JPH05139843A - Production of sintered aqueous containing boron nitride of cubic system - Google Patents

Abstract

PURPOSE:To efficiently produce a tough sintered compact having excellent chipping resistance by wetting starting raw materials comprising silicon, aluminum, iron group metal, etc., with a compound such as borazine before treating the raw materials at high temperature under high pressure. CONSTITUTION:Starting raw materials selected from both groups of a metal group of metals of the groups 4a, 5a and 6a of the periodic table, silicon, aluminum and iron group metals and a metal compound group of compounds of the metals are prepared. The starting raw materials are wetted or immersed in borazine. Borazine, borazine derivatives or a compound of B, N and H to release hydrogen and to form BN by thermal decomposition are generically named as the borazine. Then the wetted or immersed raw material is treated at high temperature under high pressure and BN formed by thermal decomposition of borazine, etc., is converted into boron nitride (CBN) of cubic system. In the operation, hydrogen in a nascent state generated by thermal decomposition of borazine removes oxygen firmly adsorbed on the raw material BN and improves conversion ratio of BN to CBN.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a sintered body containing cubic boron nitride containing at least cubic boron nitride (hereinafter abbreviated as CBN) as one of its constituent components.

[0002]

2. Description of the Related Art Many proposals have hitherto been made as a method for producing a cubic boron nitride sintered body, but these can be roughly regarded as two streams. That is, one of them is CBN once by means of ultra high pressure and high temperature.
And the obtained CBN as a binder metal and / or
Alternatively, it is a method of forming a sintered body by using a means of mixing with a compound and ultra high pressure and high temperature, and another flow is starting from boron nitride (hereinafter abbreviated as BN) as a starting material and using this as a binder metal. And / or a compound, and the BN is converted into CBN by using a means of ultra high pressure and high temperature, and at the same time, a sintered body is formed.

Needless to say, when comparing the two methods, the latter method is preferable because the former method uses the most expensive means of ultra-high pressure and high temperature twice, while the latter method requires only once. However, most of the methods actually used industrially are the former methods. The reason is quite clear. That is, in the latter method conventionally proposed, the conversion from BN to CBN is rarely performed 100%, and the residual BN significantly impairs the properties and performance of the sintered body.

As a method for improving the conversion rate to CBN to some extent, a method using a catalyst substance has been proposed. For example, as described in Japanese Patent Publication No. 51-16199, Co is added as a catalyst to hexagonal boron nitride (hereinafter abbreviated as hBN) and converted to CBN by a high pressure and high temperature reaction,
A method of sintering at the same time, or, as described in JP-B-52-17838, AIN periodic table 1b,
2b, 4a, 5a, 6a, 7a, 8 group element and one or more selected from the group consisting of silicon as a catalyst, h
A method is known in which BN is converted into CBN by a high-pressure and high-temperature reaction and simultaneously sintered.

However, CB produced by these production methods
The boron nitride sintered body containing N as a main constituent phase has a low hardness because of the presence of a metal element as a binding component and has poor properties when used as a tool material. In addition, it has thermal conductivity and chemical stability in other applications. Etc. had a low defect.

[0006]

In order to eliminate these drawbacks, the present inventors have previously proposed a method for producing a CBN sintered body using BN as a starting material, which does not use a metal catalyst at all. JP-A-55-32771 (JP-B-58-3442)
9) is that. This method uses BN as a starting material.
And A acting as a catalyst in the conversion reaction of CBN to CBN
After mixing IN, filling it in an appropriate container, and further injecting an organic solvent such as xylene, toluene, ethyl alcohol, etc. into this to adjust the oxygen content in the container to 2% by volume or less, and then BN exposed to ultra high pressure and high temperature
Is a method of obtaining a sintered body at the same time as converting CBN into CBN. According to this method, the organic solvent releases bound hydrogen in the process of ultrahigh pressure and high temperature treatment, and the hydrogen of this generator is the raw material B.
The harmful oxygen existing physically and chemically in N is removed, and BN is completely converted into CBN in combination with the catalytic action of AIN, and at the same time, a sintered body in which CBN members are bonded is obtained. .. However, as a result of further detailed study of the sintered body obtained by the above method, the present inventors have found out that it has the following drawbacks. That is, the organic solvent such as xylene and toluene acts as described above to remove harmful oxygen existing in the raw material BN, convert to CBN, and contribute to the formation of a sintered body. It is known that carbon is left behind, which hinders the bonding between CBNs and makes the strength of the sintered body insufficient.

[0007]

The present invention has been completed on the basis of the above findings, and is a group of metals of group 4a, 5a, 6a of the periodic table, silicon, aluminum and iron group metals as starting materials. And at least one selected from both groups of compounds of these metals, borazine, a derivative of borazine, and / or a compound of boron, nitrogen, and hydrogen that releases hydrogen by thermal decomposition to form boron nitride (collectively: , Borazine, etc.) in a wet or dipped state, and then filled in a suitable high-pressure container, and then embedded in a suitable high-pressure device together with the high-pressure container at a pressure of 4.5 GPa.
As described above, the temperature is raised to 700 ° C. or higher, the pressure and the temperature are maintained for an appropriate time corresponding to the selected pressure and the temperature, and BN is formed by thermal decomposition of the borazine in the starting material. Is converted into CBN and a tough sintered body containing the CBN is formed.

A feature of the present invention is that the starting material is filled in a high-pressure container in a wet or dipped state with borazine or the like before being subjected to the ultra-high pressure and high temperature treatment. The inventors have obtained the following important findings through repeated studies on their actions and effects.

First, borazine or the like is added so as to fill the voids of the mixed powder, which is the starting material, to expel air from the voids. As a result, the amount of oxygen in the container filled with the mixed powder is kept at 2% by volume or less, and by satisfying this condition, the conversion rate from BN to CBN is remarkably improved.

Secondly, the borazine and the like added so as to fill the voids are thermally decomposed in the process of heating under pressure to release hydrogen, but the hydrogen of this generator is physically and chemically converted into the raw material BN. The stubborn oxygen bound to or adsorbed on is removed to further enhance the first effect.

Thirdly, the borazine and the like are thermally decomposed in the process of heating under pressure as described above, releasing hydrogen to leave BN in the end, but the thermally decomposed BN under pressure obtained in this way has extremely high purity. While high, the degree of crystallinity is relatively low.
Is the most preferred for CBN synthesis. That is, according to the research conducted by the inventors, the activation energy required for conversion of commercial BN having high crystallinity and amorphous BN having high purity and low crystallinity obtained by thermal decomposition under pressure from borazine into CBN is , In the presence of AIN, the former is 40 to 60 Kcal / mol, while the latter is about 20 Kcal / mol, and therefore, BN with high purity and low crystallinity has a very high conversion rate to CBN. ..

That is, in the previous invention (JP-A-55-32771) by the inventors of the present invention, the added xylene and the like left harmful carbon in the CBN sintered body, whereas in the present invention, CBN was used. That is, BN having the most preferable properties for the synthesis of and the formation of its sintered body was left.

[0013]

The function and effect of the addition of borazine, which is the most important feature of the present invention, is clear, and as a result, the function and effect of the present invention is also extremely clear. This will be described in more detail.

Borazine is a liquid at room temperature and atmospheric pressure. The starting material to be filled in the high-pressure container is prepared by blending and mixing each component powder before filling, but so-called wet mixing may be performed while wetting with borazine or the like. In the conventional method, generally, dry mixing is performed, and then an appropriate green compact is made with this mixed powder, and this is filled in the above-mentioned high-pressure container, but when wet mixing with borazine as described above, the above green compact is used. It is also possible to omit the forming step and fill the high-pressure container with the mixed powder in a wet state as it is.

When adopting a method of producing a green compact by a molding press as in the conventional dry mixing, the apparent density of the green compact can be made appropriate by appropriately selecting the molding pressure. Conversely speaking, the injection amount of borazine or the like is determined according to the porosity of the green compact, and the injected borazine or the like fills all the gaps between the component particles constituting the green compact and is substantially 100%. The starting material, borazine, and the like fill the above-mentioned high-pressure container in the state of density. This not only has the effect of expelling the air existing between the gaps between the component particles, but also realizes a pressure state extremely close to the hydrostatic pressure in the high-pressure container in the process of forming the sintered body, and conversion to CBN and It can be said that it is an ideal condition for forming a sintered body.

Further, borazine, which continuously fills the space between the component particles, releases hydrogen during the sintering process and is thermally decomposed, and the hydrogen in the generator purifies each component particle in the high-pressure container. To do. The BN remaining after the thermal decomposition continuously circulates between the component particles of the starting material and is converted into CBN in the starting material under the conditions of ultrahigh pressure and high temperature to form a continuous three-dimensional network structure. To do.

When the starting material contains a hard compound such as WC or TiC, the hard compound undergoes plastic deformation under ultrahigh pressure and high temperature while undergoing sintering to form a continuous three-dimensional network structure with each other. In many cases, the network structure of CBN and the network structure of the hard compound are entangled with each other, and as a result, an extremely strong sintered body containing cubic boron nitride is formed.

When the amount of CBN is relatively small, and therefore the amount of hard compound is relatively large, the network structure of CBN may be incomplete, but in this case, the network structure of the hard compound is complete and the whole structure. Keep the strength of C and vice versa
The network structure of BN is developed and the overall strength is maintained.

The most important point of the present invention is to add borazine or the like to the starting material, as described repeatedly. Therefore, there are a great variety of embodiments that can be developed to satisfy this basic requirement.

Specific examples will be described below.

[0021]

Example 1 50% by volume TiC, 20% by volume Ti
N, 20% by volume WC, 2% by volume Ni, 1% by volume N
A starting material consisting of b and 7% by volume of Al was placed in a zirconium capsule and was subjected to embossing at a pressure of 660 kgf / cm ² to produce a green compact having a porosity of 44%. Inject borazine into this, seal the capsule and bury it in a high-pressure device, raise the pressure to 6.5 GPa first, then raise the temperature to 700 ° C., hold it here for 10 minutes, and then continue. The temperature was raised to 1400 ° C and held at this temperature for 20 minutes. The present invention sample 1 was obtained after the temperature was lowered.

A strong diffraction peak due to CBN was observed from the sample 1 of the present invention by the X-ray diffraction test, and the borazine injected during the process released hydrogen by high pressure and high temperature treatment to release C.
It was confirmed that it was converted to BN.

When the sample 1 of the present invention is observed under a microscope, the phases of the CBN converted from borazine and the TiC-TiN-WC- (Ni-Nb-Al) alloy sintered from the starting material are entangled with each other, It was recognized that it formed a three-dimensional network structure to form a tough sintered body as a whole.

A turning bit edge was produced from Sample 1 of the present invention, and an intermittent cutting test was attempted on an SCM carburized and hardened steel (surface hardness HRC62). Work material diameter 250 mm, 2 slot type, cutting speed 100 m / min, depth of cut 0.25 mm,
When an intermittent test was attempted under a feed condition of 0.15 mm / rev dry type, it was confirmed that chipping still did not occur even after cutting for 12 minutes, and that Sample 1 of the present invention was a tool material having excellent chipping resistance.

[0025]

Example 2 40% TiN-20% WC-7% Co-3
A green compact was made under the same conditions as in Example 1, using a starting material composed of 3% Al (volume%). This was embedded in a high-pressure apparatus in the same manner as in Example 1, and the holding temperature was 1500 ° C.
Sample 2 of the present invention was obtained by treating under the same conditions as in Example 1 except that the holding time was 30 minutes.

When the sample 2 of the present invention is observed under a microscope, the CBN converted and synthesized from borazine and the starting material are sintered and entangled with each other, which forms a three-dimensional network structure and is a tough sintered body as a whole. Were found to be formed.

As a result of an intermittent cutting test of Sample 2 of the present invention under the same conditions as in Example 1, chipping still did not occur even after cutting for 20 minutes, and Sample 2 of the present invention was a tool material excellent in chipping resistance. It was confirmed that

[0028]

INDUSTRIAL APPLICABILITY The present invention provides a simple and extremely efficient and economically excellent effect regarding the method for producing a sintered body of CBN, and the sintered body obtained by the method of the present invention is When used as a cutting tool, it has an excellent chipping resistance.

Claims (1)

[Claims] A starting material comprising at least one selected from the group consisting of metals of groups 4a, 5a and 6a of the periodic table, metals of silicon, aluminum and iron and compounds of those metals is borazine or borazine. And / or a method of producing a sintered body containing cubic boron nitride by wetting or soaking with a compound of boron, nitrogen and hydrogen that releases hydrogen by thermal decomposition under pressure and produces boron nitride.