CN102001634B - Method for producing zirconium nitride powder - Google Patents
Method for producing zirconium nitride powder Download PDFInfo
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- CN102001634B CN102001634B CN2010105318582A CN201010531858A CN102001634B CN 102001634 B CN102001634 B CN 102001634B CN 2010105318582 A CN2010105318582 A CN 2010105318582A CN 201010531858 A CN201010531858 A CN 201010531858A CN 102001634 B CN102001634 B CN 102001634B
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Abstract
The invention discloses a method for producing zirconium nitride powder, which comprises the following steps of: crushing sponge zirconium into granules with the granularity of less than 3mm, putting the crushed sponge zirconium granules into a vacuum furnace, supplying power for raising the temperature when the vacuum degree is 5 to 40Pa, keeping the temperature at the pre-nitrogenization temperature, stopping vacuumizing, and introducing nitrogen into the furnace for a pre-nitrogenization reaction; after the pre-nitrogenization, cutting off the power for reducing the temperature to 80 DEG C, and discharging; crushing the pre-nitrogenized materials into powder with the granularity of less than 0.075mm, putting the powder into the vacuum furnace, supplying power for raising the temperature to between 500 and 700 DEG C within 2 to 5 hours when the vacuum degree is 5 to 40Pa; stopping vacuumizing, introducing nitrogen into the furnace continuously raising the temperature to the nitrogenization temperature within 3 to 6 hours, and continuously introducing the nitrogen for nitrogenization; after the nitrogenization, cutting off the power for reducing the temperature, continuously introducing the nitrogen in the process of reducing the temperature, and discharging a zirconium nitride clinker when the temperature is reduced to 80 DEG C; and crushing the zirconium nitride clinker so as to prepare the zirconium nitride powder.
Description
Technical field
The invention belongs to the powder metallurgy production field, particularly a kind of working method of zirconium nitride powder.
Background technology
Zirconium nitride ZrN is a kind of infusible compound, is golden yellow, and decomposition temperature is high, and chemicalstability is good, has good high temperature resistant, corrosion-resistant, wear resisting property, is the good high-temperature structured material, also is superhard tool material and surface protecting material.The method of at present synthetic ZrN roughly has three kinds: one of which, metal zirconium powder Zr direct nitridation method; Its two, zirconium white ZrO
2The carbothermal reduction-nitridation method; Its three, zirconium chloride ZrCl
4Vapour deposition process.Metal zirconium powder direct nitridation method is that granularity is heated to 1200 ℃ less than the zirconium powder of 0.045mm in nitrogen, forms ZrN, and this method technology is simple; Energy consumption is low, and product ZrN purity is high, and its purity can reach 99～99.9%; Shortcoming is that reaction can not be carried out fully; Building-up process is prone to produce melting process, suppresses fusion even adopt product ZrN to make thinner, and effect is also undesirable.In addition, zirconium powder must be with zirc sponge or iodate purification zirconium through over hydrogenation---and operations such as dehydrogenation, wet-milling, oven dry are processed powder, and operation is long, and production capacity is low, and cost is high.Zirconium white carbothermal reduction-nitridation method is with ZrO
2With in nitrogen atmosphere, be heated to more than 1100 ℃ ZrO behind the C mixing
2By after the C reduction again with nitrogen N
2Synthetic ZrN, this method cost of material is cheap, and powder particle is not evenly reunited, and is fit to produce in batches, and shortcoming is that reduction process is used excessive C, causes product ZrN impurity C and O content higher, and purity is lower than 99%.ZrCl
4Though vapour deposition processization can obtain not only pure but also thin ZrN powder, by product HCl corrosive equipment only is suitable in the laboratory, using, preparation film and coating.
Summary of the invention
The technical problem that the present invention will solve is; Overcome that existing metal zirconium nitriding production process is long, cost is high and building-up process is prone to produce the problem of melting phenomenon, the working method of the zirconium nitride powder that a kind of technical process is short, production cost is low, building-up process does not produce melting phenomenon is provided.
Working method of the present invention is:
1, zirc sponge is ground into the particle of granularity less than 3mm;
2, nitrogenize in advance: the zirc sponge particle after will pulverizing places in the vacuum oven, vacuumizes earlier, and vacuum tightness reaches 5～40Pa feeding temperature-raising, continues in the temperature-rise period to vacuumize; And vacuum tightness remained in 10～100Pa scope, reach constant temperature behind the preparatory nitriding temperature, stop to vacuumize; In stove, charge into nitrogen and carry out preparatory nitrogenizing reaction, wherein, nitriding temperature is 700～900 ℃ in advance; TRT is 5～10 hours, and nitrogen pressure in furnace is 80～100kPa, and nitridation time is 3～5 hours in advance; After in advance nitrogenize finished, the cooling that has a power failure continued to charge into nitrogen in the temperature-fall period, and to keep nitrogen pressure in furnace be 100～110kPa, and temperature is reduced to 80 ℃ and come out of the stove;
3, nitrogenize: preparatory nitrogenize material is ground into granularity less than the 0.075mm powder, packs into once more in the vacuum oven, vacuumize earlier, vacuum tightness reaches 5～40Pa feeding temperature-raising; Continue in the temperature-rise period to vacuumize, and vacuum tightness is remained in 10～100Pa scope, through 2～5 hours, temperature reached 500～700 ℃; Stop to vacuumize, in stove, charge into nitrogen and continue and heat up, nitrogen pressure in furnace is 80～100kPa in the temperature-rise period, reaches nitriding temperature through 3～6 hours and is incubated; Continue to charge into nitrogen and carry out nitrogenize, wherein, nitriding temperature is 1000～1400 ℃, and nitrogen pressure in furnace is 90～100kPa; Nitridation time is 3～5 hours, and after nitrogenize finished, the cooling that has a power failure continued to charge into nitrogen in the temperature-fall period; The maintenance nitrogen pressure in furnace is 100～110kPa, when temperature is reduced to 80 ℃, stops inflated with nitrogen, and the zirconium nitride agglomerate is come out of the stove;
4, the zirconium nitride agglomerate is pulverized, promptly obtained the zirconium nitride powder.
Described zirc sponge purity is greater than 99%.
Described nitrogen gas purity is greater than 99.9%.
The granularity of described zirconium nitride powder is less than 0.05mm, and ZrN purity is 99～99.5%.
The invention has the advantages that:
1, removed zirc sponge hydrogenation---dehydrogenation powder process operation, technical process has shortened 1/3, thereby has reduced production cost, has increased production capacity, has improved production efficiency, is suitable for large-scale production.
2, adopt two steps of preparatory nitrogenize and nitrogenize to accomplish nitridation process, avoided the melting phenomenon that produces in high-temperature ammonolysis process, improved nitrogenize efficient.
Embodiment
Embodiment 1:
1.1, purity is ground into the particle of granularity less than 3mm greater than 99% zirc sponge;
1.2, in advance nitrogenize: the zirc sponge particle after will pulverizing places in the vacuum oven, vacuumizes earlier, and vacuum tightness reaches the 10Pa feeding temperature-raising, continues in the temperature-rise period to vacuumize; And vacuum tightness remained in 10～100Pa scope, reach constant temperature behind the preparatory nitriding temperature, stop to vacuumize, in stove, charge into nitrogen and carry out preparatory nitrogenizing reaction; Wherein, nitrogen gas purity is greater than 99.9%, and nitriding temperature is 750 ℃ in advance; TRT is 7 hours, and nitrogen pressure in furnace is 80～100kPa, and nitridation time is 4 hours in advance; After in advance nitrogenize finished, the cooling that has a power failure continued to charge into nitrogen in the temperature-fall period, and to keep nitrogen pressure in furnace be 100～110kPa, and temperature is reduced to 80 ℃ and come out of the stove;
1.3, nitrogenize: preparatory nitrogenize material is ground into granularity less than the 0.075mm powder, packs into once more in the vacuum oven, vacuumize earlier, vacuum tightness reaches the 20Pa feeding temperature-raising, continues in the temperature-rise period to vacuumize; And vacuum tightness remained in 10～100Pa scope, through 3 hours, temperature reached 600 ℃, stopped to vacuumize; In stove, charge into nitrogen and continue and heat up, nitrogen pressure in furnace is 80～100kPa in the temperature-rise period, reaches nitriding temperature through 4 hours and is incubated, and continues to charge into nitrogen and carries out nitrogenize; Wherein, nitrogen gas purity is greater than 99.9%, and nitriding temperature is 1200 ℃, and nitrogen pressure in furnace is 90～100kPa; Nitridation time is 4 hours, and after nitrogenize finished, the cooling that has a power failure continued to charge into nitrogen in the temperature-fall period; The maintenance nitrogen pressure in furnace is 100～110kPa, when temperature is reduced to 80 ℃, stops inflated with nitrogen, and the zirconium nitride agglomerate is come out of the stove;
1.4, the zirconium nitride agglomerate is pulverized, promptly obtain the zirconium nitride powder, through measuring, the product main chemical compositions is following: Zr:87.4%, N:11.8%, ZrN purity is 99.2%.
Embodiment 2:
2.1, purity is ground into the particle of granularity less than 3mm greater than 99% zirc sponge;
2.2, in advance nitrogenize: the zirc sponge particle after will pulverizing places in the vacuum oven, vacuumizes earlier, and vacuum tightness reaches the 10Pa feeding temperature-raising, continues in the temperature-rise period to vacuumize; And vacuum tightness remained in 10～100Pa scope, reach constant temperature behind the preparatory nitriding temperature, stop to vacuumize, in stove, charge into nitrogen and carry out preparatory nitrogenizing reaction; Wherein, nitrogen gas purity is greater than 99.9%, and nitriding temperature is 800 ℃ in advance; TRT is 9 hours, and nitrogen pressure in furnace is 80～100kPa, and nitridation time is 4 hours in advance; After in advance nitrogenize finished, the cooling that has a power failure continued to charge into nitrogen in the temperature-fall period, and to keep nitrogen pressure in furnace be 100～110kPa, and temperature is reduced to 80 ℃ and come out of the stove;
2.3, nitrogenize: preparatory nitrogenize material is ground into granularity less than the 0.075mm powder, packs into once more in the vacuum oven, vacuumize earlier, vacuum tightness reaches the 20Pa feeding temperature-raising, continues in the temperature-rise period to vacuumize; And vacuum tightness remained in 10～100Pa scope, through 4 hours, temperature reached 650 ℃, stopped to vacuumize; In stove, charge into nitrogen and continue and heat up, nitrogen pressure in furnace is 80～100kPa in the temperature-rise period, reaches nitriding temperature through 5 hours and is incubated, and continues to charge into nitrogen and carries out nitrogenize; Wherein, nitrogen gas purity is greater than 99.9%, and nitriding temperature is 1300 ℃, and nitrogen pressure in furnace is 90～100kPa; Nitridation time is 5 hours, and after nitrogenize finished, the cooling that has a power failure continued to charge into nitrogen in the temperature-fall period; The maintenance nitrogen pressure in furnace is 100～110kPa, when temperature is reduced to 80 ℃, stops inflated with nitrogen, and the zirconium nitride agglomerate is come out of the stove;
2.4, the zirconium nitride agglomerate is pulverized, promptly obtain the zirconium nitride powder, through measuring, the product main chemical compositions is following: Zr:86.9%, N:12.5%, ZrN purity is 99.4%.
Embodiment 3:
3.1, purity is ground into the particle of granularity less than 3mm greater than 99% zirc sponge;
3.2, in advance nitrogenize: the zirc sponge particle after will pulverizing places in the vacuum oven, vacuumizes earlier, and vacuum tightness reaches the 5Pa feeding temperature-raising, continues in the temperature-rise period to vacuumize; And vacuum tightness remained in 10～100Pa scope, reach constant temperature behind the preparatory nitriding temperature, stop to vacuumize, in stove, charge into nitrogen and carry out preparatory nitrogenizing reaction; Wherein, nitrogen gas purity is greater than 99.9%, and nitriding temperature is 700 ℃ in advance; TRT is 5 hours, and nitrogen pressure in furnace is 80～100kPa, and nitridation time is 5 hours in advance; After in advance nitrogenize finished, the cooling that has a power failure continued to charge into nitrogen in the temperature-fall period, and to keep nitrogen pressure in furnace be 100～110kPa, and temperature is reduced to 80 ℃ and come out of the stove;
3.3, nitrogenize: preparatory nitrogenize material is ground into granularity less than the 0.075mm powder, packs into once more in the vacuum oven, vacuumize earlier, vacuum tightness reaches the 5Pa feeding temperature-raising, continues in the temperature-rise period to vacuumize; And vacuum tightness remained in 10～100Pa scope, through 2 hours, temperature reached 500 ℃, stopped to vacuumize; In stove, charge into nitrogen and continue and heat up, nitrogen pressure in furnace is 80～100kPa in the temperature-rise period, reaches nitriding temperature through 3 hours and is incubated, and continues to charge into nitrogen and carries out nitrogenize; Wherein, nitrogen gas purity is greater than 99.9%, and nitriding temperature is 1000 ℃, and nitrogen pressure in furnace is 90～100kPa; Nitridation time is 4 hours, and after nitrogenize finished, the cooling that has a power failure continued to charge into nitrogen in the temperature-fall period; The maintenance nitrogen pressure in furnace is 100～110kPa, when temperature is reduced to 80 ℃, stops inflated with nitrogen, and the zirconium nitride agglomerate is come out of the stove;
3.4, the zirconium nitride agglomerate is pulverized, promptly obtain the zirconium nitride powder, through measuring, the product main chemical compositions is following: Zr:87.1%, N:11.9%, ZrN purity is 99%.
Embodiment 4:
4.1, purity is ground into the particle of granularity less than 3mm greater than 99% zirc sponge;
4.2, in advance nitrogenize: the zirc sponge particle after will pulverizing places in the vacuum oven, vacuumizes earlier, and vacuum tightness reaches the 40Pa feeding temperature-raising, continues in the temperature-rise period to vacuumize; And vacuum tightness remained in 10～100Pa scope, reach constant temperature behind the preparatory nitriding temperature, stop to vacuumize, in stove, charge into nitrogen and carry out preparatory nitrogenizing reaction; Wherein, nitrogen gas purity is greater than 99.9%, and nitriding temperature is 900 ℃ in advance; TRT is 10 hours, and nitrogen pressure in furnace is 80～100kPa, and nitridation time is 3 hours in advance; After in advance nitrogenize finished, the cooling that has a power failure continued to charge into nitrogen in the temperature-fall period, and to keep nitrogen pressure in furnace be 100～110kPa, and temperature is reduced to 80 ℃ and come out of the stove;
4.3, nitrogenize: preparatory nitrogenize material is ground into granularity less than the 0.075mm powder, packs into once more in the vacuum oven, vacuumize earlier, vacuum tightness reaches the 40Pa feeding temperature-raising, continues in the temperature-rise period to vacuumize; And vacuum tightness remained in 10～100Pa scope, through 5 hours, temperature reached 700 ℃, stopped to vacuumize; In stove, charge into nitrogen and continue and heat up, nitrogen pressure in furnace is 80～100kPa in the temperature-rise period, reaches nitriding temperature through 6 hours and is incubated, and continues to charge into nitrogen and carries out nitrogenize; Wherein, nitrogen gas purity is greater than 99.9%, and nitriding temperature is 1400 ℃, and nitrogen pressure in furnace is 90～100kPa; Nitridation time is 3 hours, and after nitrogenize finished, the cooling that has a power failure continued to charge into nitrogen in the temperature-fall period; The maintenance nitrogen pressure in furnace is 100～110kPa, when temperature is reduced to 80 ℃, stops inflated with nitrogen, and the zirconium nitride agglomerate is come out of the stove;
4.4, the zirconium nitride agglomerate is pulverized, promptly obtain the zirconium nitride powder, through measuring, the product main chemical compositions is following: Zr:87.6%, N:11.9%, ZrN purity is 99.5%.
Claims (4)
1. the working method of a zirconium nitride powder is characterized in that, it is produced according to following method:
(1) zirc sponge is ground into the particle of granularity less than 3mm;
(2) nitrogenize in advance: the zirc sponge particle after will pulverizing places in the vacuum oven, vacuumizes earlier, and vacuum tightness reaches 5～40Pa feeding temperature-raising, continues in the temperature-rise period to vacuumize; And vacuum tightness remained in 10～100Pa scope, reach constant temperature behind the preparatory nitriding temperature, stop to vacuumize; In stove, charge into nitrogen and carry out preparatory nitrogenizing reaction, wherein, nitriding temperature is 700～900 ℃ in advance; TRT is 5～10 hours, and nitrogen pressure in furnace is 80～100kPa, and nitridation time is 3～5 hours in advance; After in advance nitrogenize finished, the cooling that has a power failure continued to charge into nitrogen in the temperature-fall period, and to keep nitrogen pressure in furnace be 100～110kPa, and temperature is reduced to 80 ℃ and come out of the stove;
(3) nitrogenize: preparatory nitrogenize material is ground into granularity less than the 0.075mm powder, packs into once more in the vacuum oven, vacuumize earlier, vacuum tightness reaches 5～40Pa feeding temperature-raising; Continue in the temperature-rise period to vacuumize, and vacuum tightness is remained in 10～100Pa scope, through 2～5 hours, temperature reached 500～700 ℃; Stop to vacuumize, in stove, charge into nitrogen and continue and heat up, nitrogen pressure in furnace is 80～100kPa in the temperature-rise period, reaches nitriding temperature through 3～6 hours and is incubated; Continue to charge into nitrogen and carry out nitrogenize, wherein, nitriding temperature is 1000～1400 ℃, and nitrogen pressure in furnace is 90～100kPa; Nitridation time is 3～5 hours, and after nitrogenize finished, the cooling that has a power failure continued to charge into nitrogen in the temperature-fall period; The maintenance nitrogen pressure in furnace is 100～110kPa, when temperature is reduced to 80 ℃, stops inflated with nitrogen, and the zirconium nitride agglomerate is come out of the stove;
(4) the zirconium nitride agglomerate is pulverized, promptly obtained the zirconium nitride powder.
2. the working method of zirconium nitride powder according to claim 1 is characterized in that, described zirc sponge purity is greater than 99%.
3. the working method of zirconium nitride powder according to claim 1 is characterized in that, described nitrogen gas purity is greater than 99.9%.
4. the working method of zirconium nitride powder according to claim 1 is characterized in that, the granularity of described zirconium nitride powder is less than 0.05mm, and ZrN purity is 99～99.5%.
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| CN104176715B (en) * | 2013-05-22 | 2016-01-20 | 安徽港铭新材料科技有限公司 | A kind of preparation method of zirconium nitrogen alloy |
| JP6954769B2 (en) * | 2017-06-09 | 2021-10-27 | 三菱マテリアル電子化成株式会社 | Zirconium nitride powder and its manufacturing method |
| CN110329998B (en) * | 2019-07-23 | 2021-02-02 | 英特美光电（苏州）有限公司 | Method for preparing strontium nitride powder in high-pressure nitriding furnace |
| JP7339080B2 (en) | 2019-09-04 | 2023-09-05 | 三菱マテリアル電子化成株式会社 | Zirconium nitride powder and method for producing the same |
| US11697156B2 (en) | 2020-12-18 | 2023-07-11 | Mitsubishi Materials Electronic Chemicals Co., Ltd. | Zirconium nitride powder and method for producing same |
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| CN1239385C (en) * | 2003-11-28 | 2006-02-01 | 中国科学院上海硅酸盐研究所 | Method for reduction nitridation preparation of nano cubic zirconium nitride powders |
| CN100564248C (en) * | 2008-01-23 | 2009-12-02 | 吉林大学 | A kind of ball-milling preparation method of cubic-phase nano zirconium nitride |
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