CN100496696C - Method of synthesizing cubic boron nitride using alkali metal fluoride - Google Patents
Method of synthesizing cubic boron nitride using alkali metal fluoride Download PDFInfo
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- CN100496696C CN100496696C CNB2005100166525A CN200510016652A CN100496696C CN 100496696 C CN100496696 C CN 100496696C CN B2005100166525 A CNB2005100166525 A CN B2005100166525A CN 200510016652 A CN200510016652 A CN 200510016652A CN 100496696 C CN100496696 C CN 100496696C
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- boron nitride
- cubic boron
- alkali metal
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Abstract
A process for synthesizing the cubic boron nitride from the fluoride of alkali metal includes such steps as mixing hexagonal boron nitride, the mixture of LiF and Li3N and the LiH, die pressing, assembling to become block in graphite pipe, synthesizing and chemical treating to obtain red-yellow transparent cubic monocrystal.
Description
Technical field
The invention belongs to the HTHP synthetic method field of superhard material, particularly select the method for new catalyst synthesizing cubic boron nitride.
Background technology
The hardness of cubic boron nitride (cBN) is only second to diamond, because it has higher oxidation resistance temperature than diamond, and at high temperature not with excellent specific properties such as iron family element reacts, as abrasive material and make goods such as cutter, emery wheel and hone stone and be widely used in the iron and steel of high rigidity and the manufacture field of alloy material thereof.
Hexagonal boron nitride mixes with catalyst, and synthetic under HTHP is the common method of producing cubic boron nitride.General cubic boron nitride synthetic method is the catalyst synthesizing cubic boron nitride with alkali metal such as Li, Mg, Ca and alkaline-earth metal or its nitride, nitrogen boride, shortcoming such as exist synthesis temperature, pressure limit is narrow, and the conversion ratio of cubic boron nitride 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, and the method for synthesizing cubic boron nitride has obtained high strength under HTHP, the cubic boron nitride monocrystal powder of low impurity content.But the used catalyst of this method is had relatively high expectations to the purity of hexagonal boron nitride and impurity content etc., want hexagonal boron nitride purity〉99.8%, boron oxide content＜0.1% and the graphitization index＜2 synthetic result that o'clock just can obtain, as hexagonal boron nitride purity less than 98%, boron oxide content greater than 0.15% and the graphitization index greater than 3 o'clock resulting cubic boron nitride granularities just less than 300 orders, conversion ratio is also very low.
The prior art close with the present invention is that name is called " synthetic method of cubic boron nitride " Chinese patent, the patent No. 02116459.2, Granted publication CN1176009C.This patent is a synthesis material with the rough hexagonal boron nitride of purity 96%～99.8%, boron oxide content 0.01%～0.48%, graphitization index 1～6, selects LiNH
2Make catalyst with the mixture of LiH; LiNH
2After mixing by weight 6～12: 1 with LiH, mix by weight 1: 7～12 with the hexagonal boron nitride raw material again, pre-molding is after HTHP is synthetic, synthesis temperature is 1350～1800 ℃, synthesis pressure is 4.0～5.5GPa, generated time is 3～8 minutes, and purifying with fusion sodium carbonate obtains cubic boron nitride 70～80 orders, and breaking strength is more than 35 newton.
The cBN of the Chinese patent of " synthetic method of cubic boron nitride " synthesizing high-strength, transparent, equivalance shape under lower synthesis pressure and temperature, and synthetic district is wide, generated time is short, yield is high.Point out simultaneously, " in catalyst mixture, LiNH
2Contribution to the cBN nucleation is bigger, uses LiNH separately
2Can only obtain fine grain product.The nucleation amount has been controlled in the adding of LiH effectively, and promotes the g and D of cBN monocrystalline.Simultaneously, also to eliminating the boron oxide impurity influence synthetic to cBN in the raw material, inclusion enclave and defective play an important role LiH in the minimizing product.”
Summary of the invention
The technology that the present invention will solve is that problem is, selects novel catalyst and raw material proportioning, makes the purity requirement of hexagonal boron nitride raw material low, and have synthesis pressure, temperature range is wide, the conversion ratio height.
The invention provides a kind of method of synthesizing cubic boron nitride, is raw material with hexagonal boron nitride hBN, with LiF and Li
3N makes catalyst, and LiH is an additive, synthetic transparent cubic boron nitride.The mixed material that height is pressed into is by weight ratio: hexagonal boron nitride: LiF: Li
3N: LiH=1: 0.02～0.1: 0.11～0.2: 0.02～0.05, mix, synthetic under HTHP behind the pre-molding, 1000～1800 ℃ of synthesis temperatures, synthesis pressure 4.0～6.0GPa, obtains cubic boron nitride cBN product through chemical treatment at 3～8 minutes heat-insulation pressure keeping time.
The purity of hexagonal boron nitride hBN can be selected more than 95%.
HTHP is synthetic down, can carry out on the special-purpose press of superhard material.
Synthetic product is reddish yellow and crystalline form percentage of head rice height, transparent cubic boron nitride crystal.
The present invention adds LiF, and the nucleation rate of cBN improves, and the temperature, pressure zone of cBN growth simultaneously broadens, and the vitellarium of cBN increases in the sample area, thereby has improved the conversion ratio that hBN transforms to cBN.Simultaneously, the present invention reduces the purity requirement of raw material hBN, and synthesis temperature also can be lower, and product is crystalline form percentage of head rice height, transparent cubic boron nitride crystal, is more suitable for industrial production and use.
The specific embodiment
Embodiment 1
With LiF, Li
3N and LiH mixed by weight 1: 4: 1, pack into after cylindric in the graphite bush by weight mixing and in advance be pressed at 15: 85 with the hexagonal boron nitride of purity 95% again, keep the height of former stock column to equate or than the low 0.5～1mm of height of graphite-pipe with the height of graphite-pipe, put into the pyrophillite piece and be assembled into synthetic piece, synthetic at the enterprising horizontal high voltage of cubic hinge press.At 1100 ℃, under the 4.5GPa condition, heat-insulation pressure keeping 5 minutes, stop heating and treat that temperature reduces the back and takes out sample, after the soda acid purification processes, obtain the transparent cubic boron nitride crystal of reddish yellow, the cBN crystal crystalline form percentage of head rice height that obtains, the conversion ratio of cBN is 30～35%.
Embodiment 2
With LiF, Li
3N and LiH mixed by weight 4: 5: 1, pack into after cylindric in the graphite bush by weight mixing and in advance be pressed at 20: 80 with the hexagonal boron nitride of purity 95% again, keep the height of former stock column to equate or than the low 0.5～1mm of height of graphite-pipe with the height of graphite-pipe, put into the pyrophillite piece and be assembled into synthetic piece, synthetic at the enterprising horizontal high voltage of cubic hinge press.At 1700 ℃, under the 5.5GPa condition, heat-insulation pressure keeping 5 minutes stops heating and treats that temperature reduces the back and takes out sample, obtains the transparent cubic boron nitride crystal of reddish yellow after the soda acid purification processes, the cBN crystal that obtains, and crystalline form percentage of head rice height, the conversion ratio of cBN are 40%.
Embodiment 3
Sample ligand ratio, assembling, synthesis device and temperature, pressure condition are all with embodiment 1, and 3 minutes heat-insulation pressure keeping time, the cBN crystal that laboratory sample obtains after purifying is with embodiment 1, and only granularity is slightly thin, and the cBN conversion ratio is 30%.
Embodiment 4
Sample preparation and synthesis condition are all with embodiment 2, and the heat-insulation pressure keeping time is 8 minutes, and the cBN crystal that obtains after the synthetic product purification processes is with embodiment 2, and crystal size is thicker, crystalline form percentage of head rice height, cBN conversion ratio 40%.
Claims (1)
1, a kind of method with the alkali metal fluoride synthesizing cubic boron nitride is a raw material with the hexagonal boron nitride, through HTHP synthesizing cubic boron nitride product, and 1000～1800 ℃ of synthesis temperatures, synthesis pressure 4.0～6.0GPa, 3～8 minutes heat-insulation pressure keeping time; It is characterized in that, with LiF and Li
3N makes catalyst, and LiH is an additive; The mixed material that height is pressed into is by weight ratio: hexagonal boron nitride: LiF: Li
3N: LiH=1: 0.02～0.1: 0.11～0.2: 0.02～0.05; The purity of hexagonal boron nitride is selected more than 95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100166525A CN100496696C (en) | 2005-03-25 | 2005-03-25 | Method of synthesizing cubic boron nitride using alkali metal fluoride |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100166525A CN100496696C (en) | 2005-03-25 | 2005-03-25 | Method of synthesizing cubic boron nitride using alkali metal fluoride |
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| CN1686601A CN1686601A (en) | 2005-10-26 |
| CN100496696C true CN100496696C (en) | 2009-06-10 |
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| CNB2005100166525A Expired - Fee Related CN100496696C (en) | 2005-03-25 | 2005-03-25 | Method of synthesizing cubic boron nitride using alkali metal fluoride |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460560C (en) * | 2006-07-03 | 2009-02-11 | 吉林大学 | Process for the preparation of cubic boron nitride material |
| CN103272528A (en) * | 2013-05-28 | 2013-09-04 | 柳州市大荣非金属材料有限公司 | Method for synthesizing cubic boron nitrides by using alkali metal azide |
| CN103877914B (en) * | 2014-04-01 | 2016-01-27 | 山东建筑大学 | High-intensity fine particle cubic boron nitride monocrystal and synthetic method thereof and application |
| CN105386118A (en) * | 2014-08-26 | 2016-03-09 | 信阳市德隆超硬材料有限公司 | Method for synthesizing coarse particle size cubic boron nitride single crystal through magnesium-based catalyst |
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Granted publication date: 20090610 Termination date: 20100325 |