WO2019077820A1 - Procédé de production de nitrure de zirconium - Google Patents

Procédé de production de nitrure de zirconium Download PDF

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WO2019077820A1
WO2019077820A1 PCT/JP2018/026665 JP2018026665W WO2019077820A1 WO 2019077820 A1 WO2019077820 A1 WO 2019077820A1 JP 2018026665 W JP2018026665 W JP 2018026665W WO 2019077820 A1 WO2019077820 A1 WO 2019077820A1
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nitride
zirconium
gpa
powder
sintering
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PCT/JP2018/026665
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English (en)
Japanese (ja)
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史朗 川村
谷口　尚
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国立研究開発法人物質・材料研究機構
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Priority to JP2019549116A priority Critical patent/JP6850505B2/ja
Publication of WO2019077820A1 publication Critical patent/WO2019077820A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B1/00—Single-crystal growth directly from the solid state
    • C30B1/12—Single-crystal growth directly from the solid state by pressure treatment during the growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/38—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/02—Heat treatment

Definitions

  • the present invention relates to a method of producing zirconium nitride.
  • Cubic zirconium nitride (c-Zr 3 N 4 ) is expected as a hard material.
  • techniques for producing c-Zr 3 N 4 have been reported (see, for example, Non-Patent Document 1 and Non-Patent Document 2).
  • Non-Patent Document 1 c-Zr 3 is produced by reacting N 2 and metal Zr at a temperature of 2500 K to 3000 K under a pressure of 15.6 GPa to 18 GPa using a diamond anvil cell (DAC). N 4 is manufactured.
  • DAC diamond anvil cell
  • Non-Patent Document 2 c-Zr 3 N 4 is manufactured by treating Zr—N nanoparticles at 12 GPa and 1900 K using a multi-anvil type high pressure apparatus.
  • the c-Zr 3 N 4 obtained in Non-patent Document 2 is a porous sintered body, and sufficient hardness was not obtained. Also here, in view of practical use, it had to be manufactured under lower pressure.
  • Non-Patent Document 3 synthesis of c-Zr 3 N 4 is suggested under a pressure of 7.7 GPa by using a double decomposition reaction, but there is a problem that c-Zr 3 N 4 is not synthesized reproducibly. .
  • the object of the present invention is to reproduce an inorganic substance having the same crystal structure as that of cubic zirconium nitride represented by Zr 3 N 4 as a zirconium nitride with good reproducibility under low pressure It is to provide a method.
  • a method for producing a nitride of zirconium which is an inorganic substance having the same crystal structure as that of cubic zirconium nitride represented by Zr 3 N 4 , comprises a powder of a halide of zirconium; The step of reacting the raw material powder containing the powder of the nitride of the element under the pressure of 5 GPa or more and 8 GPa or less at a temperature range of more than 1100 ° C. and 2500 ° C. or less is solved, thereby solving the above problems.
  • the zirconium halide may be a material selected from the group consisting of ZrF 4 , ZrCl 4 , ZrBr 4 and ZrI 4 .
  • the nitride of the group 2 element may be a material selected from the group consisting of Be 3 N 2 , Mg 3 N 2 , Ca 3 N 2 , Sr 3 N 2 and Ra 3 N 2. .
  • the reacting step may be performed by reacting the raw material powder in a temperature range of greater than 1100 ° C. and 1600 ° C. or less under a pressure of 5.5 GPa or more and 7.7 GPa or less.
  • the reacting step may be performed by reacting the raw material powder in a temperature range of 1300 ° C. or more and 1600 ° C. or less under a pressure of 5.5 GPa or more and 7.7 GPa or less.
  • the method may further include the step of treating the product obtained in the reacting step with a solvent and removing the second phase.
  • the zirconium halide may be ZrCl 4 and the nitride of the Group 2 element may be Ca 3 N 2 . Even if the raw material powder is mixed with the powder of the zirconium halide and the powder of the nitride of the group 2 element in a molar ratio of 3: 2.5 to 3: 1.2. Good.
  • the raw material powder may contain a reaction inhibitor.
  • the raw material powder may be filled in a capsule made of Mo, and the capsule may be placed in a high pressure apparatus.
  • the reacting step may be performed by reacting the raw material powder for a time of 10 minutes to 24 hours.
  • the zirconium nitride may be represented by Zr 3-x (N, O) 4 (x is -0.5 ⁇ x ⁇ 0.5).
  • the reacting step may be performed using a belt type high pressure device.
  • the method may further include the step of shaping the product obtained in the reacting step and sintering in a temperature range of 1200 ° C. or more and 2000 ° C. or less.
  • the sintering may be performed by molding the product and sintering it under a pressure of 2 GPa to 8 GPa in a temperature range of 1300 ° C. to 1600 ° C.
  • the sintering may be performed by adjusting the particle size of the product to a particle size of 10 nm to 10 ⁇ m and sintering the product.
  • the sintering may be performed by adding a sintering aid to the product and sintering.
  • the sintering aid may be h-BN and / or c-BN.
  • the sintering may be performed using at least one device selected from the group consisting of a belt type high pressure device, a multi-anvil type high pressure device, a hot press and a hot isostatic press (HIP).
  • the method of producing a nitride of zirconium which is an inorganic substance having the same crystal structure as that of cubic zirconium nitride represented by Zr 3 N 4 according to the present invention, comprises: a powder of a halide of zirconium; The step of reacting the raw material powder containing elemental nitride powder and under a pressure of 5 GPa or more and 8 GPa or less at a temperature range of more than 1100 ° C. and 2500 ° C. or less.
  • FIG. 1 It is a perspective view which shows typically the high pressure cell provided with the capsule used for manufacture of the nitride of the zirconium which is embodiment of this invention.
  • (B) It is sectional drawing which shows typically the high pressure cell provided with the capsule used for manufacture of the nitride of the zirconium which is embodiment of this invention. It is a figure which shows typically the belt type high-pressure apparatus used for manufacture of the nitride of the zirconium which is embodiment of this invention. It is a SEM image which shows the form of the sample (sample 4) of Example 4.
  • FIG. 2 is a view showing XRD patterns of the samples of Examples 1 to 5 and Comparative Example 1; It is a figure which shows the XRD pattern of the sample of the comparative example 2.
  • FIG. It is a figure which shows the aspect of the sintered compact of Example 7.
  • FIG. It is a figure which shows the XRD pattern of the sintered compact of Example 7.
  • nitride of zirconium are inorganic substances having the same crystal structure as the crystal structure of cubic zirconium nitride represented by Zr 3 N 4 (c-Zr 3 N 4), a method of manufacturing explain.
  • c-Zr 3 N 4 cubic zirconium nitride represented by Zr 3 N 4
  • a method of manufacturing explain First, a nitride of zirconium which is an inorganic substance having the same crystal structure as c-Zr 3 N 4 in the present invention will be described.
  • Zr 3 cubic zirconium nitride represented by N 4 belongs to a cubic system, 220 of the I-4 3 d space group (International Talbes for Crystallography Space group) and occupy crystal parameters and atomic coordinate positions shown in Table 1.
  • lattice constants a, b and c indicate the lengths of the unit cell axes, and ⁇ , ⁇ and ⁇ indicate the angles between the unit cell axes.
  • the atomic coordinates indicate the position of each atom in the unit cell.
  • zirconium nitride which is an inorganic substance having a crystal structure identical to that of c-Zr 3 N 4 , may change the ratio of Zr to N, or may change other elements (for example, part of N)
  • the lattice constant is changed by replacement with O (oxygen), but the crystal structure and the site occupied by the atom and the atomic position given by its coordinates change so largely that the chemical bond between framework atoms is broken. There is nothing to do.
  • the length of the chemical bond of Zr-N calculated from lattice constants and atomic coordinates obtained by Rietveld analysis of the results of X-ray diffraction and neutron diffraction of the substance of interest in the space group of I-43d It can be determined that the crystal structure is the same if it is within ⁇ 5% of that calculated from the lattice constant and atomic coordinates of the c-Zr 3 N 4 crystal shown in Table 1. When the length of the chemical bond exceeds ⁇ 5%, the chemical bond may be broken to form another crystal. As another simple determination method, the main peak of X-ray diffraction of c-Zr 3 N 4 crystal (for example, about 10 strong diffraction intensities) may be compared with that of the target substance.
  • nitrides of zirconium present invention having the same crystal structure as the crystal structure of c-Zr 3 N 4, c -Zr 3 N 4 itself, the molar ratio of Zr and N is chemically It also includes those which deviate from the stoichiometric composition (i.e., Zr-rich or N-rich), and those in which some of Zr and N are replaced with other elements (e.g., O etc.).
  • Zr 3-x (N, O) 4 x is -0.5 ⁇ x ⁇ , assuming that zirconium nitride has a molar ratio which deviates from the stoichiometric composition and is partially substituted. There is one represented by 0.5).
  • the above-mentioned zirconium nitride is a raw material powder containing zirconium halide powder and Group 2 element nitride powder in a temperature range of more than 1100 ° C. and 2500 ° C. or less , 5 GPa or more and 8 GPa or less.
  • the inventors of the present invention have said the temperature range and pressure of the halide of zirconium (ZRX 4 : X is a halogen element) and the nitride of a group 2 element (M 3 N 2 : M is a group 2 element) It has been found that, under the reaction, the following double decomposition reaction occurs to produce a zirconium nitride having a crystal structure identical to that of c-Zr 3 N 4 . 3ZrX 4 + 2M 3 N 2 ⁇ Zr 3 N 4 + 6MX 2
  • the metathesis reaction does not proceed with the conditions of the halide of zirconium and the nitride of the Group 1 element (for example, NaN 3 or Li 3 N), c-Zr 3 N
  • the present inventors repeated various experiments and found that they have found a unique combination of raw materials that allows a double decomposition reaction to proceed under a low pressure.
  • the zirconium halide is a material selected from the group consisting of ZrF 4 , ZrCl 4 , ZrBr 4 and ZrI 4 . These halides are easy to obtain and allow the metathesis reaction to proceed. Among them, ZrCl 4 is preferable from the viewpoint of reaction efficiency.
  • the nitride of the group 2 element is a material selected from the group consisting of Be 3 N 2 , Mg 3 N 2 , Ca 3 N 2 , Sr 3 N 2 and Ra 3 N 2 . These nitrides are easy to obtain and allow the metathesis reaction to proceed. Among them, Ca 3 N 2 is preferable from the viewpoint of reaction efficiency.
  • the halide of zirconium and the nitride of the group 2 element are preferably mixed in a molar ratio of 3: 2.5 to 3: 1.2. Within this range, zirconium nitride having the same crystal structure as that of c-Zr 3 N 4 can be formed. More preferably, the halide of zirconium and the nitride of the group 2 element are mixed in a molar ratio of 3: 2. Thereby, c-Zr 3 N 4 can be produced.
  • the raw materials are preferably powders, but in this case, they are powders having a particle size of 100 nm or more and 500 ⁇ m or less. If the particle size is in this range, the progress of the metathesis reaction is promoted. More preferably, the raw material powder is preferably a powder having a particle size of 200 nm or more and 200 ⁇ m or less. In the present specification, the particle size is a volume-based median diameter (d50) measured by a microtrack or a laser scattering method.
  • the raw material powder may contain a reaction inhibitor.
  • the reaction inhibitor is not particularly limited as long as it can be diluted to suppress heat generation, and exemplarily is sodium chloride (NaCl) or a halide of a group 2 element.
  • the amount contained in the raw material powder is preferably in the range of 10 wt% to 75 wt%. Within this range, the metathesis reaction preferably proceeds.
  • the raw material powder is held in a pressure- and heat-resistant capsule which is durable even under the above-mentioned temperature range and pressure.
  • the pressure resistant capsule is made of a material not reactive with the raw material powder, but is preferably made of molybdenum (Mo).
  • Mo molybdenum
  • the bulk density of the raw material powder held in the capsule is preferably 1.3 g / cm 3 or more and 3.0 g / cm 3 or less. By setting the filling rate to satisfy such bulk density, it is possible to accelerate the metathesis reaction between powders.
  • the reacting step is preferably performed under the pressure of 5.5 GPa or more and 7.7 GPa or less at a temperature range of more than 1100 ° C. and 1600 ° C. or less. If the pressure range is this range, the above-mentioned metathesis reaction preferably proceeds.
  • the reacting step is more preferably performed under the pressure of 5.5 GPa or more and 7.7 GPa or less in the temperature range of 1300 ° C. or more and 1600 ° C. or less. If the pressure range is in this range, the above-mentioned metathesis reaction proceeds more preferably, and a zirconium nitride reduced in the second phase is obtained.
  • the reaction step is more preferably performed under the pressure of 7 GPa or more and 7.7 GPa or less in the temperature range of 1300 ° C. or more and 1600 ° C. or less. If the pressure range is in this range, the above-mentioned metathesis reaction proceeds more preferably, and a zirconium nitride reduced in the second phase is obtained.
  • the reaction time is not particularly limited, but exemplarily, the above-mentioned raw material powder is reacted in a time of 10 minutes or more and 24 hours or less. If it is less than 10 minutes, the above-mentioned metathesis reaction may not be sufficient, and it may be inefficient because the reaction does not proceed even after 24 hours.
  • the reaction may be performed using any device as long as the temperature and pressure conditions described above are satisfied, but a belt type high pressure device is preferable, for example.
  • the belt type high pressure apparatus not only fulfills the above-mentioned conditions but also can be mass-produced and is practical.
  • FIG. 1 is a view schematically showing a high-pressure cell provided with a capsule used for producing a zirconium nitride according to an embodiment of the present invention.
  • FIG.1 (a) is a perspective view of a high voltage
  • FIG.1 (b) is sectional drawing of a high voltage
  • the high-pressure cell 1 comprises a cylindrical pyrophyllite 11 and two steel rings 12A and 12B arranged in contact with the upper and lower sides of the inner wall surface of the cylinder within the pyrophyllite 11 and a steel ring 12A. 12B, a cylindrical carbon heater 15 disposed on the central axis side, a pressure- and heat-resistant capsule 16 disposed inside the carbon heater 15, and a raw material powder 17 filled inside the pressure- and heat-resistant capsule 16.
  • the filler powder 13 is filled in the gap between the pyrophyllite 11 and the carbon heater 15, and the filler powder 14 is filled in the gap between the carbon heater 15 and the pressure resistant and heat resistant capsule 16.
  • FIG. 1 shows a raw material powder 17 in which a powder 18 of a halide of zirconium, a powder 19 of a nitride of a group 2 element, and a reaction inhibitor 20 are mixed in a pressure resistant and heat resistant capsule 16. .
  • the pressure resistant and heat resistant capsule 16 is arranged coaxially in the cylindrical carbon heater 15
  • the filler powder 14 is filled in the gap between the pressure- and heat-resistant capsule 16 and the inner wall surface of the carbon heater 15, and the filler powder 14 is spread on the top of the pressure- and heat-resistant capsule 16. Seal with lid.
  • the cylindrical carbon heater 15 is disposed coaxially in the cylindrical pyrophyllite 11, and then the gap between the carbon heater 15 and the inner wall surface of the pyrophyllite 11 is filled with the powder 13 for filling.
  • the filling powders 13 and 14 include NaCl + 10 wt% ZrO 2 .
  • the steel ring 12A is pressed so as to be embedded in the filling powder 13 on the upper side of the inner wall surface of the pyrophyllite 11 and another steel ring is embedded in the filling powder 13 on the lower side of the inner wall surface of the pyrophyllite 11 Push in 12B.
  • the high pressure cell 1 in which the raw material powder 17 is filled in the pressure resistant and heat resistant capsule 16 is obtained.
  • FIG. 2 is a view schematically showing a belt type high-pressure apparatus used for producing a nitride of zirconium according to an embodiment of the present invention.
  • Conductors 26A and 26B made of thin metal plates are brought into contact with predetermined positions between the cylinders 27A and 27B of the belt type high pressure apparatus 21 and between the anvils 25A and 25B, and the description will be made with reference to FIG.
  • the high pressure cell 1 is arranged.
  • pyrophyllite 28 is filled between these members and the high pressure cell 1.
  • the anvils 25A, 25B and the cylinders 27A, 27B are moved to the high pressure cell 1 side to press the high pressure cell 1 so as to satisfy the above-mentioned conditions.
  • heating may be performed so as to satisfy the above-described conditions, and the predetermined time may be maintained.
  • a nitride of zirconium which is an inorganic substance having the same crystal structure as c-Zr 3 N 4 is obtained, but following the reacting step, the obtained product is treated with a solvent , The second phase may be removed.
  • the product may contain a halide of a Group 2 element (MX 2 ) as a second phase, as shown in the above-mentioned reaction formula.
  • MX 2 Group 2 element
  • the steps of shaping and sintering the obtained product may be further performed.
  • a product obtained by the above-mentioned reacting step as a raw material to produce a larger sintered body and processing it into a cutting tool.
  • the particle size adjustment is performed until the product satisfies the range of 10 nm to 10 ⁇ m.
  • minute sintered compact can be manufactured.
  • the particle size adjustment is performed until the reaction product becomes a powder that satisfies the range of 50 nm to 5 ⁇ m. Thereby, it is possible to manufacture a hard material which is a compact and a sintered body in which grain growth is suppressed.
  • the particle size adjustment may be performed by classification such as sieving using a wet or dry ball mill, jet mill or the like.
  • Sintering sinters a formed body (may be formed into a pellet or the like, or may be filled in a container) in a temperature range of 1200 ° C. or more and 2000 ° C. or less. In this temperature range, sintering proceeds. More preferably, the molded body is sintered in a temperature range of 1300 ° C. or more and 1600 ° C. or less under a pressure of 2 GPa or more and 8 GPa or less. Within this temperature range and under this pressure, a hard material that is a dense sintered body can be manufactured while suppressing grain growth.
  • sintering time is based also on the magnitude
  • sintering after forming, it may be sintered in a normal atmosphere furnace, but may be sintered under pressure using a belt type high pressure apparatus, a hot press, a hot isostatic press (HIP) or the like.
  • Sintering is preferably performed in a reducing atmosphere, such as in a nitrogen atmosphere.
  • a material selected from the group consisting of TiN, BN (h-BN, c-BN), WC, WN, TaC, Co, Ni and Cr may be added to the product. .
  • the amount to be added is preferably less than 10% by weight.
  • the sintering aid is preferably h-BN (hexagonal silicon nitride) and / or c-BN (cubic silicon nitride).
  • the product and the sintering aid be directly mixed and used for the addition of the sintering aid to the product; It is also contemplated to use the same material as the sintering aid for the capsule material, for example, and sinter it as it is.
  • composition analysis of a nitride of zirconium which is an inorganic substance having the same crystal structure as that of cubic zirconium nitride represented by Zr 3 N 4 manufactured by adopting the method of the present invention is performed.
  • Group 2 elements are detected in ppm order or more. Therefore, whether the nitride of zirconium, which is an inorganic substance having the same crystal structure as that of cubic zirconium nitride represented by Zr 3 N 4 , is manufactured using the method of the present invention can be determined by composition analysis. If the group 2 element is detected in the ppm order or more by performing, it can be determined that it is manufactured by the method of the present invention.
  • Example 1 In Example 1, a raw material powder of ZrCl 4 as a halide of zirconium and Ca 3 N 2 as a nitride of a group 2 element using a belt type high pressure apparatus provided with a high pressure cell shown in FIGS. 1 and 2 From the above, the zirconium nitride of the present invention was manufactured at a pressure of 7.7 GPa and a temperature of 1600.degree. Specifically, it is as follows.
  • This raw material powder is filled in a cylindrical pressure- and heat-resistant capsule made of Mo (symbol 16 in FIG. 1) closed at one end with a disk-shaped lid, and the other end is made of disk-shaped Mo. Sealed with a lid. At this time, the bulk density at the time of filling was 1.8 g / cm 3 . Next, the powder for filling (NaCl + 10 wt% ZrO 2 ) is spread on the inner bottom of a cylindrical carbon heater (symbol 15 in FIG.
  • the cylindrical carbon heater is disposed coaxially in a cylindrical pyrophyllite, and then powder for filling (NaCl + 10 wt% ZrO 2 in the gap between the carbon heater and the inner wall surface of the pyrophyllite ) was filled.
  • the high pressure cell was placed at a predetermined position of the belt-type pressing device shown in FIG.
  • the high pressure cell was pressurized to 7.7 GPa (77,000 atmospheres). Next, it was heated to 1600 ° C. in a pressurized state. In this state, the temperature and pressure were maintained for 1 hour. Thus, the raw material powder was reacted at high temperature and pressure.
  • Example 1 The temperature was returned to room temperature and normal pressure, and the product was taken out from the inside of the pressure- and heat-resistant capsule. The product was then treated in water heated to 80.degree. This dissolved and removed CaCl 2 attached to the product. The product was then dispersed in a solvent (distilled water) and spun down in a centrifuge. The resulting product is referred to as the sample of Example 1.
  • Example 1 The sample of Example 1 was observed by a scanning electron microscope (SEM, JSM-IT100, manufactured by JEOL Ltd.) and identified by powder X-ray diffraction (XRD, RINT 2200, manufactured by Rigaku Corporation). The results are shown in FIG. 4 and Table 3.
  • Example 2 The second embodiment is the same as the first embodiment except that the temperature is 1500 ° C., and therefore the description thereof is omitted.
  • the product is referred to as the sample of Example 2.
  • the sample of Example 2 was observed by SEM and identified by XRD. The results are shown in FIG. 4 and Table 3.
  • Example 3 The third embodiment is the same as the first embodiment except that the temperature is set at 1400 ° C.
  • the product is referred to as the sample of Example 3.
  • the sample of Example 3 was observed by SEM and identified by XRD. The results are shown in FIG. 4 and Table 3.
  • Example 4 The fourth embodiment is the same as the first embodiment except that the temperature is 1300 ° C.
  • the product is referred to as the sample of Example 4 (this sample is also referred to as sample 4).
  • sample 4 As in Example 1, the sample of Example 4 was observed by SEM and identified by XRD. The results are shown in FIG. 3, FIG. 4 and Table 3.
  • Example 5 In Example 5, since it is the same as that of Example 1 except temperature having been 1200 degreeC, description is abbreviate
  • Comparative Example 1 The comparative example 1 is the same as the example 1 except that the temperature is set to 1100 ° C. The product is referred to as the sample of Comparative Example 1. Similar to Example 1, the sample of Comparative Example 1 was observed by SEM and identified by XRD. The results are shown in FIG. 4 and Table 3.
  • Example 6 The sixth embodiment is the same as the first embodiment except that the pressure is 5.5 GPa and the temperature is 1400 ° C.
  • the product is referred to as the sample of Example 6. Similar to Example 1, the sample of Example 6 was observed by SEM and identified by XRD. The results are shown in Table 3.
  • Example 2 a raw material powder of ZrCl 4 as a halide of zirconium and NaN 3 instead of a nitride of a group 2 element using a belt type high pressure apparatus equipped with a high pressure cell shown in FIGS. 1 and 2 From, the nitrides of zirconium were produced at various pressures 2.5 GPa, 5.0 GPa, 7.7 GPa, various temperatures 1100 ° C., 1300 ° C. and 1500 ° C. Further, under the conditions of 7.7 GPa and 1500 ° C., Mo and Pt were respectively used as the heat and pressure resistant capsules. The molar ratio of ZrCl 4 to NaN 3 was 3:12, and the production procedure was the same as in Example 1. The various products obtained in Comparative Example 2 were observed by SEM as in Example 1 and identified by XRD. The results are shown in FIG. 5 and Table 3.
  • FIG. 3 is a SEM image showing the form of the sample (sample 4) of Example 4.
  • the sample 4 was an amorphous powder having a maximum of 10 ⁇ m and an average of several ⁇ m.
  • the samples of Examples 1 to 3, 5 and 6 were in the same manner. In particular, as the reaction temperature became higher, the particle size of the powder tended to increase.
  • FIG. 4 is a view showing XRD patterns of the samples of Examples 1 to 5 and Comparative Example 1.
  • FIG. 5 is a view showing an XRD pattern of a sample of Comparative Example 2.
  • reaction temperature is preferably 1300 ° C. or more and 1600 ° C. or less.
  • the nitride of zirconium was c-Zr 3 N 4 itself, and / or Alternatively, it can be said that the inorganic substance has a molar ratio of Zr and N slightly deviated from the stoichiometric composition.
  • O oxygen
  • a part of N may be replaced by O
  • the XRD pattern of the sample of Example 6 also showed the same pattern as the samples of Examples 1-5. From this, it was shown that a pressure range of 5 GPa or more and 8 GPa or less is preferable, including the error of the apparatus.
  • FIG. 5 shows XRD patterns of products reacted at various temperatures of 1100 ° C., 1300 ° C., and 1500 ° C. at a pressure of 7.7 GPa using a heat-resistant pressure-resistant capsule made of Mo. No diffraction peak indicating c-Zr 3 N 4 crystal was found in any of the XRD patterns. Although not shown, in Comparative Example 2, no diffraction peak indicating c-Zr 3 N 4 crystal was observed in the XRD patterns of the products obtained under all other conditions.
  • a nitride of zirconium which is an inorganic substance having the same crystal structure as the crystal structure of cubic zirconium nitride represented by Zr 3 N 4 , a powder of a halide of zirconium, and Group 2 It was shown that it is effective to include the step of reacting the raw material powder containing elemental nitride powder and at a pressure of 5 GPa or more and 8 GPa or less at a temperature range of more than 1100 ° C. and 2500 ° C. or less. .
  • Example 7 the product produced in Example 4 was sintered using a hexagonal boron nitride (h-BN) capsule by means of the belt-type pressing device of FIGS.
  • the particle size of the product was adjusted to a particle size of 10 nm to 10 ⁇ m by classification method.
  • the sized product was filled into h-BN capsules and sintered at 1400 ° C. for 15 minutes under a pressure of 7.7 GPa.
  • the surface (after polishing) of the obtained sintered body was observed, and X-ray diffraction measurement and Vickers hardness test were performed. The results are shown in FIG. 6 and FIG.
  • FIG. 6 is a view showing an aspect of the sintered body of Example 7.
  • the surface of the sintered body had a gloss, and at first glance it was not in the form of porous but in the form of a hard material.
  • FIG. 7 is a view showing an XRD pattern of the sintered body of Example 7.
  • the XRD pattern of the sintered body also shows a diffraction peak (black circles in the figure) indicating c-Zr 3 N 4 crystals, and c-Zr 3 N 4 produced also by heating for sintering. It has been confirmed that zirconium nitride having the same crystal structure as that of the above does not decompose.
  • the XRD pattern of the sintered body showed a diffraction peak showing cubic boron nitride (c-BN) in part. This suggests that h-BN used for the capsule functioned as a sintering aid.
  • a zirconium nitride having a crystal structure identical to that of c-Zr 3 N 4 is obtained, and further, this is sintered to obtain c-Zr. It has been shown that a sintered body of zirconium nitride having the same crystal structure as that of 3 N 4 can be provided.
  • a nitride of zirconium which is an inorganic substance having the same crystal structure as that of cubic zirconium nitride represented by Zr 3 N 4 excellent in hardness and wear resistance, is reproduced with good reproducibility. And it can manufacture in the pressure range which can be commercialized.
  • the nitride of zirconium thus obtained is preferable for grinding and cutting tools (for example, drills, end mills, bobs, milling cutters, lathes, pinion cutters, etc.), and in the processing tool industry, processing industry, processing equipment industry etc. It is used.

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Abstract

La présente invention concerne un procédé de production, d'un nitrure de zirconium, comme substance inorganique qui présente la même structure cristalline que celle d'un nitrure de zirconium cubique représenté par Zr3N4 avec une bonne reproductibilité sous basse pression. Ce procédé de production d'un nitrure de zirconium qui est une substance inorganique qui présente la même structure cristalline que celle d'un nitrure de zirconium cubique représenté par Zr3N4 comprend une étape de réaction d'une poudre de matière première qui comprend de la poudre d'un halogénure de zirconium et de la poudre d'un nitrure d'un élément du groupe (2) dans une plage de températures supérieures à 1 100 °C et 2 500 °C ou inférieures sous une pression de 5 à 8 GPa.
PCT/JP2018/026665 2017-10-19 2018-07-17 Procédé de production de nitrure de zirconium WO2019077820A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60186407A (ja) * 1984-03-06 1985-09-21 Toyo Soda Mfg Co Ltd 窒化ジルコニウム微粉末の製造法
JPH01502975A (ja) * 1987-01-08 1989-10-12 セレックス セラミック粉の製造方法および得られた粉末
US5110768A (en) * 1991-01-28 1992-05-05 Kaner Richard B Rapid solid-state synthesis of refractory materials
JP2002506787A (ja) * 1998-03-16 2002-03-05 エスウペ ビャンベニュ−ラコステ 耐熱性金属の粉末状複合セラミックの合成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60186407A (ja) * 1984-03-06 1985-09-21 Toyo Soda Mfg Co Ltd 窒化ジルコニウム微粉末の製造法
JPH01502975A (ja) * 1987-01-08 1989-10-12 セレックス セラミック粉の製造方法および得られた粉末
US5110768A (en) * 1991-01-28 1992-05-05 Kaner Richard B Rapid solid-state synthesis of refractory materials
JP2002506787A (ja) * 1998-03-16 2002-03-05 エスウペ ビャンベニュ−ラコステ 耐熱性金属の粉末状複合セラミックの合成方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ALI, S. ET AL.: "Solid state metathesis routes to metal nitrides; use of strontium and barium nitrides as regents and dilution effects", POLYHEDRON, vol. 16, no. 20, 1997, pages 3635 - 3640, XP002600053, ISSN: 0277-5387 *

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