrated layer of AlN and / or AlON is formed on the surface of the material.

In any of the above-mentioned embodiments, within the range satisfying the composition specified in the present invention, AlB ₂ ,
C, Si ₃ N ₄ may be contained, or Ti
One or more oxides selected from O ₂ , ZrO ₂ , Cr ₂ O ₃ , Al ₂ O ₃ and SiO ₂ or a composite oxide containing at least one of these oxides is contained. It may have been done. In addition, MgB ₂ , CaB ₆ , Ti
One or more borides selected from B ₂ , ZrB ₂ , CrB ₂ , and CrB may be contained. Furthermore, TiC, ZrC, Cr ₃ C ₂ , Al ₄ C ₃
One or two or more kinds of carbides selected from the above may be contained. Furthermore, TiN, ZrN, Cr ₂
One or more nitrides selected from N may be contained.

[0045]

Embodiments of the present invention will be described below. (Example 1) Passing through 325 mesh sieve mesh (particle size 44 μm)
Below) B ₄ C, 200 mesh sieve mesh pass (particle size 74
Al, 325 mesh screen mesh (particle size 4)
4 μm or less) 28.9 wt% Si, 56.
Mixing at a ratio of 4 wt% and 14.7 wt%, diameter 60m
m in a graphite container with a cavity of 50 mm in height and 100 in
g, and a surface pressure of 10 MPa was applied through a graphite plate having a diameter of 60 mm and a thickness of 5 mm for consolidation. Thus, a molded body having a density of 1.43 g / cm ³ was obtained. This was placed in a graphite heater furnace, exhausted with a vacuum pump, nitrogen gas was introduced, the nitrogen pressure was 0.14 MPa (absolute pressure), the temperature was raised to 700 ° C. at a heating rate of 15 ° C./min, and after holding for 3 hours The sample was again heated to 1500 ° C. at a temperature rising rate of 15 ° C./min, kept for 3 hours and then left to cool.

The weight of the sintered body thus obtained is 1
42 g, and the bulk density was 2.27 g / cm ³ . BN, AlN, and SiC were identified by X-ray diffraction. The composition estimated by calculation is BN: 32.7 wt%, AlN: 5
It was 4.1 wt% and SiC: 13.2 wt%.

This sintered body was placed in an atmospheric furnace and set at 1500 ° C.
After heating for 1 hour and allowing to cool, the weight increase was measured.
As a result, the increase in weight was as small as 0.12%. Two specimens divided into 1/4 and one specimen divided into 1/2 were prepared from this sintered body, the former was subjected to a corrosion resistance test, and a test piece for bending test of 3 mm x 4 mm x 40 mm was cut out from the latter. It was

A cubic 13Cr steel (steel containing Cr: 13.0% by weight, C: 0.20% by weight, Si: 0.8% by weight) having a side of 5 mm was provided on one side of the corrosion resistance test piece, and the other had a diameter of 10 mm. 5 mm tablet-like powder compact with a height of 5 mm (SiO
₂ 35.2 wt%, Al ₂ O ₃ 4.1 wt%, CaO 2
(7.5 wt%) was placed thereon, and the mixture was heated to 1550 ° C. in an argon atmosphere, kept at 1550 ° C. for 2 hours, and then allowed to cool. Then, the contact angle of the 13Cr steel after solidification and the contact angle of the slag generated from the tablet-shaped powder compact were measured.
As a result, the contact angle of the 13Cr steel was 110 degrees and the contact angle of the slag was 96 degrees, and this BN-containing material was difficult to wet with molten steel and molten slag, and no reaction was observed at the contact interface. The result of the 3-point bending test with a span length of 30 mm is 8
It was 0 MPa, and it was confirmed that it was at a level usable as a refractory for casting.

(Example 2) B ₄ C having a particle size of 325 mesh pass (particle size of 44 μm or less), Al having a particle size of 200 mesh pass (particle size of 74 μm or less), 325
S with a mesh pass particle size (particle size 44 μm or less)
i, Al ₂ O ₃ having a particle size of 10 μm or less is 22.8
wt%, 44.6 wt%, 11.6 wt%, 21.0w
Mix at a ratio of t%, and fill 100 g of a graphite container having a cavity with a diameter of 60 mm and a height of 50 mm, and a diameter of 60 m.
A sheet pressure of 10 MPa was applied through a graphite plate of m and a thickness of 5 mm to perform consolidation. Thus, a molded product having a density of 1.62 g / cm ³ was obtained. This was placed in a graphite heater furnace, and after evacuation with a vacuum pump, nitrogen gas was introduced and the nitrogen pressure was adjusted to 0.1.
4 MPa (absolute pressure), 70 at a heating rate of 15 ° C / min
After heating to 0 ℃ and holding for 3 hours, the heating rate is 15 ℃ / mi again.
The mixture was heated to 1500 ° C. with n, held for 3 hours, and then allowed to cool.

The weight of the sintered body thus obtained is 1
It was 46 g and the bulk density was 2.37 g / cm ³ . BN, AlN, SiC, and Al ₂ O ₃ were identified by X-ray diffraction. The composition estimated by calculation is BN: 28.0 wt%,
AlN: 46.3 wt%, SiC: 11.3 wt%, A
l ₂ O _3: it was 14.4wt%.

This sintered body was placed in an atmospheric furnace and kept at 1500 ° C.
After heating for 1 hour and allowing to cool, the weight increase was measured.
As a result, the weight increase was as small as 0.05%. Two specimens divided into 1/4 and one specimen divided into 1/2 were prepared from this sintered body, the former was subjected to a corrosion resistance test, and a test piece for bending test of 3 mm x 4 mm x 40 mm was cut out from the latter. It was

One of the corrosion-resistant test pieces was a cubic 13Cr steel (a steel containing Cr: 13.0% by weight, C: 0.20% by weight, Si: 0.8% by weight) having a side of 5 mm, and the other had a diameter. 5 mm tablet-like powder compact with a height of 5 mm (SiO
₂ 35.2 wt%, Al ₂ O ₃ 4.1 wt%, CaO 2
(7.5 wt%) was placed thereon, and the mixture was heated to 1550 ° C. in an argon atmosphere, kept at 1550 ° C. for 2 hours, and then allowed to cool. Then, the contact angle of the 13Cr steel after solidification and the contact angle of the slag generated from the tablet-shaped powder compact were measured.
As a result, the contact angle of the 13Cr steel was 110 degrees and the contact angle of the slag was 92 degrees, and this BN-containing material was difficult to be wet with molten steel and molten slag, and no reaction was observed at the contact interface. The result of the 3-point bending test with a span length of 30 mm is 1
It was 10 MPa, and it was confirmed that it was at a level usable as a refractory for casting.

Example 3 B ₄ C having a particle size of 325 mesh pass (particle size of 44 μm or less), Al having a particle size of 200 mesh pass (particle size of 74 μm or less), 325
S with a mesh pass particle size (particle size 44 μm or less)
i, Al ₂ O ₃ having a particle size of 10 μm or less is 22.8
wt%, 44.6 wt%, 11.6 wt%, 21.0w
Mix at a ratio of t%, and fill 100 g of a graphite container having a cavity with a diameter of 60 mm and a height of 50 mm, and a diameter of 60 m.
A sheet pressure of 10 MPa was applied through a graphite plate of m and a thickness of 5 mm to perform consolidation. Thus, a molded product having a density of 1.62 g / cm ³ was obtained. This was placed in a graphite heater furnace, and after evacuation with a vacuum pump, nitrogen gas was introduced and the nitrogen pressure was adjusted to 0.1.
4 MPa (absolute pressure), 70 at a heating rate of 15 ° C / min
After heating to 0 ℃ and holding for 3 hours, the heating rate is 15 ℃ / mi again.
It was heated to 1900 ° C. with n, held for 6 hours, and then left to cool.

The weight of the sintered body thus obtained is 1
It was 45 g and the bulk density was 2.37 g / cm ³ . BN, AlN, AlON, SiC, Al ₂ O by X-ray diffraction
₃ were identified.

This sintered body was placed in an atmospheric furnace and set at 1500 ° C.
After heating for 1 hour and allowing to cool, the weight increase was measured.
As a result, the weight increase was as small as 0.03%. Two specimens divided into 1/4 and one specimen divided into 1/2 were prepared from this sintered body, the former was subjected to a corrosion resistance test, and a test piece for bending test of 3 mm x 4 mm x 40 mm was cut out from the latter. It was

A cubic 13Cr steel (a steel containing Cr: 13.0 wt%, C: 0.20 wt%, Si: 0.8 wt%) having a side of 5 mm was provided on one side of the corrosion resistance test piece, and the other was of a diameter. 5 mm tablet-like powder compact with a height of 5 mm (SiO
₂ 35.2 wt%, Al ₂ O ₃ 4.1 wt%, CaO 2
(7.5 wt%) was placed thereon, and the mixture was heated to 1550 ° C. in an argon atmosphere, kept at 1550 ° C. for 2 hours, and then allowed to cool. Then, the contact angle of the 13Cr steel after solidification and the contact angle of the slag generated from the tablet-shaped powder compact were measured.
As a result, the contact angle of the 13Cr steel was 110 ° and the contact angle of the slag was 95 °, and this BN-containing material was difficult to be wet with molten steel and molten slag, and no reaction was observed at the contact interface. The result of the 3-point bending test with a span length of 30 mm is 1
It was 20 MPa, and it was confirmed that it was at a level usable as a refractory for casting.

(Example 4) B ₄ C having a particle size of 325 mesh pass (particle size of 44 μm or less), Al having a particle size of 200 mesh pass (particle size of 74 μm or less), 325
S with a mesh pass particle size (particle size 44 μm or less)
i, Al ₂ O ₃ having a particle size of 10 μm or less is 22.8
wt%, 44.6 wt%, 11.6 wt%, 21.0w
Mix at a ratio of t%, and fill 100 g of a graphite container having a cavity with a diameter of 60 mm and a height of 50 mm, and a diameter of 60 m.
A sheet pressure of 10 MPa was applied through a graphite plate of m and a thickness of 5 mm to perform consolidation. Thus, a molded product having a density of 1.62 g / cm ³ was obtained. This was placed in a graphite heater furnace, and after evacuation with a vacuum pump, nitrogen gas was introduced and the nitrogen pressure was adjusted to 0.1.
4 MPa (absolute pressure), 70 at a heating rate of 15 ° C / min
After heating to 0 ℃ and holding for 3 hours, the heating rate is 15 ℃ / mi again.
The mixture was heated to 2200 ° C. with n, held for 5 hours and then allowed to cool.

The weight of the sintered body thus obtained is 1
42 g, and the bulk density was 2.41 g / cm ³ . BN, AlON, and SiC were identified by X-ray diffraction. The composition estimated by calculation is BN: 28.0 wt%, AlON:
It was 60.7 wt% and SiC: 11.3 wt%.

This sintered body was placed in an atmospheric furnace and set at 1500 ° C.
After heating for 1 hour and allowing to cool, the weight increase was measured.
As a result, the weight increase was as small as 0.03%. Two specimens divided into 1/4 and one specimen divided into 1/2 were prepared from this sintered body, the former was subjected to a corrosion resistance test, and a test piece for bending test of 3 mm x 4 mm x 40 mm was cut out from the latter. It was

A cubic 13Cr steel (a steel containing Cr: 13.0% by weight, C: 0.20% by weight, Si: 0.8% by weight) having a side of 5 mm was provided on one side of the corrosion resistance test piece, and the other had a diameter of 10 mm. 5 mm tablet-like powder compact with a height of 5 mm (SiO
₂ 35.2 wt%, Al ₂ O ₃ 4.1 wt%, CaO 2
(7.5 wt%) was placed thereon, and the mixture was heated to 1550 ° C. in an argon atmosphere, kept at 1550 ° C. for 2 hours, and then allowed to cool. Then, the contact angle of the 13Cr steel after solidification and the contact angle of the slag generated from the tablet-shaped powder compact were measured.
As a result, the contact angle of the 13Cr steel was 110 degrees and the contact angle of the slag was 92 degrees, and this BN-containing material was difficult to be wet with molten steel and molten slag, and no reaction was observed at the contact interface. The result of the 3-point bending test with a span length of 30 mm is 1
It was 70 MPa, and it was confirmed that it was at a level usable as a refractory for casting.

Example 5 B ₄ C having a particle size of 325 mesh pass (particle size of 44 μm or less), Al having a particle size of 200 mesh pass (particle size of 74 μm or less), and SiO ₂ having an average particle size of 5 μm were used. 23.8 wt% and 50.
Mixed at a ratio of 3 wt% and 25.9 wt% and a diameter of 60 m
m in a graphite container with a cavity of 50 mm in height and 100 in
g, and a surface pressure of 10 MPa was applied through a graphite plate having a diameter of 60 mm and a thickness of 5 mm for consolidation. Thus, a molded product having a density of 1.46 g / cm ³ was obtained. This was placed in a graphite heater furnace, exhausted with a vacuum pump, nitrogen gas was introduced, the nitrogen pressure was 0.14 MPa (absolute pressure), the temperature was raised to 700 ° C. at a heating rate of 15 ° C./min, and after holding for 3 hours The sample was again heated to 1500 ° C. at a temperature rising rate of 15 ° C./min, kept for 3 hours and then left to cool.

The weight of the sintered body thus obtained is 1
42 g, and the bulk density was 2.08 g / cm ³ . BN, AlN, SiC, and Al ₂ O ₃ were identified by X-ray diffraction. The composition estimated by calculation is BN: 30.1 wt%,
AlN: 37.2 wt%, SiC: 12.1 wt%, A
I ₂ O ₃ : It was 20.6 wt%.

This sintered body was placed in an atmospheric furnace and set at 1500 ° C.
After heating for 1 hour and allowing to cool, the weight increase was measured.
As a result, the weight increase was as small as 0.17%. Two specimens divided into 1/4 and one specimen divided into 1/2 were prepared from this sintered body, the former was subjected to a corrosion resistance test, and a test piece for bending test of 3 mm x 4 mm x 40 mm was cut out from the latter. It was

A cubic 13Cr steel (a steel containing Cr: 13.0% by weight, C: 0.20% by weight, Si: 0.8% by weight) having a side of 5 mm was used for one side of the corrosion resistance test piece, and the other side had a diameter of 10 mm. 5 mm tablet-like powder compact with a height of 5 mm (SiO
₂ 35.2 wt%, Al ₂ O ₃ 4.1 wt%, CaO 2
(7.5 wt%) was placed thereon, and the mixture was heated to 1550 ° C. in an argon atmosphere, kept at 1550 ° C. for 2 hours, and then allowed to cool. Then, the contact angle of the 13Cr steel after solidification and the contact angle of the slag generated from the tablet-shaped powder compact were measured.
As a result, the contact angle of the 13Cr steel was 110 ° and the contact angle of the slag was 95 °, and this BN-containing material was difficult to be wet with molten steel and molten slag, and no reaction was observed at the contact interface. The result of the 3-point bending test with a span length of 30 mm is 7
It was 2 MPa, and it was confirmed that it was at a level usable as a refractory for casting.

Example 6 B ₄ C having a particle size of 325 mesh pass (particle size of 44 μm or less), Al having a particle size of 200 mesh pass (particle size of 74 μm or less), and SiO ₂ having an average particle size of 5 μm were used. 23.8 wt% and 50.
Mixed at a ratio of 3 wt% and 25.9 wt% and a diameter of 60 m
m in a graphite container with a cavity of 50 mm in height and 100 in
g, and a surface pressure of 10 MPa was applied through a graphite plate having a diameter of 60 mm and a thickness of 5 mm for consolidation. Thus, a molded product having a density of 1.46 g / cm ³ was obtained. This was placed in a graphite heater furnace, exhausted with a vacuum pump, nitrogen gas was introduced, the nitrogen pressure was 0.14 MPa (absolute pressure), the temperature was raised to 700 ° C. at a heating rate of 15 ° C./min, and after holding for 3 hours The sample was again heated to 1900 ° C. at a temperature rising rate of 15 ° C./min, held for 6 hours and then left to cool.

The weight of the sintered body thus obtained is 1
It was 40 g and the bulk density was 2.18 g / cm ³ . BN, AlN, AlON, SiC, Al ₂ O by X-ray diffraction
₃ were identified.

This sintered body was placed in an atmospheric furnace and set at 1500 ° C.
After heating for 1 hour and allowing to cool, the weight increase was measured.
As a result, the weight increase was as small as 0.05%. Two specimens divided into 1/4 and one specimen divided into 1/2 were prepared from this sintered body, the former was subjected to a corrosion resistance test, and a test piece for bending test of 3 mm x 4 mm x 40 mm was cut out from the latter. It was

A cubic 13Cr steel (steel containing 13.0% by weight of Cr, 0.20% by weight of C, 0.8% by weight of Si) having a side of 5 mm was provided on one side of the corrosion resistance test piece, and a diameter of the other was set on the other side. 5 mm tablet-like powder compact with a height of 5 mm (SiO
₂ 35.2 wt%, Al ₂ O ₃ 4.1 wt%, CaO 2
(7.5 wt%) was placed thereon, and the mixture was heated to 1550 ° C. in an argon atmosphere, kept at 1550 ° C. for 2 hours, and then allowed to cool. Then, the contact angle of the 13Cr steel after solidification and the contact angle of the slag generated from the tablet-shaped powder compact were measured.
As a result, the contact angle of the 13Cr steel was 110 ° and the contact angle of the slag was 95 °, and this BN-containing material was difficult to be wet with molten steel and molten slag, and no reaction was observed at the contact interface. The result of the 3-point bending test with a span length of 30 mm is 1
It was confirmed to be 00 MPa, which is a level that can be used as a refractory for casting.

Example 7 B ₄ C having a particle size of 325 mesh pass (particle size of 44 μm or less), Al having a particle size of 200 mesh pass (particle size of 74 μm or less), and SiO ₂ having an average particle size of 5 μm were used. 23.8 wt% and 50.
Mixed at a ratio of 3 wt% and 25.9 wt% and a diameter of 60 m
m in a graphite container with a cavity of 50 mm in height and 100 in
g, and a surface pressure of 10 MPa was applied through a graphite plate having a diameter of 60 mm and a thickness of 5 mm for consolidation. Thus, a molded product having a density of 1.46 g / cm ³ was obtained. This was placed in a graphite heater furnace, exhausted with a vacuum pump, nitrogen gas was introduced, the nitrogen pressure was 0.14 MPa (absolute pressure), the temperature was raised to 700 ° C. at a heating rate of 15 ° C./min, and after holding for 3 hours The sample was again heated to 2200 ° C. at a temperature rising rate of 15 ° C./min, kept for 5 hours and then left to cool.

The weight of the sintered body thus obtained is 1
It was 39 g and the bulk density was 2.21 g / cm ³ . BN, AlON, and SiC were identified by X-ray diffraction. Estimated composition by calculation is BN: 30.1 wt%, AlON: 5
It was 7.8 wt% and SiC: 12.1 wt%.

This sintered body was placed in an atmospheric furnace, and 1500 ° C.
After heating for 1 hour and allowing to cool, the weight increase was measured.
As a result, the weight increase was as small as 0.03%. Two specimens divided into 1/4 and one specimen divided into 1/2 were prepared from this sintered body, the former was subjected to a corrosion resistance test, and a test piece for bending test of 3 mm x 4 mm x 40 mm was cut out from the latter. It was

One side of a corrosion-resistant test piece was a cubic 13Cr steel (a steel containing Cr: 13.0% by weight, C: 0.20% by weight, Si: 0.8% by weight) having a side of 5 mm, and the other side had a diameter. 5 mm tablet-like powder compact with a height of 5 mm (SiO
₂ 35.2 wt%, Al ₂ O ₃ 4.1 wt%, CaO 2
(7.5 wt%) was placed thereon, and the mixture was heated to 1550 ° C. in an argon atmosphere, kept at 1550 ° C. for 2 hours, and then allowed to cool. Then, the contact angle of the 13Cr steel after solidification and the contact angle of the slag generated from the tablet-shaped powder compact were measured.
As a result, the contact angle of the 13Cr steel was 110 degrees and the contact angle of the slag was 98 degrees, and this BN-containing material was difficult to wet with molten steel and molten slag, and no reaction was observed at the contact interface. The result of the 3-point bending test with a span length of 30 mm is 1
It was 90 MPa, and it was confirmed that it was at a level usable as a refractory for casting.

Example 8 B ₄ C having a particle size of 325 mesh pass (particle size of 44 μm or less), Al having a particle size of 200 mesh pass (particle size of 74 μm or less), SiO ₂ having an average particle size of 5 μm, ZrO ₂ having an average particle diameter of 3.5 μm was added to 22.8 wt%, 44.6 wt% and 11.6 w, respectively.
t%, 21.0 wt% and mixed with a diameter of 60 mm,
A graphite container having a cavity with a height of 50 mm was filled with 100 g, and a surface pressure of 10 MPa was applied through a graphite plate having a diameter of 60 mm and a thickness of 5 mm for consolidation. In this way, the density 1.
A molded body of 71 g / cm ³ was obtained. This was placed in a graphite heater furnace, exhausted with a vacuum pump, nitrogen gas was introduced, the nitrogen pressure was 0.14 MPa (absolute pressure), the temperature was raised to 700 ° C. at a heating rate of 15 ° C./min, and after holding for 3 hours The temperature was raised again to 15 ° C./min to 1500 ° C., kept for 3 hours, and then allowed to cool.

The weight of the sintered body thus obtained is 1
It was 45 g and had a bulk density of 2.51 g / cm ³ . BN, AlN, SiC, ZrO ₂ and ZrN were identified by X-ray diffraction.

This sintered body was placed in an atmospheric furnace and set at 1500 ° C.
After heating for 1 hour and allowing to cool, the weight increase was measured.
As a result, the weight increase was as small as 0.29%. Two specimens divided into 1/4 and one specimen divided into 1/2 were prepared from this sintered body, the former was subjected to a corrosion resistance test, and a test piece for bending test of 3 mm x 4 mm x 40 mm was cut out from the latter. It was

One side of a corrosion-resistant test piece was a cubic 13Cr steel (steel containing Cr: 13.0% by weight, C: 0.20% by weight, Si: 0.8% by weight) having a side of 5 mm, and the other side had a diameter. 5 mm tablet-like powder compact with a height of 5 mm (SiO
₂ 35.2 wt%, Al ₂ O ₃ 4.1 wt%, CaO 2
(7.5 wt%) was placed thereon, and the mixture was heated to 1550 ° C. in an argon atmosphere, kept at 1550 ° C. for 2 hours, and then allowed to cool. Then, the contact angle of the 13Cr steel after solidification and the contact angle of the slag generated from the tablet-shaped powder compact were measured.
As a result, the contact angle of the 13Cr steel was 110 degrees and the contact angle of the slag was 105 degrees, and this BN-containing material was difficult to wet with molten steel and molten slag, and no reaction was observed at the contact interface. The result of the 3-point bending test with a span length of 30 mm was 65 MPa, which was confirmed to be at a level that can be used as a refractory for casting.

(Example 9) B ₄ C passing through a mesh of 325 mesh (particle size 44 μm or less), Al passing through a mesh of 200 mesh (particle size 74 μm or less), passing through a mesh of 325 mesh (particle size 44 μm) The following) Si is 28.9
wt%, 56.4 wt%, and 14.7 wt% are mixed, filled in a urethane rubber container and sealed, and 50 MPa.
It was consolidated by applying water pressure. Thus a density of 1.63
Three compacts with g / cm ³ were obtained. 30 from these
Three rectangular parallelepiped samples of mm × 30 mm × 90 mm were cut out. These were placed in a graphite heater furnace, exhausted with a vacuum pump, nitrogen gas was introduced, the nitrogen pressure was 0.14 MPa (absolute pressure), and the temperature was raised to 700 ° C. at a heating rate of 15 ° C./min and held for 3 hours. , 1500 again at a heating rate of 15 ° C / min
The mixture was heated to ℃, kept for 3 hours and then left to cool. In this way 3
A sintered body of a book was obtained.

One end of one of the three sintered bodies was fixed to the rotary shaft and inserted into the alumina crucible from the upper side, and 13
Filled with Cr steel chips. The crucible was sealed with Ar gas, heated to 1550 ° C., held at 1550 ° C. for 20 hours while rotating the sample at a rotation speed of 60 rpm, and then left to cool. After that, cut the crucible together with 10 from the dipping tip.
The diagonal distance of the cross section of the sample at the position on mm was determined. As a result, a decrease of 0.2 mm was recognized, and it was confirmed that the change was slight.

Next, the second sintered body sample was fixed to the rotating shaft and inserted into the graphite crucible from above, and slag powder (SiO ₂ 35.2 wt%, Al ₂ O ₃ 4.1 wt%,
CaO 27.5 wt%) was filled. Ar this crucible
After sealing with gas and heating to 1550 ° C, the rotation speed is 60r
The sample was kept at 1550 ° C. for 20 hours while rotating at pm, and then left to cool. Then, the crucible was cut, and the diagonal distance of the cross section of the sample at a position 10 mm above the immersion tip was obtained. As a result, a decrease of 0.4 mm was recognized, and it was confirmed that the change was slight.

Furthermore, the third sample was taken 10
The powder was cut at a position of mm, and the powder was cut out with an electric drill from the range from the surface to 2 mm and from two points within 10 mm from the surface and subjected to X-ray diffraction. As a result, BN, Al
N, SiC were identified. Estimated average composition by calculation is B
N32.7wt%, AlN54.1wt%, SiC1
Although it was 3.2 wt%, a difference was observed in the X-ray diffraction intensity ratio of AlN and BN between the surface and the inside. When the maximum peak ratio AlN / BN value of X-ray diffraction was compared, this value was 7.8 on the surface, while it was 4.0 inside, and the ratio of both was 1.95. By touching with an electric drill, it was confirmed that the hardness rapidly decreased 8 mm inside from the surface.

For comparison, using the same raw material as the above sample, molding was performed under the same conditions to obtain three compacts, which were sintered without being cut out under the same conditions as the above. After producing a sintered body, these surfaces are
30mm x 30mm x 90mm by shaving with a thickness of 3mm
A rectangular parallelepiped sample of a book was obtained.

Under these conditions, two of these 13Cr steel chips and slag powder (SiO ₂ 35.2 wt%, Al ₂ O ₃ 4.1 wt%,
The same test was performed using CaO 27.5 wt%) to determine the change in the diagonal distance of the sample cross section at a position 10 mm above the immersion tip. As a result, reductions of 2.4 mm and 2.9 mm were recognized, respectively, and the wear amount was larger than that of the above sample.

Further, as a result of X-ray diffraction similarly performed on the third sample, BN, AlN, and SiC were identified, but a significant difference in the value of the maximum peak ratio AlN / BN between the surface and the inside was recognized. I couldn't do it. By the way, even by palpation with an electric drill, no difference in hardness was observed between the surface and the inside.

(Example 10) B ₄ C passing through a mesh of 325 mesh (particle diameter of 44 μm or less), Al passing through a mesh of 200 mesh (particle diameter of 74 μm or less), S having an average particle diameter of 5 μm
iO ₂ is 23.8 wt%, 50.3 wt% and 2 respectively
The mixture was mixed at a ratio of 5.9 wt%, filled into a urethane rubber container and sealed, and a water pressure of 50 MPa was applied for consolidation. Thus, three molded bodies having a density of 1.66 g / cm ³ were obtained. From these, three rectangular parallelepiped samples of 30 mm × 30 mm × 90 mm were cut out. These were placed in a graphite heater furnace, exhausted with a vacuum pump, nitrogen gas was introduced, and the nitrogen pressure was 0.14 MPa (absolute pressure).
After heating to 700 ° C. at a heating rate of 1 min / min and holding for 3 hours, the temperature was raised again to 1500 ° C. at a heating rate of 15 ° C./min, and after holding for 3 hours, it was allowed to cool. In this way, three sintered bodies were obtained.

One end of one of the three sintered bodies was fixed to the rotating shaft and inserted into the alumina crucible from the upper side, and 13
Filled with Cr steel chips. The crucible was sealed with Ar gas, heated to 1550 ° C., held at 1550 ° C. for 20 hours while rotating the sample at a rotation speed of 60 rpm, and then left to cool. After that, cut the crucible together with 10 from the dipping tip.
The diagonal distance of the cross section of the sample at the position on mm was determined. As a result, a decrease of 0.3 mm was recognized, and it was confirmed that the change was slight.

Next, the second sintered body sample was fixed to the rotating shaft and inserted into the graphite crucible from above, and slag powder (SiO ₂ 35.2 wt%, Al ₂ O ₃ 4.1 wt%,
CaO 27.5 wt%) was filled. Ar this crucible
After sealing with gas and heating to 1550 ° C, the rotation speed is 60r
The sample was kept at 1550 ° C. for 20 hours while rotating at pm, and then left to cool. Then, the crucible was cut, and the diagonal distance of the cross section of the sample at a position 10 mm above the immersion tip was obtained. As a result, a decrease of 0.4 mm was recognized, and it was confirmed that the change was slight.

Furthermore, the third sample was taken 10
The powder was cut at a position of mm, and the powder was cut out with an electric drill from the range from the surface to 2 mm and from two points within 10 mm from the surface and subjected to X-ray diffraction. As a result, BN, Al
N, SiC were identified. Estimated average composition by calculation is B
N30.1wt%, AlN37.2wt%, SiC1
2.1 wt% and Al ₂ O ₃ 20.6 wt%, but A
As for the X-ray diffraction intensity ratio of 1N and BN, a difference was recognized between the surface and the inside. When the maximum peak ratio AlN / BN value of X-ray diffraction was compared, this value was 8.0 on the surface, whereas it was 4.7 inside, and the ratio of both was 1.70. By the way, it was confirmed by touching with an electric drill that the hardness rapidly decreased 7 mm inside from the surface.

For comparison, using the same raw material as the above sample, molding was performed under the same conditions to obtain three compacts, which were sintered without being cut out under the same conditions as the above. After producing a sintered body, these surfaces are
30mm x 30mm x 90mm by shaving with a thickness of 3mm
A rectangular parallelepiped sample of a book was obtained.

Under these same conditions as the above sample, two of these 13Cr steel chips and slag powder (SiO ₂ 35.2 wt%, Al ₂ O ₃ 4.1 wt%,
The same test was performed using CaO 27.5 wt%) to determine the change in the diagonal distance of the sample cross section at a position 10 mm above the immersion tip. As a result, reductions of 3.2 mm and 3.9 mm were recognized, respectively, and the amount of wear was larger than that of the above sample.

Further, as a result of X-ray diffraction performed similarly on the third sample, BN, AlN, SiC and Al ₂ O _{3 were obtained.}
Was identified, but the maximum peak ratio AlN /
No significant difference was found in the BN value. By the way, even by palpation with an electric drill, no difference in hardness was observed between the surface and the inside.

(Example 11) B ₄ C passing through a 325-mesh sieve mesh (particle size: 44 μm or less), Al passing through a 200-mesh sieve mesh (particle size: 74 μm or less), S having an average particle diameter of 5 μm
iO ₂ is 23.8 wt%, 50.3 wt% and 2 respectively
The mixture was mixed at a ratio of 5.9 wt%, filled into a urethane rubber container and sealed, and a water pressure of 50 MPa was applied for consolidation. Thus, three molded bodies having a density of 1.66 g / cm ³ were obtained. From these, three rectangular parallelepiped samples of 30 mm × 30 mm × 90 mm were cut out. These were placed in a graphite heater furnace, exhausted with a vacuum pump, nitrogen gas was introduced, and the nitrogen pressure was 0.14 MPa (absolute pressure).
After heating to 700 ° C. at a heating rate of 1 min / min and holding for 3 hours, the temperature was raised again to 1900 ° C. at a temperature rising rate of 15 ° C./min, holding for 6 hours, and then allowed to cool. In this way, three sintered bodies were obtained.

One end of one of the three sintered bodies was fixed to the rotating shaft and inserted into the alumina crucible from the upper side, and 13
Filled with Cr steel chips. The crucible was sealed with Ar gas, heated to 1550 ° C., held at 1550 ° C. for 20 hours while rotating the sample at a rotation speed of 60 rpm, and then left to cool. After that, cut the crucible together with 10 from the dipping tip.
The diagonal distance of the cross section of the sample at the position on mm was determined. As a result, a decrease of 0.2 mm was recognized, and it was confirmed that the change was slight.

Next, the second sintered body sample was fixed to the rotary shaft and inserted into the graphite crucible from above, and slag powder (SiO ₂ 35.2 wt%, Al ₂ O ₃ 4.1 wt%,
CaO 27.5 wt%) was filled. Ar this crucible
After sealing with gas and heating to 1550 ° C, the rotation speed is 60r
The sample was kept at 1550 ° C. for 20 hours while rotating at pm, and then left to cool. Then, the crucible was cut, and the diagonal distance of the cross section of the sample at a position 10 mm above the immersion tip was obtained. As a result, a decrease of 0.5 mm was recognized, and it was confirmed that the change was slight.

Further, the third sample was taken 10
The powder was cut at a position of mm, and the powder was cut out with an electric drill from the range from the surface to 2 mm and from two points within 10 mm from the surface and subjected to X-ray diffraction. As a result, BN, Al
N, SiAl ₇ O ₂ N ₇ , SiC, Al ₂ O ₃ were identified. AlN and AlON (here, SiAl ₇ O ₂
As for the X-ray diffraction intensity ratio of N ₇ ) and BN, a difference was recognized between the surface and the inside. Maximum peak ratio of X-ray diffraction (AlN + AlO
When compared with the value of N) / BN, this value is 7.0 on the surface.
However, the internal ratio was 3.7, and the ratio of the both was 1.89.

For comparison, using the same raw material as the above sample, molding was performed under the same conditions to obtain three compacts, which were sintered without being cut out under the same conditions as the above. After producing a sintered body, these surfaces are
30mm x 30mm x 90mm by shaving with a thickness of 3mm
A rectangular parallelepiped sample of a book was obtained.

Under these same conditions as the above sample, two of these 13Cr steel chips and slag powder (SiO ₂ 35.2 wt%, Al ₂ O ₃ 4.1 wt%,
The same test was performed using CaO 27.5 wt%) to determine the change in the diagonal distance of the sample cross section at a position 10 mm above the immersion tip. As a result, reductions of 3.7 mm and 4.4 mm, respectively, were recognized, and the abrasion amount was larger than that of the above sample.

Further, as a result of X-ray diffraction performed similarly on the third sample, BN, AlN, SiAl ₇ O ₂ N
₇ , SiC, and Al ₂ O ₃ were identified, but no significant difference in the maximum peak ratio (AlN + AlON) / BN value was observed between the surface and the inside. The data of Examples 1 to 11 are collectively shown in Tables 1, 2 and 3.

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

[Table 3]

[0101]

As described above, according to the present invention, inexpensive B ₄ is used without using expensive BN and AlN powders.
A boron nitride-containing material having excellent corrosion resistance to molten metal and molten slag, using C and Al as starting materials, and a method for producing the same are provided. Further, by forming a concentrated layer of AlN and / or AlON on the surface according to the present invention, a boron nitride-containing material further excellent in wear resistance against molten metal and molten slag, and a method for producing the same are provided. The material of the present invention has extremely excellent corrosion resistance and wear resistance to molten metal and molten slag, and since it can be manufactured at low cost, its application range is extremely wide.

Claims (12)

[Claims] 1. A B ₄ C content of 10-70 wt%, 30-90.
A material obtained by heating a mixed powder containing Al of 10 wt% and Si of 10 to 60 wt% to 1300 to 2300 ° C. in a nitriding atmosphere.
˜48 wt% AlN, 6-30 wt% SiC 2. 10 to 70 wt% B ₄ C, 30 to 90
A mixed powder containing wt% Al and 10 to 60 wt% Si was heated to 1300 to 2300 ° C. in a nitriding atmosphere to obtain 22 to 90 wt% BN and 4 to 48 wt% Al.
A method for producing a boron nitride-containing material, comprising obtaining a boron nitride-containing material containing N and 6 to 30 wt% SiC. 3. 22-90 wt% BN, 4-48 wt
% Of AlN and / or AlON, 6~30wt% of SiC, boron nitride containing material characterized by containing Al ₂ O ₃ of 4～30Wt%. 4. 10 to 70 wt% B ₄ C, 30 to 90
A material obtained by heating a mixed powder containing Al of 10 wt% and SiO _{2 of 10} to 60 wt% to 1300 to 2300 ° C. in a nitriding atmosphere, and 22 to 90 wt% of B
N, 4-48 wt% AlN and / or AlON,
6-30 wt% SiC, 4-30 wt% Al ₂ O ₃
A boron-nitride-containing material comprising: 5. 10 to 70 wt% B ₄ C, 30 to 90
A mixed powder containing wt% Al and 10 to 60 wt% SiO ₂ was heated to 1300 to 2300 ° C. in a nitriding atmosphere to obtain 22 to 90 wt% BN and 4 to 48 wt% Al.
N and / or AlON, 6-30 wt% SiC,
A method for producing a boron nitride-containing material, comprising obtaining a boron nitride-containing material containing ₄ to ₃₀ wt% of Al ₂ O ₃ . 6. BN of 22-90 wt%, 4-48 wt
% AlON, 6-30 wt% SiC, boron nitride containing material. 7. 10 to 70 wt% B ₄ C, 30 to 90
A material obtained by heating a mixed powder containing Al at 10 wt% and SiO _{2 at 10} to 60 wt% to 1700 to 2300 ° C. in a nitriding atmosphere, and 22 to 90 wt% B.
N, 4-48 wt% AlON, 6-30 wt% Si
A boron nitride-containing material comprising C. 8. 10 to 70 wt% B ₄ C, 30 to 90
A mixed powder containing wt% Al and 10 to 60 wt% SiO ₂ was heated to 1700 to 2300 ° C. in a nitriding atmosphere to obtain 22 to 90 wt% BN and 4 to 48 wt% Al.
A method for producing a boron nitride-containing material, comprising obtaining a boron nitride-containing material containing ON and 6 to 30 wt% SiC. 9. 22-90 wt% BN, 4-48 wt
% AlN and / or AlON, 6-30 wt% SiC, having a surface with a concentrated layer of AlN and / or AlON having a thickness of 2-10 mm. 10. BN X in the range of up to 2 mm from the surface
AlN and AlO with respect to the diffraction intensity of the maximum peak of line diffraction
Ratio of sum of diffraction intensities of maximum peaks of X-ray diffraction of N (AlN
10. The boron nitride-containing material according to claim 9, wherein the ratio of the value of (+ AlON) / BN and the value of (AlN + AlON) / BN within 10 mm or more from the surface is 1.3 or more. 11. 10 to 70 wt% B ₄ C, 30 to 9
0 wt% Al, 10-60 wt% Si or SiO
_The mixed powder containing ₂ is 1300 to 230 in a nitriding atmosphere.
A material obtained by heating to 0 ° C., which is 22 to 90
Boron nitride containing wt% BN, 4 to 48 wt% AlN and / or AlON, 6 to 30 wt% SiC, and having a concentrated layer of AlN and / or AlON having a thickness of 2 to 10 mm on the surface. Contained material. 12. 10 to 70 wt% B ₄ C, 30 to 9
0 wt% Al, 10-60 wt% Si or SiO
_The mixed powder containing ₂ is 1300 to 230 in a nitriding atmosphere.
Heated to 0 ° C., 22-90 wt% BN, 4-48
wt% AlN and / or AlON, 6-30 wt
% Of SiC and a boron nitride-containing material having a concentrated layer of AlN and / or AlON having a thickness of 2 to 10 mm on the surface thereof is obtained.