CN103272528A - Method for synthesizing cubic boron nitrides by using alkali metal azide - Google Patents
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Abstract
The invention discloses a method for synthesizing cubic boron nitrides by using an alkali metal azide, which relates to a high-temperature and high-pressure synthesis method for superhard materials. The method is implemented by taking hexagonal boron nitride as a raw material and taking a mixture of alkali metal nitrides and azide as a catalytic agent through the steps of uniformly mixing the raw material and the catalytic agent, carrying out pre-compaction forming on the obtained mixture, assembling the obtained object in a pyrophyllite synthesis block, and synthesizing cubic boron nitrides under high-temperature and high-pressure conditions, wherein the synthesis temperature is 1,000-1,800 DEG C, the synthetic pressure is 4.0-6.0 GPa, and the synthesis time is 3-15 minutes; and carrying out purification treatment on a synthetic product so as to obtain a cubic boron nitride single crystal product. According to the invention, through adding the alkali metal azide in a catalytic agent system, a nitrogen-rich environment is provided, the influence of impurities such as boron oxides on cBN synthesis is suppressed, the nucleation of cubic boron nitrides is promoted, the growth rate and conversion rate of cubic boron nitrides are improved, the requirements on the purity of hexagonal boron nitride are reduced, and the quality of products is good, and therefore, the method has important application value in the field of the industrialized production of cubic boron nitride superhard materials.
Description
Technical field
The present invention relates to a kind of HTHP synthetic method of superhard material, particularly a kind of method with alkali metal azide synthesizing cubic boron nitride monocrystalline.
Background technology
Cubic boron nitride (cBN) is that a kind of hardness is only second to adamantine superhard material, but its heat endurance is better than diamond, and it has extremely strong chemical inertness to iron family element and alloy thereof, at high temperature not with iron family element generation chemical reaction, therefore, cBN is specially adapted to process iron family element, and it is made goods such as cutter, emery wheel and hone bar and has been widely used in the iron and steel of high rigidity and the manufacture field of alloy material thereof as abrasive material.
Usually cubic boron nitride is (10GPa, 2000 under HTHP
oC) be directly transformed by hexagonal boron nitride, having under the situation of catalyst, the condition of synthesizing cubic boron nitride can be reduced significantly.General cubic boron nitride synthetic method is catalyst with alkali metal such as lithium, magnesium, calcium and alkaline-earth metal or its nitride, nitrogen boride, is the raw material synthesizing cubic boron nitride with the hexagonal boron nitride.Shortcomings such as tradition catalyst system synthesizing cubic boron nitride exists hexagonal boron nitride purity requirement height, and the speed of growth is slow, conversion ratio is low.For example, Japan Patent JP56-140013 is disclosed to be raw material with hexagonal boron nitride (hBN), and lithium nitride, CaCl2 are made catalyst, have synthesized the cubic boron nitride monocrystal powder of high strength, low impurity content under HTHP.But the used catalyst of this method is higher to the purity requirement of hexagonal boron nitride, hexagonal boron nitride purity greater than 99.8%, boron oxide content be lower than 0.1% and the graphitization index less than the synthetic effect that just can obtain in 2 o'clock, when being lower than above-mentioned requirements as hexagonal boron nitride purity, the speed of growth of cubic boron nitride will obviously descend, and conversion ratio is also very low.
Granted publication number a kind of for the Chinese patent of CN100496696C discloses " with the method for alkali metal fluoride synthesizing cubic boron nitride ".This patent is done raw material with hexagonal boron nitride, with LiF and Li
3The N mixture is catalyst, adds LiH as additive, mixes the back pre-molding, reinstalls and is assembled into synthetic piece in the graphite-pipe.Synthesis temperature is 1000-1800 ℃, synthesis pressure 4.0-6.0GPa, and generated time 3-8 minute, synthetic product obtained the transparent cubic boron nitride monocrystal of reddish yellow after chemical treatment, and the cubic boron nitride speed of growth and the conversion ratio of this patent are still not high enough.
Summary of the invention
The technical problem to be solved in the present invention is: provide a kind of method with alkali metal azide synthesizing cubic boron nitride, to improve the speed of growth and the conversion ratio of cubic boron nitride.
The technical scheme that solves the problems of the technologies described above is: a kind of method with alkali metal azide synthesizing cubic boron nitride, this method be a kind of be raw material with the hexagonal boron nitride, under high-temperature and high-pressure conditions, add the method for catalyst synthesizing cubic boron nitride monocrystalline, described catalyst is the catalyst mixture that comprises alkali metal nitride and alkali metal azide, and this alkali metal nitride and alkali metal azide are by weight ratio: 1:0.01～0.5; Described hexagonal boron nitride raw material and catalyst mixture are by weight ratio: 1:0.1～0.3; Described high-temperature and high-pressure conditions refers to: 1000～1800 ℃ of synthesis temperatures, synthesis pressure 4.0～6.0GPa, 3～15 minutes heat-insulation pressure keeping time.
Further technical scheme of the present invention is: this method may further comprise the steps:
A. get the raw materials ready: being raw material with the hexagonal boron nitride, is that the mixture of 1:0.01～0.5 is that catalyst mixture is got the raw materials ready with alkali metal nitride and alkali metal azide by weight ratio;
B. mix and pre-molding: be by weight ratio: the ratio of hexagonal boron nitride raw material: catalyst mixture=1:0.1～0.3 is got material respectively, is pressed into cylindric bar in advance after evenly mixing;
C. synthetic: cylindric bar is packed in the synthetic piece of pyrophillite, synthesize at top press pyrophillite is synthetic packaged, synthesis temperature is 1000～1800 ℃, and synthesis pressure is 4.0～6.0Gpa;
D. heat-insulation pressure keeping: heat-insulation pressure keeping 3～15 minutes stops to heat the back and waits for 1～3 minute;
E. get material, cooling: slowly be depressurized to normal pressure, take out cylindric bar, be cooled to room temperature;
F. purify: cooled cylindric bar is carried out the soda acid purification processes, make the cubic boron nitride monocrystal product.
Further technical scheme more of the present invention is: the described cubic boron nitride monocrystal product that makes is to dark amber transparent sheet cubic boron nitride monocrystal from faint yellow.
Further technical scheme of the present invention is: the purity of described alkali metal nitride and alkali metal azide is more than 99%, and the purity of described hexagonal boron nitride is more than 95%.
Because adopt said structure, the method for usefulness alkali metal azide synthesizing cubic boron nitride of the present invention compared with prior art has following beneficial effect:
1. can improve the speed of growth and the conversion ratio of cubic boron nitride:
Because the present invention is by add alkali metal azide in the typical alkali metal nitride catalyst system of synthesizing cubic boron nitride, this alkali metal azide provides a rich nitrogen environment, suppressed the influence synthetic to cBN of impurity such as boron oxide, promoted the nucleation of cubic boron nitride, improve the speed of growth of cubic boron nitride, thereby improved the conversion ratio of cubic boron nitride.
2. can reduce the requirement to hexagonal boron nitride purity:
Because the present invention is by add the speed of growth and the conversion ratio that alkali metal azide improves cubic boron nitride in alkali metal nitride catalyst system, therefore the requirement to hexagonal boron nitride purity is not very high, and the purity of generally only requiring hexagonal boron nitride is to get final product more than 95%.
3. good product quality:
The product that the present invention makes is for crystal size is even to dark amber transparent sheet cubic boron nitride monocrystal from faint yellow, the transparency height, and crystalline form is complete.
Below, the technical characterictic to the method for usefulness alkali metal azide synthesizing cubic boron nitride of the present invention is further described in conjunction with the embodiments.
The specific embodiment
Embodiment one:
A kind of method with alkali metal azide synthesizing cubic boron nitride, this method be a kind of be raw material with the hexagonal boron nitride, under high-temperature and high-pressure conditions, add the method for catalyst synthesizing cubic boron nitride monocrystalline, it may further comprise the steps:
A. get the raw materials ready: the hexagonal boron nitride with purity 95% is raw material, is 99% lithium nitride Li with purity
3N and sodium azide NaN
3Be that catalyst mixture is got the raw materials ready for the mixture of 1:0.1 by weight ratio;
B. mix and pre-molding: be by weight ratio: the ratio of hexagonal boron nitride raw material: catalyst mixture=1:0.2 is got material respectively, is pressed into cylindric bar in advance after evenly mixing;
C. synthetic: cylindric bar is packed in the synthetic piece of pyrophillite, synthesize at cubic hinge press pyrophillite is synthetic packaged, synthesis temperature is 1200 ℃, and synthesis pressure is 4.5Gpa;
D. heat-insulation pressure keeping: heat-insulation pressure keeping 8 minutes stops to heat the back and waits for 2 minutes;
E. get material, cooling: slowly be depressurized to normal pressure, take out cylindric bar, be cooled to room temperature;
F. purify: cooled cylindric bar is carried out the soda acid purification processes, make the cubic boron nitride monocrystal product, this cubic boron nitride monocrystal product is faint yellow transparent sheet cubic boron nitride monocrystal.
The conversion ratio of above-mentioned cubic boron nitride is 35-40%.
Embodiment two:
A kind of method with alkali metal azide synthesizing cubic boron nitride, this method be a kind of be raw material with the hexagonal boron nitride, under high-temperature and high-pressure conditions, add the method for catalyst synthesizing cubic boron nitride monocrystalline, it may further comprise the steps:
A. get the raw materials ready: the hexagonal boron nitride with purity 95% is raw material, is 99% lithium nitride Li with purity
3N and sodium azide NaN
3Be that catalyst mixture is got the raw materials ready for the mixture of 1:0.3 by weight ratio;
B. mix and pre-molding: be by weight ratio: the ratio of hexagonal boron nitride raw material: catalyst mixture=1:0.25 is got material respectively, is pressed into cylindric bar in advance after evenly mixing;
C. synthetic: cylindric bar is packed in the synthetic piece of pyrophillite, synthesize at belt type press pyrophillite is synthetic packaged, synthesis temperature is 1500 ℃, and synthesis pressure is 5.5Gpa;
D. heat-insulation pressure keeping: heat-insulation pressure keeping 10 minutes stops to heat the back and waits for 2 minutes;
E. get material, cooling: slowly be depressurized to normal pressure, take out cylindric bar, be cooled to room temperature;
F. purify: cooled cylindric bar is carried out the soda acid purification processes, make the cubic boron nitride monocrystal product, this cubic boron nitride monocrystal product is dark amber transparent sheet cubic boron nitride monocrystal.
The conversion ratio of above-mentioned cubic boron nitride is 40%.
Embodiment three:
A kind of method with alkali metal azide synthesizing cubic boron nitride, the basic step of this method and parameter are all with embodiment two, institute's difference: the described heat-insulation pressure keeping time is 5 minutes, prepared cubic boron nitride monocrystal product is with embodiment 2, but granularity is slightly thin, color is shallow slightly, and the conversion ratio of cBN is 30%.
Embodiment four:
A kind of method with alkali metal azide synthesizing cubic boron nitride, this method be a kind of be raw material with the hexagonal boron nitride, under high-temperature and high-pressure conditions, add the method for catalyst synthesizing cubic boron nitride monocrystalline, it may further comprise the steps:
A. get the raw materials ready: the hexagonal boron nitride with purity 96% is raw material, is 99.5% lithium nitride Li with purity
3N and sodium azide NaN
3Be that catalyst mixture is got the raw materials ready for the mixture of 1:0.01 by weight ratio;
B. mix and pre-molding: be by weight ratio: the ratio of hexagonal boron nitride raw material: catalyst mixture=1:0.1 is got material respectively, is pressed into cylindric bar in advance after evenly mixing;
C. synthetic: cylindric bar is packed in the synthetic piece of pyrophillite, synthesize at cubic hinge press pyrophillite is synthetic packaged, synthesis temperature is 1000 ℃, and synthesis pressure is 4.0Gpa;
D. heat-insulation pressure keeping: heat-insulation pressure keeping 3 minutes stops to heat the back and waits for 1 minute;
E. get material, cooling: slowly be depressurized to normal pressure, take out cylindric bar, be cooled to room temperature;
F. purify: cooled cylindric bar is carried out the soda acid purification processes, make the cubic boron nitride monocrystal product, this cubic boron nitride monocrystal product is faint yellow transparent sheet cubic boron nitride monocrystal.
The conversion ratio of above-mentioned cubic boron nitride is 35%.
Embodiment five:
A kind of method with alkali metal azide synthesizing cubic boron nitride, this method be a kind of be raw material with the hexagonal boron nitride, under high-temperature and high-pressure conditions, add the method for catalyst synthesizing cubic boron nitride monocrystalline, it may further comprise the steps:
A. get the raw materials ready: the hexagonal boron nitride with purity 98% is raw material, is 99.8% lithium nitride Li with purity
3N and sodium azide NaN
3Be that catalyst mixture is got the raw materials ready for the mixture of 1:0.01 by weight ratio;
B. mix and pre-molding: be by weight ratio: the ratio of hexagonal boron nitride raw material: catalyst mixture=1:0.3 is got material respectively, is pressed into cylindric bar in advance after evenly mixing;
C. synthetic: cylindric bar is packed in the synthetic piece of pyrophillite, synthesize at cubic hinge press pyrophillite is synthetic packaged, synthesis temperature is 1800 ℃, and synthesis pressure is 4.0Gpa;
D. heat-insulation pressure keeping: heat-insulation pressure keeping 15 minutes stops to heat the back and waits for 2.5 minutes;
E. get material, cooling: slowly be depressurized to normal pressure, take out cylindric bar, be cooled to room temperature;
F. purify: cooled cylindric bar is carried out the soda acid purification processes, make the cubic boron nitride monocrystal product, this cubic boron nitride monocrystal product is the transparent sheet cubic boron nitride monocrystal of buff.
The conversion ratio of above-mentioned cubic boron nitride is 40%.
Embodiment six:
A kind of method with alkali metal azide synthesizing cubic boron nitride, this method be a kind of be raw material with the hexagonal boron nitride, under high-temperature and high-pressure conditions, add the method for catalyst synthesizing cubic boron nitride monocrystalline, it may further comprise the steps:
A. get the raw materials ready: the hexagonal boron nitride with purity 95% is raw material, is 99% lithium nitride Li with purity
3N and sodium azide NaN
3Be that catalyst mixture is got the raw materials ready for the mixture of 1:0.5 by weight ratio;
B. mix and pre-molding: be by weight ratio: the ratio of hexagonal boron nitride raw material: catalyst mixture=1:0.3 is got material respectively, is pressed into cylindric bar in advance after evenly mixing;
C. synthetic: cylindric bar is packed in the synthetic piece of pyrophillite, synthesize at cubic hinge press pyrophillite is synthetic packaged, synthesis temperature is 1800 ℃, and synthesis pressure is 6.0Gpa;
D. heat-insulation pressure keeping: heat-insulation pressure keeping 15 minutes stops to heat the back and waits for 3 minutes;
E. get material, cooling: slowly be depressurized to normal pressure, take out cylindric bar, be cooled to room temperature;
F. purify: cooled cylindric bar is carried out the soda acid purification processes, make the cubic boron nitride monocrystal product, this cubic boron nitride monocrystal product is dark amber transparent sheet cubic boron nitride monocrystal.
The conversion ratio of above-mentioned cubic boron nitride is 45%.
Embodiment seven:
A kind of method with alkali metal azide synthesizing cubic boron nitride, this method be a kind of be raw material with the hexagonal boron nitride, under high-temperature and high-pressure conditions, add the method for catalyst synthesizing cubic boron nitride monocrystalline, it may further comprise the steps:
A. get the raw materials ready: the hexagonal boron nitride with purity 96% is raw material, is 99.5% lithium nitride Li with purity
3N and sodium azide NaN
3Be that catalyst mixture is got the raw materials ready for the mixture of 1:0.5 by weight ratio;
B. mix and pre-molding: be by weight ratio: the ratio of hexagonal boron nitride raw material: catalyst mixture=1:0.1 is got material respectively, is pressed into cylindric bar in advance after evenly mixing;
C. synthetic: cylindric bar is packed in the synthetic piece of pyrophillite, synthesize at cubic hinge press pyrophillite is synthetic packaged, synthesis temperature is 1000 ℃, and synthesis pressure is 6.0Gpa;
D. heat-insulation pressure keeping: heat-insulation pressure keeping 12 minutes stops to heat the back and waits for 3 minutes;
E. get material, cooling: slowly be depressurized to normal pressure, take out cylindric bar, be cooled to room temperature;
F. purify: cooled cylindric bar is carried out the soda acid purification processes, make the cubic boron nitride monocrystal product, this cubic boron nitride monocrystal product is amber transparent sheet cubic boron nitride monocrystal.
The conversion ratio of above-mentioned cubic boron nitride is 35%.
As a kind of conversion of above-described embodiment one to embodiment seven, described alkali metal nitride and alkali metal azide are generally by weight ratio: 1:0.01～0.5; Described hexagonal boron nitride raw material and catalyst mixture are generally by weight ratio: 1:0.1～0.3.
As another conversion of above-described embodiment one to embodiment seven, described synthesis temperature is generally 1000～1800 ℃, and synthesis pressure is generally 4.0～6.0GPa, and the heat-insulation pressure keeping time was generally 3～15 minutes.
Another conversion as above-described embodiment one to embodiment seven, described alkali metal nitride can also be other alkali metal nitrides such as CaCl2, sodium nitride, magnesium nitride, and described alkali metal azide can also be other alkali metal azide such as Azide calcium, Azide magnesium, Azide calcium lithium.
Claims (4)
1. method with alkali metal azide synthesizing cubic boron nitride, this method be a kind of be raw material with the hexagonal boron nitride, under high-temperature and high-pressure conditions, add the method for catalyst synthesizing cubic boron nitride monocrystalline, it is characterized in that: described catalyst is the catalyst mixture that comprises alkali metal nitride and alkali metal azide, and this alkali metal nitride and alkali metal azide are by weight ratio: 1:0.01～0.5; Described hexagonal boron nitride raw material and catalyst mixture are by weight ratio: 1:0.1～0.3; Described high-temperature and high-pressure conditions refers to: 1000～1800 ℃ of synthesis temperatures, synthesis pressure 4.0～6.0GPa, 3～15 minutes heat-insulation pressure keeping time.
2. the method with alkali metal azide synthesizing cubic boron nitride according to claim 1, it is characterized in that: this method may further comprise the steps:
A. get the raw materials ready: being raw material with the hexagonal boron nitride, is that the mixture of 1:0.01～0.5 is that catalyst mixture is got the raw materials ready with alkali metal nitride and alkali metal azide by weight ratio;
B. mix and pre-molding: be by weight ratio: the ratio of hexagonal boron nitride raw material: catalyst mixture=1:0.1～0.3 is got material respectively, is pressed into cylindric bar in advance after evenly mixing;
C. synthetic: cylindric bar is packed in the synthetic piece of pyrophillite, synthesize at top press pyrophillite is synthetic packaged, synthesis temperature is 1000～1800 ℃, and synthesis pressure is 4.0～6.0Gpa;
D. heat-insulation pressure keeping: heat-insulation pressure keeping 3～15 minutes stops to heat the back and waits for 1～3 minute;
E. get material, cooling: slowly be depressurized to normal pressure, take out cylindric bar, be cooled to room temperature;
F. purify: cooled cylindric bar is carried out the soda acid purification processes, make the cubic boron nitride monocrystal product.
3. the method with alkali metal azide synthesizing cubic boron nitride according to claim 2 is characterized in that: the described cubic boron nitride monocrystal product that makes for from faint yellow to dark amber transparent sheet cubic boron nitride monocrystal.
4. according to claim 1 or 2 or 3 described methods with alkali metal azide synthesizing cubic boron nitride, it is characterized in that: the purity of described alkali metal nitride and alkali metal azide is more than 99%, and the purity of described hexagonal boron nitride is more than 95%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369192A (en) * | 2018-11-29 | 2019-02-22 | 盐城师范学院 | A kind of preparation method of cubic boron nitride |
| CN109650900A (en) * | 2018-12-19 | 2019-04-19 | 郑州中南杰特超硬材料有限公司 | A kind of synthetic method of pure phase polycrystal cubic boron nitride cylinder |
| CN113444490A (en) * | 2021-06-25 | 2021-09-28 | 郑州益奇超硬材料有限公司 | Polycrystalline cubic boron nitride abrasive and preparation method thereof |
| CN115044978A (en) * | 2022-07-08 | 2022-09-13 | 郑州沃德超硬材料有限公司 | Preparation method of large-particle CBN |
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| RU2034642C1 (en) * | 1991-04-03 | 1995-05-10 | Институт физики твердого тела и полупроводников АН Беларуси | Charge for producing monocrystals of cubical boron nitride |
| CN1686601A (en) * | 2005-03-25 | 2005-10-26 | 吉林大学 | Method of synthesizing cubic boron nitride using alkali metal fluoride |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2034642C1 (en) * | 1991-04-03 | 1995-05-10 | Институт физики твердого тела и полупроводников АН Беларуси | Charge for producing monocrystals of cubical boron nitride |
| CN1686601A (en) * | 2005-03-25 | 2005-10-26 | 吉林大学 | Method of synthesizing cubic boron nitride using alkali metal fluoride |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369192A (en) * | 2018-11-29 | 2019-02-22 | 盐城师范学院 | A kind of preparation method of cubic boron nitride |
| CN109650900A (en) * | 2018-12-19 | 2019-04-19 | 郑州中南杰特超硬材料有限公司 | A kind of synthetic method of pure phase polycrystal cubic boron nitride cylinder |
| CN113444490A (en) * | 2021-06-25 | 2021-09-28 | 郑州益奇超硬材料有限公司 | Polycrystalline cubic boron nitride abrasive and preparation method thereof |
| CN113444490B (en) * | 2021-06-25 | 2022-08-26 | 郑州益奇超硬材料有限公司 | Polycrystalline cubic boron nitride abrasive and preparation method thereof |
| CN115044978A (en) * | 2022-07-08 | 2022-09-13 | 郑州沃德超硬材料有限公司 | Preparation method of large-particle CBN |
| CN115044978B (en) * | 2022-07-08 | 2023-06-02 | 郑州沃德超硬材料有限公司 | Preparation method of large-particle CBN |
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Application publication date: 20130904 |