JPH0524922A - Diamond-containing combined sintered compact with high hardness and high density and production of the same - Google Patents

Abstract

PURPOSE:To produce a diamond-containing combined sintered compact with high hardness and high density in the gentle sintering conditions of relatively low pressure and temp. Where diamond is not thermodynamically stable, to mass-produce relevant sintered compact, and to produce a large-sized member having complicated shape. CONSTITUTION:The diamond-containing combined sintered compact is made by applying diamond powder as they are or a coating material and by sintering the applied diamond powder at a pressure of <2000MPa and a temp. not exceeding 1850 deg.C the dense and high hardness binder having >=85% density and >=600 Vickers hardness is obtd. and the raw materials of the relevant binder are mixed. In the quasi-stable sintering condition where the pressure is <=2000MPa and the temp. does not exceed 1850 deg.C, the compact is sintered for a proper time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dense and high hardness composite sintered body containing diamond and a method for producing the same.

[0002]

2. Description of the Related Art A dense, high-hardness, high-hardness, high-density composite sintered body containing diamond prevents a phase transition of diamond to a graphite phase, and In order to sinter into diamond, diamond was produced at ultrahigh pressure and temperature above 2000 MPa, which is thermodynamically stable. For example, the report of T.NOMA et al. (J. Mater. S
According to cie. 19 (1984) 2319-2322), diamond is sintered at 6000 MPa (60 kb) at temperatures above 1300 ° C. These sintering conditions are extremely strict as extreme conditions,
For example, it could not occur without using an ultrahigh pressure device such as a girdle type or belt type.

[0003]

Therefore, due to the restriction of using the ultrahigh pressure device such as the girdle type or belt type, which generates an ultrahigh pressure exceeding 2000 MPa, the diamond-containing high hardness and high density composite firing is performed. It was difficult to mass-produce the aggregate, and the production cost was high, and a large-sized product could not be produced.

However, Hall
According to the experiment under ultrahigh pressure, even if the diamond is not thermodynamically stable, if it is thermodynamically metastable, the phase transition takes an extremely long time, so that the diamond is practically stable. The line is reported as an upper limit that exists in fact (HTHall, Science, 169 (1970) 8
68-869). Therefore, according to this, even under conditions of low pressure and high temperature that are not stable with respect to the thermodynamic equilibrium line, at a temperature that does not exceed the line, for example, when the pressure is up to about 35 kb,
Up to 1400K (about 1100 ℃), diamond is practically stable.

[0005]

[Figure 1]

That is, at the time of sintering a diamond-containing high-hardness high-density composite sintered body using a high-performance, dense and high-hardness binder and diamond, at least the high-performance, dense and high-hardness bond is obtained. If a pressure that is effective only for promoting the densification of the material is applied, it is possible to manufacture a high-hardness high-density composite sintered body containing diamond, and it is possible to apply a relatively loose ultra-high pressure of less than 2000 MPa. High-pressure device, for example, piston-cylinder (PC) type ultra-high pressure device, or ultra-high pressure H that can pressurize up to 1000 MPa as known technology
IP device or hot isostatic press (HIP: Hot Isostatic Pres excluding the ultra high pressure HIP device)
s) device or hot press (HP: Hot Pr)
ess) device can be used.

Therefore, for example, the PC type ultra high pressure device,
Alternatively, a raw material for a dense and high-hardness binder that is capable of sufficiently dense sintering and has high performance by using an ultra-high pressure HIP device, or an HIP device other than the ultra-high pressure HIP device, or an HP device is searched for. Then, the PC type ultra high pressure device, the ultra high pressure HIP device, or the HIP excluding the ultra high pressure HIP device
Unlike the above-mentioned girdle type or belt type ultra-high pressure device that generates ultra-high pressure exceeding 2000 MPa, it is easy to mass-produce and it is possible to manufacture large-sized sintered compacts by the device or HP device. Therefore, the above drawbacks are solved.

[0008]

DISCLOSURE OF THE INVENTION The present invention is a PC type ultra high pressure device capable of operating a relatively gentle ultra high pressure of less than 2000 MPa, or an ultra high pressure HIP device capable of pressurizing up to 1000 MPa,
Alternatively, by using a HIP device or an HP device other than the ultra-high pressure HIP device, the temperature at which diamond actually exists in a stable state in each sintering environment is experimentally investigated, and at the same time, the temperature As a result of diligent research on the density and hardness of the binder that can be applied as a sufficiently dense and highly sinterable binder, the diamond powder is 1% to 90% by volume, and the balance is pressure. Is less than 2000MPa, 18
By sintering at a temperature not exceeding 50 ° C, a density of 85
% Or more, consisting of a dense and high-hardness binder having a Vickers hardness of 600 or more, the raw material of the binder is mixed in a volume of 99% to 10%, and the mixture is subjected to pressure or pressure after molding.
If the temperature is less than 2000MPa, the temperature does not exceed 1850 ℃, the diamond is not thermodynamically stable, but is sintered for a suitable time under the conditions of metastable pressure and temperature, or the diamond powder particles are coated with a coating material. Coated diamond powder by volume of 1% ~
90%, the balance is a dense and high-hardness binder with a density of 85% or more and a Vickers hardness of 600 or more by being sintered at a pressure of less than 2000 MPa and a temperature not exceeding 1850 ° C. After mixing 99% to 10% by volume of the above raw materials, and pressing or molding the mixture, the pressure is less than 2000MPa, the temperature does not exceed 1850 ℃, the diamond is not thermodynamically stable. Invented a method for producing a diamond-containing high-hardness high-density composite sintered body, which substantially does not contain a graphite phase, by appropriately sintering under a metastable pressure / temperature sintering condition. Body in volume
1% to 90%, the rest is sintered at a pressure of less than 2000MPa and at a temperature not exceeding 1850 ℃, resulting in a density of 85% or more,
Mixing 99% to 10% by volume of the binder raw material, which is a dense and high hardness binder with Vickers hardness of 600 or more,
After the mixture is molded or stamped, the pressure is 2000MP.
less than a, the temperature does not exceed 1850 ℃, diamond is not thermodynamically stable, but it is composed of a sintered body that is sintered for a suitable time under the conditions of metastable pressure and temperature. 1% to 90% content, the balance is sintered at a pressure of less than 2000MPa and at a temperature not exceeding 1850 ℃, so that a dense and high-hardness binder with a density of 85% or more and a Vickers hardness of 600 or more can be obtained. Which has a density of 85% or more and a Vickers hardness of 600 or more, a high hardness and high density composite sintered body containing diamond, or a coating material is added to the diamond powder particles by external addition. 1% ~ 90% by volume of coated diamond powder, the balance is 0.1% ~ 2000% coating, the balance is less than 2000MPa, 1850
By sintering at a temperature not exceeding ℃, the density is 85%.
As described above, the binder raw material made of a dense and high-hardness binder having a Vickers hardness of 600 or more is mixed in a volume of 99% to 10%, and the pressure of the mixture is 20% or more after molding or molding.
It is composed of a sintered body that is less than 00MPa, the temperature does not exceed 1850 ℃, and the diamond is not thermodynamically stable, but is sintered for an appropriate time under the conditions of metastable pressure and temperature. 1% to 89.9% content, coating material, and pressure of less than 2000MPa and sintering at a temperature not exceeding 1850 ℃, resulting in a dense and high hardness bond with a density of 85% or more and a Vickers hardness of 600 or more. Material by volume
99% to 10.1%, density 85% or more, Vickers hardness 60
The present invention is to provide a high hardness and high density composite sintered body containing diamond having 0 or more, and to provide these.

Description of Means Diamond Raw Material Diamond as the raw material powder of the present invention may be either a natural product or a synthetic product. The particle size of the diamond is not particularly limited and is a size suitable for use as a product after sintering within a range that can be produced as the raw material. In the case of a natural product, an ultra-high purity product can be selected, which is preferable. When diamond is a synthetic product, it is preferable to remove as much as possible the substance used as the catalyst during the synthesis in order to suppress the phase transition to these graphite phases. The most preferable example of the synthetic product is, for example, a physical vapor deposition method (PVD method) or a chemical vapor deposition method (CVD).
Method), ultra-high-purity diamond synthesized via the gas phase can be selected. When synthesized into a thin film,
Grind before using, paying attention to contamination by impurities.
When it is synthesized in a granular or powder form, it can be used as it is. As a high-purity example other than this, a single crystal can be selected. Alternatively, diamond powder obtained by actively removing impurities can be selected.

The coating material diamond reacts with carbon so as not to promote the phase transition to the graphite phase, or to enhance the sinterability of the diamond powder particles and the raw material of the binder, for example. In order to generate a substance, the diamond powder particles are used as a coating material in Periodic Table 1b, 2
a, 3a, 4a, 5a, 6a, 7a, 8 group metals, rare earth metals, Si, B
, Al, or a coating material composed of one or more selected from compounds containing one or more of them. On the diamond powder surface coated in this way, if necessary, further, the periodic table 1b,
2a, 3a, 4a, 5a, 6a, 7a, Group 8 metals, rare earth metals, Si,
One or more selected from B, Al, or a compound containing at least one of them may be coated in a single layer or multiple layers. The coating amount that can be applied to diamond is the periodic table 1b, 2a, 3a,
4a, 5a, 6a, 7a, Group 8 metals, rare earth metals, Si, B, Al,
Alternatively, 0.1% to 2000% by volume of diamond can be coated with one or more selected from the compounds containing one or more of these by external addition to diamond. Or, the periodic table 1b, 2a, 3a, 4a, 5a, 6a, 7a, 8
The amount of one or more selected from the group metals, rare earth metals, Si, B, and Al added to diamond by external addition is
It can coat 0.1% to 1000% by volume. The coating material made of a compound is preferably Periodic Table 1b,
2a, 3a, 4a, 5a, 6a, 7a, Group 8 metals, rare earth metals, Si,
At least one selected from B 2, Al oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides, oxycarbonitrides, borides, and silicides is selected.

The coating method is the PVD method (preferably,
Sputtering method, ion plating method), CVD
Method, a plating method, a dipping method using a molten salt bath (preferably a disproportionation reaction method), or the like.

The raw material of the binder according to the present invention has a minor axis of 50.
When a fibrous substance composed of one or more kinds of metals or compounds having a shape of 0 μm or less and a ratio of the major axis to the minor axis of 2 or more is included, the high hardness and high density composite sintered body containing diamond of the present invention has high strength. This is preferable because it can be expected to have toughness. In the present invention, a rod-shaped substance having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more and / or continuous fibers and / or crystals formed of continuous fibers by melt-spinning into a fiber shape Short fibers consisting of self-supporting fibers that themselves take the form of fibers and /
Alternatively, it is composed of a whisker formed by unidirectional crystal growth into a fiber shape. The whisker (beard crystal)
Is a true crystal that is defined by the fact that in its formation, the phenomenon of a phase change or a chemical reaction affecting the entire volume does not occur, and / or a crystal of a crystal produced by a phase change or a chemical change affecting the entire volume. A single crystal with a broad definition of whiskers and / or a cross-sectional area of 8 × 10 ^-5 in ² or less and a length of 10 times or more of the average diameter, which refers to a single crystal that has become a long needle-like crystal by growing only the plane. It consists of whiskers.

As the fibrous substance, periodic table 1b, 2
a, 3a, 4a, 5a, 6a, 7a, 8 group metal, rare earth metal, B, S
i, Al, or a fibrous substance composed of one or more kinds of compounds containing one or more of these and having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more . In the compound, more specifically, the periodic table 1b, 2
a, 3a, 4a, 5a, 6a, 7a, 8 group metal, rare earth metal, B, S
i, containing one or more of oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides, oxycarbonitrides, borides, and silicides of Al, with a minor axis of 500 μm or less, A fibrous substance having a shape in which the ratio of the major axis to the minor axis is 2 or more is used. Preferably, for example, Ta, Zr, Cr, Si, C, W, B
, Mo, Nb, V, Al ₂ O ₃ , Fe ₂ C, B ₄ C, SiC, TiC, Fe
₃ C, Ta ₂ C, Nb ₂ C, Si ₃ N ₄ , Cr ₂ N, AlN, Si ₂ ON ₂ , TiN with a minor axis of 500 μm or less and a major axis relative to the minor axis. A fibrous material having a shape with a ratio of 2 or more is selected.

Alternatively, the fibrous substance having a shape in which the minor axis is 500 μm or less and the ratio of the major axis to the minor axis is 2 or more is formed on the surface of the fibrous material by periodic table 1b, 2a, 3a, 4a,
5a, 6a, 7a, group 8 metal, rare earth metal, B, Si, Al, or a coating material consisting of one or more compounds containing at least one of these, and A coated fibrous material having a ratio of 2 or more is used. In the compound, more specifically,
The fibrous substance having a shape in which the minor axis is 500 μm or less and the ratio of the major axis to the minor axis is 2 or more is formed on the surface of the fibrous material by periodic table 1b, 2a, 3a, 4a, 5a, One or more of 6a, 7a, 8 group metals, rare earth metals, B, Si, Al oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides, oxycarbonitrides, borides, and silicides A coating substance having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more, which is formed by coating a coating material, is used. Suitably, on the surface of the fibrous material, for example,
B, Ti, Zr, Hf, Ta, Nb, V, SiC, TiC, ZrC, B ₄ C
, WC, HfC, TaC, NbC, Si ₃ N ₄ , TiN, ZrN, AlN,
HfN, TaN, TiB, TiB ₂ , ZrB ₂ , LaB ₆ , MoSi ₂ , BP, Al
A coated fibrous substance having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more, which is formed by coating a coating material made of one or more kinds of ₂ O ₃ , is selected. The coating method for coating the coating material includes a dipping method using a molten salt bath, an electroplating method, an electroless plating method, a clad method, a PVD method (for example, a sputtering method, an ion plating method), and CVD. It can be done by the law. Alternatively, the fibrous substance or the coated fibrous substance having a shape in which the minor axis is 500 μm or less and the ratio of the major axis to the minor axis is 2 or more is a fibrous material or a coated fibrous material. , The oxide film is provided on the surface of the fibrous substance or the coated fibrous substance by being oxidized in an oxidizing atmosphere, and the minor axis is 500.
A coated fibrous substance or a coated fibrous substance having a shape in which the ratio of the major axis to the minor axis is 2 or more at μm or less can be selected.

On the other hand, as the raw material of the binder for the high-pressure boron nitride-containing high hardness and high density composite sintered body of the present invention and the method for producing the same, the pressure is less than 2000 MPa and the temperature is not more than 1850 ° C. The raw material of the binder, which is a dense and high-hardness binder having a density of 85% or more and a Vickers hardness of 600 or more, is selected by the sintering. Preferably, a raw material for the binder is selected which does not promote the phase transition of diamond into the graphite phase. Alternatively, by sintering at a pressure of less than 2000 MPa and not exceeding 1850 ° C, the density of the reaction product formed by reacting with carbon is 85% or more and the Vickers hardness is 600 or more. A raw material of the binder, which is a binder, is selected. More preferably, the pressure is less than 2000 MPa,
By sintering at a temperature not exceeding 50 ° C, the density
90% or more dense and / or Vickers hardness of 800
A raw material for the binder, which is made of the above-mentioned high-hardness binder, is selected. The raw material of the binder is Periodic Table 1b, 2a, 3a,
4a, 5a, 6a, 7a, Group 8 metals, rare earth metals, Si, B, Al,
Alternatively, one containing a raw material powder consisting of one or more selected from compounds containing one or more of these is selected. In the compound, more specifically, the periodic table 1b, 2a,
3a, 4a, 5a, 6a, 7a, 8 group metals, rare earth metals, Si, B,
A raw material powder made of one or more selected from Al oxide, nitride, carbide, oxynitride, oxycarbide, carbonitride, oxycarbonitride, boride, and silicide is selected.

In the case of alumina which is an oxide of Al, a fine raw material having high purity and easy sinterability, for example, alumina produced by the pyrolysis method of ammonium-aluminum carbonate described in JP-A-63-151616. Also, normal sintering under normal pressure is suitable because it densifies at a temperature of about 1400 ° C. Furthermore, if the fine and high-purity alumina powder contains up to 10% by volume of magnesia (MgO) and / or titania (TiO _x , X = 1-2), which has the effect of promoting the sintering of alumina, JP-A-63-1
High-purity alumina other than the alumina described in 51616,
For example, by the Bayer method, organoaluminum hydrolysis method, ammonium alum pyrolysis method, ethylene chlorohydrin method, underwater spark discharge method, etc., high purity and easy sinterability of 99% or more consisting of fine particles of 1 μm or less. Alumina can be used.

Other than the above-mentioned alumina, zirconium oxide, preferably yttrium-added partially stabilized zirconia (2-4 mol% Y ₂ O ₃ -Zr), which is easily sinterable and is produced by a coprecipitation method.
O ₂ ) powder or alumina-zirconia-based powder (FC report, 1 [5] (1983) 13-17) and titanium oxide titania powder (TiO ₂ : 15th high-pressure discussion meeting Proceedings, (197
3) P174) is selected.

As the titanium nitride, titanium nitride is used.
(TiN: Yamada Soga, Journal of Ceramic Industry, 89, (1981) 621-625) is also available.

Upper limit of temperature Particularly high-purity diamond, for example, high-quality natural diamond or synthetic product, is subjected to PVD method or CVD method.
Ultra-high-purity diamond synthesized through the gas phase,
If ultra-high-purity diamond that has been synthesized under ultra-high pressure for a long time is used, it is degassed and encapsulated in a capsule capable of transmitting pressure to carry out ultra-high pressure HIP sintering or HIP sintering, or in vacuum or in an inert gas. By performing HP sintering, diamond is practically stable up to 1850 ° C., which is much higher than 1100 ° C. reported by Hall, even if it is not in a thermodynamically stable state. However, when it exceeds 1850 ° C, it undergoes a phase transition to a graphite phase in a short time. Generally, in the case of synthetic diamond, a catalyst for synthesis may remain as impurities. However, if one made of high-purity diamond obtained by actively removing impurities is used, both natural products and synthetic products have diamond up to 1700 ° C. by the same sintering method. Alternatively, if a known diamond which does not contain fine particles and preferably has a particle size of 3 μm or more is used, diamond is present up to 1600 ° C. in both natural products and synthetic products by the same sintering method. Alternatively, in the case of known relatively high-purity diamond, both natural products and synthetic products have diamond up to 1500 ° C. by the same sintering method. However, in the case of known general synthetic diamond, the temperature up to 1400 ° C. is suitable.

Therefore, the upper limit of the sintering temperature is 1850 ° C.
As mentioned above, depending on the quality of the diamond used,
Since the temperature at which diamond exists is different, it is necessary to set the sintering temperature according to the quality of the diamond raw material.
When it is necessary to set the sintering temperature close to the temperature corresponding to the quality of the diamond raw material, it is necessary to carefully control the sintering temperature.

Pressure Range The present invention is, as described above, a PC type ultrahigh pressure device or an ultrahigh pressure H which is capable of operating a relatively gentle ultrahigh pressure of less than 2000 MPa.
Regarding the production of a diamond-containing high hardness and high density composite sintered body using an IP device, a HIP device or a HP device, the upper limit of the sintering temperature is 1850 ° C. It clarifies the application conditions of the material and clearly shows that it is not necessary to apply a pressure for the diamond to be in a thermodynamically stable state.

Therefore, when the PC type ultra high pressure device is used, the pressure may be less than 2000 MPa, but it is 1500 when considering the durability of the PC type ultra high pressure device.
It is preferable not to exceed MPa. As a known technique for generating pressure, HIP pressure can act up to 1000 MPa in the case of an ultra-high pressure HIP device, and up to 200 MPa in the HIP device and HP device excluding the ultra-high pressure HIP device.

In particular, the ultrahigh pressure HIP device or the ultrahigh pressure HIP
When using HIP equipment other than IP equipment, the density of 85% or more or the density is obtained by sintering diamond powder or coated diamond powder at a pressure of less than 2000 MPa at a temperature not exceeding 1850 ° C. 90% or more, Vickers hardness of 600 or more or Vickers hardness of 800 or more, made of a dense and high-hardness binder, made by mixing the raw materials of the binder, the mixture can be pressure-transmitted after the mold is molded or stamped By degassing and encapsulating the container, which has been degassed and sealed in a container capable of further pressure transmission, by repeating degassing and encapsulation more than once, the pressure is less than 2000 MPa and the temperature is less than 2000 MPa. The diamond may not be thermodynamically stable at 1850 ° C., but may be sintered for a suitable time under a metastable sintering condition of pressure and temperature.

The Vickers hardness of the diamond-containing high hardness and high density composite sintered body obtained by sintering by the above method is
It is possible to manufacture a high-hardness high-density composite sintered compact containing diamond, which has a high hardness of 800 or more and / or a density of 90% or more.

The diamond-containing high hardness and high density composite sintered body of the present invention and the method for producing the same will be described below with reference to examples.

[0026]

【Example】

Example 1 The surface of diamond powder particles was coated with alumina, which is an oxide of Al, by a sputtering method, and the coated diamond powder particles were used as a raw material of an inorganic material, which had high purity and were easily sinterable. Alumina
63-151616) and a method for producing a high hardness and high density composite sintered body containing diamond and a method for producing the same will be described in more detail.

Diamond powder particles (particle size 0 to 1 μm)
Using alumina as a target, the surface of was coated with diamond by sputtering to a volume of 10% by external addition.

33% by volume of the coated diamond powder particles was used as the raw material powder for the binder, and was disclosed in
-151616 gazette, high purity with an average particle size of 0.2 μm
65.4% by volume of easily sinterable alumina powder, and magnesia (MgO) and titania as sintering aids for the alumina powder.
(TiO _x , x = 1-2) was added in a volume of 0.6% and 1.0%, respectively. Using an alumina ball mill, these were wet mixed in acetone for 2 hours. Then, the mixed powder was vacuum dried at 10 ⁻⁶ torr and 200 ° C.

[0029] Next, a disk-shaped mold having a diameter of 16 mm and a thickness of 5 mm was embossed, and the molded body was placed in a capsule made of Pyrex glass filled with hBN powder, and a pressure of 10 ^-6 torr, 400 ° C,
It was degassed for 12 hours and then sealed.

The capsule is placed in a HIP device using argon gas as a pressure medium, and the sintering temperature is 1200 ° C. and the sintering pressure is 15
It was held at 0 MPa for 3 hours for sintering. Thereafter, the furnace was cooled, the pressure was released, and the sintered body was taken out.

As shown in Table 1, the sintered body has a density of 98.1.
% Is very precise, and the Vickers micro hardness is Hv
(0.5 / 10): 2620, which was a very high hardness.

[0032]

[Table 1]

When the crystal phase of the sintered body of Example 1 was examined by X-ray diffraction, diffraction peaks other than those of diamond and alumina were not recognized.

Examples 2 to 3 The coated diamond and magnesia (M
gO) and titania (TiO _x , X = 1-2) in a mixing ratio of alumina of 50:50 to 60:40, the sample size is 8 mm in diameter,
Except that the thickness was set to 5 mm, it was prepared in substantially the same manner as in the manufacturing method of Example 1, and thereafter, using an ultra high pressure HIP apparatus, the sintering temperature was
Sintering was performed at 1200 ° C. and a sintering pressure of 1000 MPa for 3 hours.

The sintered body has a density of 92.0 as shown in Table 1.
% To 94.8%, it was very dense, and the Vickers microhardness was Hv (0.5 / 10): 2300 to 2780, which was a very high hardness.

When the crystal phases of the sintered bodies of Examples 2 to 3 were examined by X-ray diffraction, diffraction peaks other than those of diamond and alumina were not recognized.

Examples 4 to 5 Titanium carbide (TiC) was added to the surface of diamond powder particles (particle size 0 to 1 μm) by external addition to diamond to be about 10% by volume. Coating was performed by a dipping method (disproportionation reaction method) using a molten salt bath.

50% to 60% by volume of the coated diamond powder particles are used as a raw material powder for the binder, and a high-purity, easy-to-use powder having an average particle size of 0.2 μm described in JP-A-63-151616 is used. 48.4% to 38.4% by volume of sinterable alumina powder,
And magnesia (Mg
O) and titania (TiO _x , X = 1-2) were added by volume of 0.6% and 1.0%, respectively. Using an alumina ball mill, these were wet mixed in acetone for 2 hours. Then 10 ^-6 to
The mixed powder was vacuum dried at rr and 200 ° C.

Next, a disc-shaped die having a diameter of 10 mm and a thickness of 8 mm was embossed and embedded in a pyrophyllite pressure medium having an hBN compact on the outside, which was used in a piston-cylinder (PC) type ultra-high pressure device. Set, sintering temperature 1200 ℃,
The sintering pressure was 1800 MPa and the sintering was performed for 3 hours. After that, the temperature was lowered and the pressure was lowered to take out the sintered body.

The sintered body has a density of 94.6 as shown in Table 1.
It was very dense at ~ 96.1, and had a very high Vickers microhardness of Hv (0.5 / 10): 3110-3150.

No diffraction peak other than diamond, titanium carbide and alumina was observed in any of the sintered bodies by X-ray diffraction.

Example 6 to Example 8 A mixed powder prepared in the same manner as in Example 2 to Example 3 was used as a sample, and the sintering conditions were 1800 MPa, 1200 ° C. to 1300 ° C., and 30 minutes to
Sintering was performed in the same manner as in Examples 4 to 5 except that the time was set to 3 hours.

The sintered body has a density of 95.0 as shown in Table 1.
% To 96.3%, it was very dense, and the Vickers microhardness was very high, Hv (0.5 / 10): 2410 to 2930.

When the crystal phases of the sintered bodies of Examples 6 to 8 were examined by X-ray diffraction, diffraction peaks other than those of diamond and alumina were not recognized.

Example 9 TiC was used as a target on the surface of coarse high-purity diamond particles (particle size 37 to 44 μm), and the amount of external addition to diamond was about 5% by volume by sputtering. Was coated.

50% by volume of the coated diamond particles was used as a raw material powder for a binder, and was disclosed in Japanese Patent Laid-Open No. 63-151.
The high-purity, easily-sinterable alumina powder having an average particle size of 0.2 μm described in Japanese Patent No. 616 is 48.4% by volume, and magnesia (MgO) and titania (TiO 2) are used as sintering aids for the alumina powder.
_x , X = 1-2) was added by 0.6% and 1.0% by volume, respectively. Using an alumina ball mill, these were wet mixed in acetone for 2 hours. Then, the mixed powder was vacuum dried at 10 ⁻⁶ torr and 200 ° C.

Next, a disk-shaped product having a diameter of 16 mm and a thickness of 5 mm was embossed and the molded product was placed in a capsule made of Pyrex glass filled with hBN powder, at 10 ⁻⁶ torr, 700 ° C.
It was degassed for 12 hours and then sealed.

The capsule is placed in a HIP device using argon gas as a pressure medium, and the sintering temperature is 1600 ° C. and the sintering pressure is 15
It was held at 0 MPa for 1 hour and sintered. Thereafter, the furnace was cooled, the pressure was released, and the sintered body was taken out.

As shown in Table 1, the sintered body had a density of 99.8
% Is very precise, and the Vickers micro hardness is Hv
(10/30): 3230, which was very high hardness.

When the crystal phase of the sintered body of Example 9 was examined by X-ray diffraction, diffraction peaks other than those of diamond, TiC and alumina were not recognized.

Examples 10 to 11 The mixture ratio of the coated diamond of Example 9 to alumina containing magnesia (MgO) and titania (TiO _x , X = 1-2) and SiC whiskers was 35:55: 10 ~ 45: 4
5:10 and prepared in the same manner as in the manufacturing method of Example 9, and then using a HIP device, sintering temperature 1600 ° C., sintering pressure
It was held at 150 MPa for 3 hours and sintered.

As shown in Table 1, the sintered body had a density of 98.7.
% To 99.6%, it was very dense, and the Vickers microhardness was Hv (20/30): 3080 to 3120, which was a very high hardness.

When the crystal phases of the sintered bodies of Examples 10 to 11 were examined by X-ray diffraction, diamond, TiC,
No diffraction peaks other than those of alumina and SiC were observed.

[0054]

[Effects of the Invention] The diamond-containing high hardness and high density composite sintered body of the present invention and the method for producing the same contain 1% to 90% by volume of diamond powder, and the balance does not exceed 1850 ° C when the pressure is less than 2000 MPa. By sintering the material at a temperature of 85% or more and a Vickers hardness of 600 or more, which is a dense and high-hardness binder, the binder material is mixed in a volume of 99% to 10%, and the mixture is mixed. The pressure is 20
Manufacture of diamond-containing high-hardness and high-density composite sintered body, which is less than 00MPa, temperature does not exceed 1850 ℃, and diamond is not thermodynamically stable but is sintered for a suitable time under metastable sintering conditions of pressure and temperature. Method, or by coating diamond powder particles with a coating material, the coated diamond powder is baked at a temperature of 1% to 90% by volume and the balance at a pressure of less than 2000 MPa and not exceeding 1850 ° C. By binding, the density is 85% or more, Vickers hardness
The raw material of the binder, which is made of a dense and high-hardness binder of 600 or more, is mixed in a volume of 99% to 10%, and the mixture is molded or embossed, and the pressure is less than 2000 MPa and the temperature is less than 2000 MPa. But
A method for producing a diamond-containing high-hardness high-density composite sintered body, which does not exceed 1850 ° C, and is not thermodynamically stable in diamond, but is sintered for a suitable period of time under metastable pressure and temperature sintering conditions. The body is 1% to 90% by volume, and the rest is sintered at a pressure of less than 2000MPa and at a temperature not exceeding 1850 ℃, resulting in a density of 85% or more, Vickers hardness.
The raw material of the binder, which consists of a dense and high-hardness binder of 600 or more, is mixed in a volume of 99% to 10%, and after the mixture is molded or embossed, the pressure is less than 2000 MPa and the temperature is 18
It is composed of a sintered body that does not exceed 50 ° C, and is not thermodynamically stable, but is sintered for a suitable time under metastable pressure and temperature sintering conditions. Diamond is 1% to 90% by volume. By containing the balance, the pressure is less than 2000MPa, and by sintering at a temperature not exceeding 1850 ℃,
Density 85% or more, Vickers hardness 600 or more consisting of dense and high hardness binder, density 85% or more, Vickers hardness 600
The diamond-containing high-hardness high-density composite sintered body characterized by having the above, or the diamond powder particles, is coated with a coating material, and the diamond is coated with 0.1% to 2000% by external addition. 1% to 90% of coated diamond powder by volume,
The balance is a dense and high-hardness binder with a density of 85% or more and a Vickers hardness of 600 or more, which is obtained by sintering at a pressure of less than 2000 MPa and not exceeding 1850 ° C. , 99% to 10% by volume, after mixing or embossing the mixture, the pressure is less than 2000MPa, the temperature does not exceed 1850 ℃, the diamond is not thermodynamically stable but metastable. It is composed of a sintered body that is sintered for an appropriate period of time under pressure and temperature sintering conditions, contains 1% to 89.9% by volume of diamond, contains a coating material, and
The pressure is less than 2000MPa, and the sintering is performed at a temperature not exceeding 1850 ℃, resulting in a density of 85% or more and a Vickers hardness of 600.
It provides a high-hardness, high-density composite sintered body containing diamond having a density of 85% or more and a Vickers hardness of 600 or more, which is 99% to 10.1% by volume of the dense and high-hardness binder described above. By the manufacturing method of the high hardness and high density composite sintered body containing, substantially no graphite phase,
Since it is possible to manufacture a dense and high-hardness, high-hardness, high-density composite sintered body containing diamond, the drawbacks due to the limitation of using an ultra-high pressure generator for generating ultra-high pressure exceeding 2000 MPa can be solved. In particular, the ultra high pressure HIP device or the ultra high pressure H
When a HIP device other than the IP device is used, it is possible to manufacture a sintered body having a complicated shape, and the present invention has a great advantage in industrial production.

[Brief description of drawings]

FIG. 1 is a pressure / temperature diagram showing a stable region of diamond.

[Explanation of symbols] Thermodynamic equilibrium line of diamond Line where diamond is actually stable according to Hall's report

Claims (72)

[Claims] 1. A diamond powder having a volume of 1% to 90% and the balance being sintered at a pressure of less than 2000 MPa and at a temperature not exceeding 1850 ° C., so that the density is 85% or more and the Vickers hardness is 600 or more. The dense and high-hardness binder, which is a raw material for the binder, is mixed in a volume of 99% to 10%, and after the mixture is molded or embossed, the pressure is less than 2000 MPa and the temperature is 1850. A method for producing a high-hardness and high-density composite sintered body containing diamond, which is characterized in that the diamond is not thermodynamically stable, but is sintered for a suitable time under a sintering condition of metastable pressure and temperature not exceeding ℃ . 2. The coated diamond powder, which is obtained by coating diamond powder particles with a coating material, is 1% to 90% by volume, and the balance is 2000 MPa.
By sintering at a temperature of 1850 ° C or less, the binder material, which is a dense and high-hardness binder having a density of 85% or more and a Vickers hardness of 600 or more, is 99% in volume.
After mixing ~ 10%, the mixture is molded or stamped and the pressure is less than 2000MPa and the temperature does not exceed 1850 ℃.
A process for producing a diamond-containing high hardness and high density composite sintered body, which comprises sintering diamond for an appropriate period of time under a pressure-temperature sintering condition that is not thermodynamically stable but is metastable. 3. The coating material has a pressure of 2000 MPa.
The method for producing a diamond-containing high-hardness high-density composite sintered body according to claim 2, characterized in that the coating material does not accelerate the phase transition of diamond into a graphite phase at a temperature below 1850 ° C. 4. The coating material has a pressure of 2000 MPa.
The diamond-containing high hardness and high density composite sintering according to claim 2 or 3, wherein the coating material is a coating material that reacts with carbon to form a reaction product at a temperature of less than 1850 ° C. Body manufacturing method. 5. The coating material is a periodic table 1b,
2a, 3a, 4a, 5a, 6a, 7a, Group 8 metals, rare earth metals, Si,
5. The diamond according to claim 2, wherein the coating material is composed of B, Al, or one or more kinds selected from compounds containing one or more kinds thereof. Manufacturing method of high hardness and high density composite sintered body containing. 6. The surface of the coated diamond powder is further coated with a coating material of Periodic Table 1b,
2a, 3a, 4a, 5a, 6a, 7a, Group 8 metals, rare earth metals, Si,
A multi-coated diamond powder, which is obtained by coating one or more layers selected from B, Al, or one or more selected from compounds containing at least one of these, 2. A method for producing a diamond-containing high hardness and high density composite sintered body according to claim 3, claim 4 or claim 5. 7. The periodic table as the coating material
1b, 2a, 3a, 4a, 5a, 6a, 7a, Group 8 metals, rare earth metals,
It is characterized in that the additive amount of at least one selected from compounds containing at least one of Si, B, and Al to diamond is 0.1% to 2000% by volume by external addition. The method for producing a diamond-containing high hardness and high density composite sintered body according to claim 2, claim 3, claim 4, claim 5, or claim 6. 8. The periodic table as the coating material
1b, 2a, 3a, 4a, 5a, 6a, 7a, Group 8 metals, rare earth metals,
The amount of one or more selected from Si, B, and Al added to diamond by external addition is 0.1% to 1000% by volume.
%, The method for producing a diamond-containing high-hardness high-density composite sintered body according to claim 2, claim 3, claim 4, claim 5, or claim 6. 9. The coating material is the periodic table 1b,
2a, 3a, 4a, 5a, 6a, 7a, Group 8 metals, rare earth metals, Si,
B, Al oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides, oxycarbonitrides, borides, silicides characterized by comprising one or more selected from The method for producing a diamond-containing high hardness and high density composite sintered body according to claim 2, claim 3, claim 4, claim 5, claim 6 or claim 7. 10. The pressure is less than 2000 MPa at 1850 ° C.
By sintering at a temperature that does not exceed the temperature, the density of the binder is 85% or more and the Vickers hardness of 600 or more is a dense and high-hardness binder. The diamond-containing high hardness and high density according to claim 1 or 2, comprising a fibrous substance composed of one or more kinds of metals or compounds having a shape in which the ratio of the major axis to the major axis is 2 or more. Manufacturing method of composite sintered body. 11. A fibrous substance having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more is a periodic table 1b, 2a, 3a, 4a, 5a, 6a. , 7a, 8 metals, rare earth metals, B, Si, Al, or one or more compounds containing one or more of these, with a minor axis of 500 μ
The method for producing a diamond-containing high-hardness high-density composite sintered body according to claim 10, wherein the fibrous material has a shape of m or less and a ratio of the major axis to the minor axis of 2 or more. 12. The fibrous substance having a shape having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more is a periodic table 1b, 2a, 3a, 4a, 5a, 6a. , 7a, 8 group metals, rare earth metals, B, Si, Al oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides, oxycarbonitrides, borides, silicides Containing, minor axis 500 μm
The production of a diamond-containing high-hardness high-density composite sintered body according to claim 10 or 11, wherein the fibrous substance has a shape in which the ratio of the major axis to the minor axis is 2 or more. Law. 13. The fibrous material having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more is SiC, TiC, B ₄ C, Si ₃ N ₄ , AlN, TiN, Al ₂ O ₃ , C
, W, B, Mo, Nb, Ta, V, and Zr, having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more. The method for producing a diamond-containing high hardness and high density composite sintered body according to claim 10, 11 or 12. 14. A fibrous substance having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more is formed on the surface of the fibrous substance by periodic table 1b, 2a, 3a, 4a,
50a, 6a, 7a, 8 group metal, rare earth metal, B, Si, Al, or a coating material consisting of one or more compounds containing at least one of these, with a minor axis of 50
14. The coated fibrous substance having a shape of 0 μm or less and a ratio of the major axis to the minor axis being 2 or more, claim 10, claim 11, claim 12 or claim 13. Method for producing high hardness and high density composite sintered body containing diamond of. 15. The coated fibrous material having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more is formed on the surface of the fibrous material in Periodic Table 1b. , 2a, 3a, 4a, 5a, 6a, 7a, Group 8 metals, rare earth metals, B, Si, Al oxides, nitrides, carbides, oxynitrides,
Coating with one or more types of oxycarbides, carbonitrides, oxycarbonitrides, borides, and silicides, with a minor axis of 500 μm or less, and a ratio of the major axis to the minor axis of 2 or more. 15. The diamond-containing high hardness and high density composite sintered body according to claim 10, 11, 12, 13 or 14, wherein the coated fibrous material has a shape of Manufacturing method. 16. The coated fibrous material having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more is B, Ti,
Zr, Hf, Ta, Nb, V, SiC, TiC, ZrC, B ₄ C, WC, Hf
C, TaC, NbC, Si ₃ N ₄ , TiN, ZrN, AlN, HfN, TaN
_{, TiB, TiB 2, ZrB 2} , LaB 6, MoSi 2, BP, made by coating a coating material consisting of one or more of Al ₂ O _3, a short diameter of 500 [mu] m or less, the major axis with respect to the minor axis 16. The diamond-containing high-content according to claim 10, claim 11, claim 12, claim 13, claim 14 or claim 15, characterized in that it is composed of a coated fibrous substance having a ratio of 2 or more. Hardness High density composite sintered body manufacturing method. 17. The fibrous substance or coated fibrous substance, wherein the minor axis is 500 μm or less and the ratio of the major axis to the minor axis is 2 or more. A fibrous substance or a coated fibrous substance is provided with an oxide film on the surface of the fibrous substance or the coated fibrous substance by oxidization of a particulate substance in an oxidizing atmosphere. And the ratio is 2
The method for producing a diamond-containing high-hardness high-density composite sintered body according to claim 10, which is made of the fibrous substance having the above-mentioned shape or a coated fibrous substance. 18. The pressure is less than 2000 MPa and the temperature is 1850 ° C.
By sintering at a temperature that does not exceed 85%, it is a dense and high-hardness binder with a density of 85% or more and a Vickers hardness of 600 or more.
By sintering at a temperature not exceeding 50 ° C, a density of 85
% Or more, a Vickers hardness of 600 or more, a dense and high hardness, and a raw material of the binder, which is a binder that does not promote the phase transition of the diamond into a graphite phase. The method for producing a diamond-containing high hardness and high density composite sintered body according to claim 2 or 10. 19. The pressure is less than 2000 MPa and the temperature is 1850 ° C.
By sintering at a temperature that does not exceed, the density of the binder is 85% or more and the Vickers hardness is 600 or more.
By sintering at a temperature not exceeding 50 ° C., a dense and high-hardness binder containing a reaction product formed by reacting with carbon has a density of 85% or more and a Vickers hardness of 600 or more. The method for producing a diamond-containing high-hardness high-density composite sintered body according to claim 1, claim 2, claim 10 or claim 18, which is made of a raw material. 20. The pressure is less than 2000 MPa, at 1850 ° C.
By sintering at a temperature that does not exceed, the density of 85% or more, Vickers hardness of 600 or more dense and high hardness binder, the raw material of the binder, the periodic table 1b, 2a, 3a, Four
a, 5a, 6a, 7a, 8 group metals, rare earth group metals, Si, B, A
l, or claim 1, claim 2, claim 10, characterized in that it comprises a raw material powder consisting of one or more selected from the compounds containing one or more of these. The method for producing a high hardness and high density composite sintered body containing diamond according to claim 18 or claim 19. 21. The pressure is less than 2000 MPa at 1850 ° C.
By sintering at a temperature that does not exceed, the density of 85% or more, Vickers hardness of 600 or more dense and high hardness binder, the raw material of the binder, the periodic table 1b, 2a, 3a, Four
a, 5a, 6a, 7a, 8 group metals, rare earth group metals, Si, B, Al
Of the oxide, nitride, carbide, oxynitride, oxycarbide, carbonitride, oxycarbonitride, boride, or silicide of a raw material powder. The method for producing a diamond-containing high hardness and high density composite sintered body according to claim 1, claim 2, claim 10, claim 18, claim 19 or claim 20, which is characterized. 22. The pressure is less than 2000 MPa, and the temperature is 1850 ° C.
By sintering at a temperature that does not exceed the limit, a dense and high-hardness binder with a density of 85% or more and a Vickers hardness of 600 or more is used. Selected from among alumina powder containing up to 10% magnesia (MgO) and / or titania (TiO _x , X = 1-2) as auxiliary agent, partially stabilized zirconia powder, titania powder or titanium nitride. The diamond-containing high hardness according to claim 1, claim 2, claim 10, claim 18, claim 19, claim 20 or claim 21, characterized in that the powder contains one or more kinds of powder. Manufacturing method of high-density composite sintered body. 23. The pressure is less than 2000 MPa, at 1850 ° C.
The binder is made of a dense and high-hardness binder with a density of 85% or more and a Vickers hardness of 600 or more by sintering at a temperature that does not exceed the limit, the raw material of the binder is ammonium aluminum carbonate pyrolysis method, buyer Method, organic aluminum hydrolysis method, ammonium alum pyrolysis method, ethylene chlorohydrin method, underwater spark discharge method 1μ
Alumina powder consisting of particles of m or less or magnesia (MgO) and / or titania (TiO _x , X = 1-
2. Alumina powder containing up to 10% of 2) is included, Claim 1, Claim 2, Claim 18, Claim 19, Claim 20, Claim 21, Claim 21 or The method for producing a high hardness and high density composite sintered body containing diamond according to claim 22. 24. The pressure is less than 2000 MPa, at 1850 ° C.
By sintering at a temperature not exceeding the above, the raw material of the binder, which is a dense and high-hardness binder having a density of 85% or more and a Vickers hardness of 600 or more, is manufactured by the coprecipitation method.
A partially stabilized zirconia powder composed of particles having a particle size of not more than μm is included, Claim 1, Claim 2, Claim 10, Claim 18, Claim 19, Claim 20, and Claim 2.
The method for producing a diamond-containing high hardness and high density composite sintered body according to claim 1 or 23. 25. The pressure is less than 2000 MPa and the temperature is 18
A diamond-containing high-hardness high-density composite sintered body that does not exceed 50 ° C and is not thermodynamically stable, but sinters for a suitable time under metastable sintering conditions of pressure and temperature is less than 2000MPa. An ultra-high pressure device capable of generating a gentle ultra-high pressure.
Claim 3, Claim 4, Claim 5, Claim 6, Claim 7,
Claim 8, Claim 9, Claim 10, Claim 11, Claim 12, Claim 13, Claim 14, Claim 15, Claim 1
6, claim 17, claim 18, claim 19, claim 2
0, claim 21, claim 22, claim 23 or claim 2
4. The method for producing a diamond-containing high hardness and high density composite sintered body according to 4. 26. The pressure is less than 2000 MPa and the temperature is 18
A diamond-containing high-hardness high-density composite sintered body manufacturing device that does not exceed 50 ° C. and is not thermodynamically stable but is sintered for a suitable time under metastable pressure and temperature sintering conditions is an ultra-high pressure HIP. It consists of an apparatus, Claim 1, Claim 2, Claim 3, Claim 4, Claim 5, Claim 6, Claim 7, Claim 8, Claim 9, Claim 10, Claim. 11, claim 12, claim 13, claim 14, claim 15, claim 16, claim 17, claim 18, claim 19, claim 20, claim 21, claim 22, claim 2.
The method for producing a diamond-containing high-hardness high-density composite sintered body according to claim 3 or 24. 27. The pressure is less than 2000 MPa and the temperature is 18
The diamond-containing high-hardness high-density composite sintered body manufacturing device that does not exceed 50 ° C and that is not thermodynamically stable, but is sintered for a suitable time under metastable sintering conditions of pressure and temperature It is a HIP device excluding a HIP device, Claim 1, Claim 2, Claim 3, Claim 4, Claim 5, Claim 6, Claim 7, Claim 8, Claim 9 and Claim. Claim 10, Claim 11, Claim 12, Claim 1
3, claim 14, claim 15, claim 16, claim 1
7, claim 18, claim 19, claim 20, claim 2
The method for producing a diamond-containing high hardness and high density composite sintered body according to claim 1, claim 22, claim 23 or claim 24. 28. The pressure is less than 2000 MPa and the temperature is 18
The HP device is a manufacturing device of diamond-containing high hardness and high density composite sintered body, which does not exceed 50 ° C and diamond is not thermodynamically stable, but is sintered for a suitable time under the conditions of metastable pressure and temperature. Claim 1, claim 2, claim 3, claim 4, claim 5, claim 6, claim 7, claim 8, claim 9, claim 10, claim 1 characterized in that
1, claim 12, claim 13, claim 14, claim 1
5, claim 16, claim 17, claim 18, claim 1
9, claim 20, claim 21, claim 22, claim 23
Alternatively, the method for producing a diamond-containing high hardness and high density composite sintered body according to claim 24. 29. The pressure according to claim 1, wherein said diamond is not thermodynamically stable but has a metastable pressure / temperature sintering condition, and the pressure does not exceed 1500 MPa. 3, claim 4, claim 5, claim 6, claim 7, claim 8, claim 9, claim 10, claim 11,
Claim 12, Claim 13, Claim 14, Claim 15, Claim 16, Claim 17, Claim 18, Claim 19, Claim 20, Claim 21, Claim 22, Claim 23, Claim. 24, claim 25, claim 26, claim 27, or the manufacturing method of a diamond-containing high hardness and high density composite sintered compact according to claim 28. 30. The diamond is not thermodynamically stable, but the temperature under a metastable sintering condition of pressure and temperature does not exceed 1700 ° C. 1, claim 2, claim 2 Claim 3, Claim 4, Claim 5, Claim 6, Claim 7, Claim 8, Claim 9, Claim 10, Claim 11, Claim 12, Claim 13, Claim 14, and Claim 15. , Claim 16, claim 17, claim 18, claim 19, claim 20, claim 21, claim 22, claim 23, claim 2
4, claim 25, claim 26, claim 27, claim 28
30. The method for producing a high hardness and high density composite sintered body containing diamond according to claim 29. 31. The temperature which is not thermodynamically stable but has a metastable sintering condition of pressure and temperature which does not exceed 1600 ° C. Claim 3, Claim 4, Claim 5, Claim 6, Claim 7, Claim 8, Claim 9, Claim 10, Claim 11, Claim 12, Claim 13, Claim 14, and Claim 15. , Claim 16, claim 17, claim 18, claim 19, claim 20, claim 21, claim 22, claim 23, claim 2
4, claim 25, claim 26, claim 27, claim 28
30. The method for producing a high hardness and high density composite sintered body containing diamond according to claim 29. 32. The temperature according to claim 1, wherein the diamond is not thermodynamically stable but has a metastable sintering condition of pressure and temperature which does not exceed 1500 ° C. Claim 3, Claim 4, Claim 5, Claim 6, Claim 7, Claim 8, Claim 9, Claim 10, Claim 11, Claim 12, Claim 13, Claim 14, and Claim 15. , Claim 16, claim 17, claim 18, claim 19, claim 20, claim 21, claim 22, claim 23, claim 2
4, claim 25, claim 26, claim 27, claim 28
30. The method for producing a high hardness and high density composite sintered body containing diamond according to claim 29. 33. The temperature according to claim 1, wherein the diamond is not thermodynamically stable but has a metastable sintering condition of pressure and temperature which does not exceed 1400 ° C. Claim 3, Claim 4, Claim 5, Claim 6, Claim 7, Claim 8, Claim 9, Claim 10, Claim 11, Claim 12, Claim 13, Claim 14, and Claim 15. , Claim 16, claim 17, claim 18, claim 19, claim 20, claim 21, claim 22, claim 23, claim 2
4, claim 25, claim 26, claim 27, claim 28
30. The method for producing a high hardness and high density composite sintered body containing diamond according to claim 29. 34. The raw material of the binder has a pressure of 2000 MPa.
And a Vickers hardness of 800 or more due to sintering at a temperature not exceeding 1850 ° C.
It is the raw material of the said binder, Claim 1, Claim 2, Claim 3, Claim 4, Claim 5, Claim 6, Claim 7, Claim 8, Claim 9, Claim. 10. Claim 1
1, claim 12, claim 13, claim 14, claim 1
5, claim 16, claim 17, claim 18, claim 1
9, claim 20, claim 21, claim 22, claim 2
3, claim 24, claim 25, claim 26, claim 2
7, claim 28, claim 29, claim 30, claim 3
34. The method for producing a diamond-containing high hardness and high density composite sintered body according to claim 1, 32 or 33. 35. The raw material of the binder has a pressure of 2000 MPa.
The raw material of the binder, which is a dense binder having a density of 90% or more when sintered at a temperature not higher than 1850 ° C. Claim 3, Claim 4, Claim 5, Claim 6, Claim 7, Claim 8, Claim 9, Claim 10, Claim 11, Claim 1
2, claim 13, claim 14, claim 15, claim 1
6, claim 17, claim 18, claim 19, claim 2
0, claim 21, claim 22, claim 23, claim 2
4, claim 25, claim 26, claim 27, claim 2
8, claim 29, claim 30, claim 31, claim 3
2. The method for producing a diamond-containing high hardness and high density composite sintered body according to claim 33 or claim 34. 36. Degassing and encapsulating the container, which is formed by degassing and encapsulating the mixture in a container capable of pressure transmission, after the mixture has been molded or embossed by repeating one or more times. According to claim 1, multiple degassing encapsulation of two or more is carried out, claim 1, claim 3, claim 4, claim 5, claim 6, claim 7, claim 8, claim. Claim 9, Claim 10, Claim 11, Claim 12, Claim 1
3, claim 14, claim 15, claim 16, claim 1
7, claim 18, claim 19, claim 20, claim 2
1, claim 22, claim 23, claim 24, claim 2
5, claim 26, claim 27, claim 28, claim 2
9, claim 30, claim 31, claim 32, claim 3
3. The method for producing a diamond-containing high hardness and high density composite sintered body according to claim 34 or claim 35. 37. Diamond powder in a volume of 1% to 90%,
The balance is a dense and high-hardness binder with a density of 85% or more and a Vickers hardness of 600 or more by sintering at a pressure of less than 2000 MPa and not exceeding 1850 ° C. , 99% to 10% by volume, after mixing or embossing the mixture, the pressure is less than 2000MPa, the temperature does not exceed 1850 ℃, the diamond is not thermodynamically stable but metastable. It is composed of a sintered body that is sintered for an appropriate time under pressure and temperature sintering conditions, contains 1% to 90% by volume of diamond, and the balance is at a pressure of less than 2000 MPa and not exceeding 1850 ° C. By sintering, it consists of a dense and high-hardness binder with a density of 85% or more and a Vickers hardness of 600 or more.
A high-hardness, high-density composite sintered body containing diamond, which has 600 or more. 38. A coated diamond powder, which is obtained by coating diamond powder particles with a coating material to the diamond in an externally added amount of 0.1% to 2000%, and a volume of 1% to 90%. %, The balance is
The pressure is less than 2000MPa, and the sintering is performed at a temperature not exceeding 1850 ℃, resulting in a density of 85% or more and a Vickers hardness of 600.
The above-mentioned dense and high-hardness binding material, which is a raw material for the binding material, is mixed in a volume of 99% to 10%, and the mixture is mixed with
Or after embossing, pressure is less than 2000MPa, temperature is 1850 ℃
The diamond is not thermodynamically stable, but is composed of a sintered body that is sintered for a suitable time under the conditions of metastable pressure and temperature, and contains 1% to 89.9% by volume of diamond. , Coating material and pressure is 20
By sintering at a temperature of less than 00 MPa and not exceeding 1850 ° C, a dense and high-hardness binder with a density of 85% or more and a Vickers hardness of 600 or more can be formed by 99% to 10.1% by volume.
A diamond-containing high hardness and high density composite sintered body, which has a Vickers hardness of 5% or more and 600 or more. 39. The coating material has a pressure of 2000 MPa.
39. The diamond-containing high hardness and high density composite sintered body according to claim 38, which is made of a coating material which does not promote the phase transition of diamond into a graphite phase at a temperature of less than a and not exceeding 1850 ° C. 40. The coating material has a pressure of 2000 MPa.
The diamond-containing high hardness and high density composite calcination according to claim 38 or 39, wherein the coating material is a coating material that reacts with carbon to form a reaction product at a temperature of less than a and not exceeding 1850 ° C. Union. 41. The coating material is a periodic table 1b,
2a, 3a, 4a, 5a, 6a, 7a, Group 8 metals, rare earth metals, S
The high diamond content according to claim 38, 39 or 40, characterized in that it comprises i, B 2, Al, or one or more selected from compounds containing one or more of these. Hardness and high density composite sintered body. 42. On the surface of the coated diamond powder particles, as a coating material, a periodic table 1b, 2a, 3a, 4a, 5a, 6a, 7a, 8 group metal, rare earth metal, Si, B 2, 39. A multi-coated diamond powder, which is obtained by coating one or more layers of Al or one or more selected from compounds containing one or more of these, 39. Item 39. The diamond-containing high hardness and high density composite sintered body according to Item 39, 40 or 41. 43. The coating material is a periodic table 1b,
2a, 3a, 4a, 5a, 6a, 7a, Group 8 metals, rare earth metals, S
i, B, Al oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides, oxycarbonitrides, borides, and silicides. The diamond-containing high-hardness high-density composite sintered body according to claim 38, 39, 40, 41 or 42, which is characterized. 44. The pressure is less than 2000 MPa, and the temperature is 1850 ° C.
By sintering at a temperature that does not exceed the temperature, the density of the binder is 85% or more and the Vickers hardness of 600 or more is a dense and high-hardness binder. 39. The diamond-containing high hardness and high density composite according to claim 37 or 38, characterized in that it comprises a fibrous substance made of one kind of metal or compound having a shape in which the ratio of the major axis to the major diameter is 2 or more. Sintered body. 45. The fibrous substance having a shape having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more is produced by periodic table 1b, 2a, 3a, 4a, 5a, 6a. , 7a, 8 metals, rare earth metals, B, Si, Al, or one or more compounds containing one or more of these, with a minor axis of 500 μ
The diamond-containing high hardness and high density composite sintered body according to claim 44, wherein the fibrous material has a shape in which the ratio of the major axis to the minor axis is 2 or more when m or less. 46. The fibrous material having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more is a periodic table 1b, 2a, 3a, 4a, 5a, 6a. , 7a, 8 group metals, rare earth metals, B, Si, Al oxides, nitrides, carbides, oxynitrides, oxycarbides, carbonitrides, oxycarbonitrides, borides, silicides Containing, minor axis 500 μm
46. The diamond-containing high hardness and high density composite sintered body according to claim 44 or claim 45, characterized in that the fibrous substance has a shape in which the ratio of the major axis to the minor axis is 2 or more. 47. The fibrous material having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more is SiC, TiC, B ₄ C, Si ₃ N ₄ , AlN, TiN, Al ₂ O ₃ , C
, W, B, Mo, Nb, Ta, V, and Zr, having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more. 47. The diamond-containing high hardness and high density composite sintered body according to claim 44, 45 or 46. 48. The fibrous substance having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more is formed on the surface of the fibrous substance by periodic table 1b, 2a, 3a, 4a,
50a, 6a, 7a, 8 group metal, rare earth metal, B, Si, Al, or a coating material consisting of one or more compounds containing at least one of these, with a minor axis of 50
48. The coated fibrous material having a shape of 0 μm or less and a ratio of the major axis to the minor axis being 2 or more, claim 44, claim 45, claim 46 or claim 47. High hardness and high density composite sintered body containing diamond. 49. The coated fibrous material having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more is formed on the surface of the fibrous material in Periodic Table 1b. , 2a, 3a, 4a, 5a, 6a, 7a, Group 8 metals, rare earth metals, B, Si, Al oxides, nitrides, carbides, oxynitrides,
Coating with one or more types of oxycarbides, carbonitrides, oxycarbonitrides, borides, and silicides, with a minor axis of 500 μm or less, and a ratio of the major axis to the minor axis of 2 or more. 49. The diamond-containing high hardness and high density composite sintered body according to claim 44, claim 45, claim 46, claim 47 or claim 48, which is made of a coated fibrous substance. 50. The coated fibrous material having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more is B, Ti,
Zr, Hf, Ta, Nb, V, SiC, TiC, ZrC, B ₄ C, WC, Hf
C, TaC, NbC, Si ₃ N ₄ , TiN, ZrN, AlN, HfN, Ta
N, TiB, TiB ₂ , ZrB ₂ , LaB ₆ , MoSi ₂ , BP, Al ₂ O ₃ coated with a coating material consisting of one or more types, the minor axis is 500 μm or less, and the major axis with respect to the minor axis The diamond-containing material according to claim 44, claim 45, claim 46, claim 47, claim 48 or claim 49, characterized in that it comprises a coated fibrous material having a ratio of 2 or more. High hardness and high density composite sintered body. 51. The fibrous substance or coated fibrous substance having a minor axis of 500 μm or less and a ratio of the major axis to the minor axis of 2 or more is fibrous substance or coated fiber. A fibrous substance or a coated fibrous substance is provided with an oxide film on the surface of the fibrous substance or the coated fibrous substance by oxidization of a particulate substance in an oxidizing atmosphere. Ratio to 2
The diamond-containing high-hardness high-density composite sintered body according to claim 44, characterized in that the fibrous material having the above-mentioned shape or the coated fibrous material is used. 52. The pressure is less than 2000 MPa, and the temperature is 1850 ° C.
By sintering at a temperature that does not exceed 85%, it is a dense and high-hardness binder with a density of 85% or more and a Vickers hardness of 600 or more.
By sintering at a temperature not exceeding 50 ° C, a density of 85
38. The bonding material as a raw material of the bonding material, wherein the bonding material is a dense material having a Vickers hardness of 600% or more and a hardness of 600% or more, and which does not promote a phase transition of the diamond into a graphite phase. 38. The high hardness and high density composite sintered body containing diamond according to claim 38 or claim 44. 53. The pressure is less than 2000 MPa and 1850 ° C.
By sintering at a temperature that does not exceed, the density of the binder is 85% or more and the Vickers hardness is 600 or more.
By sintering at a temperature not exceeding 50 ° C., a dense and high-hardness binder containing a reaction product formed by reacting with carbon has a density of 85% or more and a Vickers hardness of 600 or more. The diamond-containing high hardness and high density composite sintered body according to claim 37, 38, 44 or 52, which is made of a raw material. 54. The pressure is less than 2000 MPa and the temperature is 1850 ° C.
By sintering at a temperature that does not exceed, the density of 85% or more, Vickers hardness of 600 or more dense and high hardness binder, the raw material of the binder, the periodic table 1b, 2a, 3a, Four
a, 5a, 6a, 7a, 8 group metal, rare earth metal, Si, B, Al,
Or 37, claim 38, claim 44, claim 52, or claim 37, which comprises a raw material powder consisting of one or more selected from compounds containing one or more of these. The high hardness and high density composite sintered body containing diamond according to claim 53. 55. At a pressure of less than 2000 MPa and at a temperature of 1850 ° C.
By sintering at a temperature that does not exceed, the density of 85% or more, Vickers hardness of 600 or more dense and high hardness binder, the raw material of the binder, the periodic table 1b, 2a, 3a, Four
a, 5a, 6a, 7a, 8 metal, rare earth metal, Si, B, Al oxide, nitride, carbide, oxynitride, oxycarbide, carbonitride, oxycarbonitride, boride, silicide The diamond according to claim 37, 38, 44, 52, 53 or 54, characterized in that it comprises a raw material powder consisting of one or more selected from the above. Containing high hardness and high density composite sintered body. 56. At a pressure of less than 2000 MPa and at a temperature of 1850 ° C.
By sintering at a temperature that does not exceed the limit, a dense and high-hardness binder with a density of 85% or more and a Vickers hardness of 600 or more is used. Selected among alumina powder containing up to 10% magnesia (MgO) and / or titania (TiO _x , X = 1-2) as auxiliary agent, partially stabilized zirconia powder, titania powder or titanium nitride 38. The method according to claim 37, claim 38 or claim 4, characterized in that the powder contains one or more kinds of powder.
4, claim 52, claim 53, claim 54 or claim 5
5. The high hardness and high density composite sintered body containing diamond according to 5. 57. The pressure is less than 2000 MPa and the temperature is 1850 ° C.
The binder is made of a dense and high-hardness binder with a density of 85% or more and a Vickers hardness of 600 or more by sintering at a temperature that does not exceed the limit, the raw material of the binder is ammonium aluminum carbonate pyrolysis method, buyer Method, organic aluminum hydrolysis method, ammonium alum pyrolysis method, ethylene chlorohydrin method, underwater spark discharge method 1μ
Alumina powder consisting of particles of m or less or magnesia (MgO) and / or titania (TiO _x , X = 1-
38. A method according to claim 37, 38, 44, characterized in that it comprises an alumina powder containing up to 10% of 2).
The diamond-containing high hardness and high density composite sintered body according to claim 52, claim 53, claim 54, claim 55 or claim 56. 58. The pressure is less than 2000 MPa and the temperature is 1850 ° C.
By sintering at a temperature not exceeding the above, the raw material of the binder, which is a dense and high-hardness binder having a density of 85% or more and a Vickers hardness of 600 or more, is manufactured by the coprecipitation method.
38. A method according to claim 37, 38, 44, 52, 53, 54, 55 or 55, characterized in that it comprises a partially stabilized zirconia powder consisting of particles of less than or equal to μm. Item 56. A high-hardness high-density composite sintered body containing diamond according to Item 56. 59. The pressure is less than 2000 MPa and the temperature is 18
A diamond-containing high-hardness high-density composite sintered body that does not exceed 50 ° C and is not thermodynamically stable, but sinters for a suitable time under metastable sintering conditions of pressure and temperature is less than 2000MPa. 38. The device according to claim 37, wherein the device is an ultrahigh pressure device capable of generating a gentle ultrahigh pressure.
8, claim 39, claim 40, claim 41, claim 4
2, claim 43, claim 44, claim 45, claim 4
6, claim 47, claim 48, claim 49, claim 5
0, claim 51, claim 52, claim 53, claim 5
4, claim 55, claim 56, claim 57 or claim 5.
8. The high hardness and high density composite sintered body containing diamond according to item 8. 60. The pressure is less than 2000 MPa and the temperature is 18
A diamond-containing high-hardness high-density composite sintered body manufacturing device that does not exceed 50 ° C. and is not thermodynamically stable but is sintered for a suitable time under metastable pressure and temperature sintering conditions is an ultra-high pressure HIP. Claim 37, Claim 38, Claim 39, Claim 40, Claim 41, Claim 42, Claim 43, Claim 44, Claim 4 characterized by consisting of a device.
5, claim 46, claim 47, claim 48, claim 4
9, claim 50, claim 51, claim 52, claim 5
3, claim 54, claim 55, claim 56, claim 57
59. The diamond-containing high hardness and high density composite sintered body according to claim 58. 61. The pressure is less than 2000 MPa and the temperature is 18
The diamond-containing high-hardness high-density composite sintered body manufacturing device that does not exceed 50 ° C and that is not thermodynamically stable, but is sintered for a suitable time under metastable sintering conditions of pressure and temperature 38. The device according to claim 37, 38 or 3, wherein the device is a HIP device other than the HIP device.
9, claim 40, claim 41, claim 42, claim 4
3, claim 44, claim 45, claim 46, claim 4
7, claim 48, claim 49, claim 50, claim 5
1, claim 52, claim 53, claim 54, claim 5
The diamond-containing high hardness and high density composite sintered body according to claim 5, claim 56, claim 57 or claim 58. 62. The pressure is less than 2000 MPa and the temperature is 18
The HP device is a manufacturing device of diamond-containing high hardness and high density composite sintered body, which does not exceed 50 ° C and diamond is not thermodynamically stable, but is sintered for a suitable time under the conditions of metastable pressure and temperature. 38.
Claim 38, Claim 39, Claim 40, Claim 41, Claim 42, Claim 43, Claim 44, Claim 45, Claim 46, Claim 47, Claim 48, Claim 49, Claim. 50, claim 51, claim 52, claim 53, claim 5
4, claim 55, claim 56, claim 57 or claim 5.
8. The high hardness and high density composite sintered body containing diamond according to item 8. 63. The pressure according to claim 37, wherein said diamond is not thermodynamically stable but is metastable under a pressure-temperature sintering condition, wherein said pressure does not exceed 1500 MPa. 39, claim 40, claim 41, claim 42, claim 43, claim 44, claim 45, claim 46, claim 47, claim 48, claim 49, claim 5.
0, claim 51, claim 52, claim 53, claim 5
4, claim 55, claim 56, claim 57, claim 5
8, claim 59, claim 60, claim 61 or claim 6.
2. The high hardness and high density composite sintered body containing diamond according to 2. 64. The temperature according to claim 37, wherein the diamond is not thermodynamically stable, but has a metastable sintering condition of pressure and temperature which does not exceed 1700 ° C. 37. Claim 39, Claim 40, Claim 41, Claim 42, Claim 43, Claim 44, Claim 45, Claim 4
6, claim 47, claim 48, claim 49, claim 5
0, claim 51, claim 52, claim 53, claim 5
4, claim 55, claim 56, claim 57, claim 5
8, claim 59, claim 60, claim 61, claim 62
A high-hardness high-density composite sintered body containing diamond according to claim 63. 65. The method according to claim 37, wherein the diamond is not thermodynamically stable, but the temperature under a metastable sintering condition of pressure and temperature does not exceed 1600 ° C. Claim 39, Claim 40, Claim 41, Claim 42, Claim 43, Claim 44, Claim 45, Claim 4
6, claim 47, claim 48, claim 49, claim 5
0, claim 51, claim 52, claim 53, claim 5
4, claim 55, claim 56, claim 57, claim 5
8, claim 59, claim 60, claim 61, claim 62
A high-hardness high-density composite sintered body containing diamond according to claim 63. 66. The method according to claim 37, wherein the temperature at which the diamond is not thermodynamically stable but is metastable under a pressure-temperature sintering condition does not exceed 1500 ° C. Claim 39, Claim 40, Claim 41, Claim 42, Claim 43, Claim 44, Claim 45, Claim 4
6, claim 47, claim 48, claim 49, claim 5
0, claim 51, claim 52, claim 53, claim 5
4, claim 55, claim 56, claim 57, claim 5
8, claim 59, claim 60, claim 61, claim 62
A high-hardness high-density composite sintered body containing diamond according to claim 63. 67. The temperature according to claim 37, wherein the diamond is not thermodynamically stable but has a metastable sintering condition of pressure and temperature which does not exceed 1400 ° C. 37. Claim 39, Claim 40, Claim 41, Claim 42, Claim 43, Claim 44, Claim 45, Claim 4
6, claim 47, claim 48, claim 49, claim 5
0, claim 51, claim 52, claim 53, claim 5
4, claim 55, claim 56, claim 57, claim 5
8, claim 59, claim 60, claim 61, claim 62
A high-hardness high-density composite sintered body containing diamond according to claim 63. 68. The raw material of the binder has a pressure of 2000 MPa.
And a Vickers hardness of 800 or more due to sintering at a temperature not exceeding 1850 ° C.
38. The material of the binder, wherein the binder is a raw material.
Claim 38, Claim 39, Claim 40, Claim 41, Claim 42, Claim 43, Claim 44, Claim 45, Claim 46, Claim 47, Claim 48, Claim 49, Claim. 50, claim 51, claim 52, claim 53, claim 5
4, claim 55, claim 56, claim 57, claim 5
8, claim 59, claim 60, claim 61, claim 6
2, claim 63, claim 64, claim 65, claim 66
A diamond-containing high hardness high density composite sintered body according to claim 67. 69. The raw material of the binder has a pressure of 2000 MPa.
37. The method according to claim 37, wherein the temperature is less than 1850 ° C., and the material is a dense binder having a density of 90% or more when sintered at a temperature not exceeding 1850 ° C.
Claim 39, Claim 40, Claim 41, Claim 42, Claim 43, Claim 44, Claim 45, Claim 46, Claim 47, Claim 48, Claim 49, Claim 50, Claim. 51, claim 52, claim 53, claim 54, claim 5
5, claim 56, claim 57, claim 58, claim 5
9, claim 60, claim 61, claim 62, claim 6
3, claim 64, claim 65, claim 66, claim 67
69. The diamond-containing high hardness and high density composite sintered body according to claim 68. 70. The high hardness and high density composite sintered body containing diamond according to claim 37, 38 or 3, wherein the Vickers hardness is 800 or higher.
9, claim 40, claim 41, claim 42, claim 4
3, claim 44, claim 45, claim 46, claim 4
7, claim 48, claim 49, claim 50, claim 5
1, claim 52, claim 53, claim 54, claim 5
5, claim 56, claim 57, claim 58, claim 5
9, claim 60, claim 61, claim 62, claim 6
3, claim 64, claim 65, claim 66, claim 6
70. The diamond-containing high hardness and high density composite sintered body according to claim 68 or claim 69. 71. The high density and high density composite sintered body containing diamond according to claim 37, claim 38, claim 39 or claim 4, wherein the density is 90% or more dense.
0, claim 41, claim 42, claim 43, claim 4
4, claim 45, claim 46, claim 47, claim 4
8, claim 49, claim 50, claim 51, claim 5
2, claim 53, claim 54, claim 55, claim 5
6, claim 57, claim 58, claim 59, claim 6
0, claim 61, claim 62, claim 63, claim 6
4, claim 65, claim 66, claim 67, claim 6
The diamond-containing high-hardness high-density composite sintered body according to claim 69 or claim 70. 72. One or more times of degassing and encapsulating the mixture, which is obtained by degassing and encapsulating the mixture in a container capable of pressure transmission, after the molding or embossing. 37, 38, 39, characterized in that a double or more multiple deaeration encapsulation is performed by
Claim 40, Claim 41, Claim 42, Claim 43, Claim 44, Claim 45, Claim 46, Claim 47, Claim 48, Claim 49, Claim 50, Claim 51, Claim. 52, claim 53, claim 54, claim 55, claim 5
6, claim 57, claim 58, claim 59, claim 6
0, claim 61, claim 62, claim 63, claim 6
4, claim 65, claim 66, claim 67, claim 6
A diamond-containing high hardness and high density composite sintered body according to claim 8, claim 69, claim 70 or claim 71.