CN1323738A - Prepn. of nanometer boron nitride micro powder - Google Patents
Prepn. of nanometer boron nitride micro powder Download PDFInfo
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Abstract
The present invention relates to method of preparing boron nitride nanometer fine powder using organic solvent liquid phase chemical reaction, said method dissolves the boron source in organic solvent, stir and add nitrogen source, then react in closed container under 50-600 deg.C or in open container under the protection of inert gas and 50-300 deg.C, after reaction is complete, it is suction filtered and dried to obtain bexagonal boron nitride nanometer fine powder. The apparent effect of present invention is that the reaction is carried out under normal or low pressure, so that it can realize low cost and large scale production.
Description
The technical field is as follows: the invention relates to a method for preparing boron nitride nano micro powder by utilizing liquid phase chemical reaction in an organic solvent under the conditions of low temperature and low pressure, belonging to super-hard nano materials.
Background art: the boron nitride nanometer micro powder comprises hexagonal boron nitride nanometer micro powder and cubic boron nitride nanometer micro powder. The hexagonal boron nitride nanometer micro powder has attracted people's attention due to the high heat conductivity, good chemical stability, excellent lubricating property and sintering property. However, the currently used boron nitride lubricating material, the high-stability high-temperature-resistant heating container and the like are all made of hexagonal boron nitride micro-powder, the particles are large and poor in uniformity, the phenomenon seriously reduces the lubricating effect of the material on one hand, and on the other hand, the heating container is too high in sintering temperature and too strong in brittleness. After the hexagonal boron nitride nanometer micro powder is added into the lubricating oil, the nanometer particles tend to be firstly deposited at the defect position of the friction surface, so that the defect repairing effect is achieved, the lubricating effect can be obviously improved, and the mechanical life is greatly prolonged; as a heating container material, the hexagonal boron nitride nanometer micro powder can greatly reduce the sintering temperature (the maximum cooling amplitude can reach 1800 ℃), can obviously improve the density and the toughness of the container, and can improve the heat conductivity of the container. The main methods for preparing hexagonal boron nitride powder (mainly micron powder) are mostly solid phase reaction methods, the uniformity is poor, the required reaction temperature is high (700-.
The large-size high-purity cubic boron nitride polycrystal can be used as a high-energy ray window or a high-efficiency radiating fin and has very important application prospect. At present, only Japan develops a centimeter-level high-purity cubic boron nitride polycrystal wafer, but the adopted method needs to refine hexagonal boron nitride (hBN) raw material at a high temperature of 2300 ℃ and has special requirements on press equipment. The high-purity cubic boron nitride polycrystal is obtained by converting a hexagonal boron nitride raw material into a cubic phase by 100%, and the characteristics of low melting point and high activity of the hexagonal boron nitride nanometer micro powder are very favorable for reducing the pressure in the process of synthesizing the cubic boron nitride by a solid phase method and realizing 100% conversion into the cubic boron nitride. Cubic boron nitride (cBN) is the semiconductor material with the widest forbidden band and can be used as a high-temperature semiconductor and a high-energy ray window material. Its thermal conductivity is second to diamond, but its stability is higher than diamond, so it is the best heat sink material. The hardness of cubic boron nitride is slightly lower than that of diamond, but no chemical reaction occurs between cubic boron nitride and iron group elements, which can greatly prolong the service life of the cutter and improve the machining precision, so that it becomes the best cutting and grinding material for most metals and alloys. Cubic boron nitride is considered one of the most promising materials for the 21 st century. The wide application of the cubic boron nitride tool has decisive effects of greatly improving the integral level of the machining industry and improving the product grade. The cubic boron nitride nanopowder has excellent properties that are not possessed by the usual micron-sized cubic boron nitride: firstly, the nano cubic boron nitride has high activity, the sintering temperature is greatly reduced when the nano cubic boron nitride is used as a raw materialto prepare a ceramic body, the bonding agent which is originally necessary when a cutter and a drill bit are manufactured by micron cubic boron nitride can be completely abandoned, and the cubic boron nitride nano micro powder is directly sintered into the superhard ceramic body with compact structure and stable chemical property. Under the condition of properly controlling the grain size growth process, the toughness of the ceramic body can be greatly improved while the hardness of the ceramic body is kept, and the service lives of a cutter and a drill bit are obviously prolonged; and secondly, the cubic boron nitride nano micro powder is easier to form a firm bonding layer with other materials (matrixes), and the characteristic provides unique advantage for manufacturing the super-hard coating with high stability. The reason for this phenomenon is that the cubic boron nitride nanopowder is easily penetrated into the microdefects on the surface of the substrate, and forms a whole with other cubic boron nitride nanopowder in the sintering process, which is equivalent to forming a mixed layer between the substrate and the cubic boron nitride layer, which is very beneficial to improving the compactness and bonding firmness of the superhard coating. Because of the important practical value of cubic boron nitride, the synthesis method of cubic boron nitride has been systematically explored for many years. For a long time, cubic boron nitride has been considered as a stable phase of boron nitride under high temperature and high pressure, and can be synthesized only by a high-temperature and high-pressure method with high consumption and low yield. In 1988, the Solozhenko proposed that cubic boron nitride be a stable phase at atmospheric pressure and temperatures below 1200 ℃ according to theoretical calculations of thermodynamics. The results of a series of subsequent synthesis experiments have shown that cubic boron nitride can be synthesized in low-pressure regions where it was thought impossible to synthesize cubic boron nitride in the past, such as: cubic boron nitride (hBN) was synthesized in 1993 by Singh et al at 2.5GPa, in 1994 by Soro screening (Solozhenko) at 2.0GPa and in 1995 by Lorenz (Lorenz) at 0.5GPa, using different catalysts, starting from hexagonal boron nitride (hBN). The synthetic pressure is much lower than the pressure above 4.0GPa that is considered necessary for synthesizing the cubic boron nitride in the past, which shows that the Solozhenko phase diagram is correct, and the low-pressure or normal-pressure synthesis of the cubic boron nitride is feasible. However, it is not easy to find the existing methods for synthesizing cubic boron nitride by comprehensive analysis, and these methods are still solid phase high pressure methods, and the required temperature and pressure are still high, and the requirements for equipment conditions are very strict, so that it is difficult to form a large production scale.
The invention content is as follows:
aiming at the problems in the prior art, the invention provides a technical scheme for preparing hexagonal boron nitride nano micro powder and cubic boron nitride nano micro powder with fine granularity and uniform size by using a liquid phase reaction method in an organic solvent, so that the low-cost mass synthesis of boron nitride materials is realized, and a foundation is laid for the wide application of boron nitride tools.
The technical scheme of the invention comprises the following steps:
(1) under the protection of inert atmosphere, dissolving a soluble boron source in an organic solvent subjected to oxygen removal and water removal, stirring while dissolving, and continuously stirring for 10-80 minutes to obtain a solution with the concentration of 0.01-10 mol/L;
(2) slowly adding a stoichiometric ratio of a nitrogen source tothe previously obtained boron source solution with stirring; if the solid source is needed to be ground;
(3) stirring the solution for 0.5-5 hours, putting the solution into a closed reaction container, heating the solution to 50-600 ℃ at a filling rate of 30-95 percent, and reacting the solution for 3-120 hours under a shaking condition; or heating the uniformly stirred mixed solution to 50-300 ℃ in an open container under the protection of inert atmosphere, and reacting for 5-120 hours under the condition of continuous and rapid stirring;
(4) after the reaction is finished, the product is filtered by an organic solvent with the temperature of 30-200 ℃ for 1-8 times, and then is filtered by deionized water for several times until the filtrate is neutral;
(5) the obtained powder is dried in vacuum or inert atmosphere to obtain the boron nitride nanometer micro powder with uniform particles.
After the powder is dried and heated in vacuum at 40-80 ℃, the hexagonal boron nitride nanometer micro powder with even particles and several to hundreds of nanometers in particle size is obtained.
The organic solvent subjected to oxygen removal and water removal in the step (1) is obtained by distilling the organic solvent to be used, adding active alkali metal, alkaline earth metal sheet or compound thereof as an oxygen removal and water removal agent, and preserving the mixture in an inert atmosphere for later use; the common oxygen and water removing agent is sodium tablet, calcium hydride.
The preparation method of the cubic boron nitride nanometer micropowder is that crystal grains for inducing the growth of the cubic boron nitride are added into the reaction vessel according to the amount of 0.01 to 200 g/L solution in the step (3). In the step (4), inorganic acid or alkali is used for removing the crystal grainswith the induction effect, and then deionized water is used for suction filtration. The crystal grains for inducing the growth of the cubic boron nitride are metal, II-VI group semiconductors, III-V group semiconductors, oxide semiconductors and salts with a cubic crystal structure, good stability and lattice parameters similar to those of the cubic boron nitride. When the crystal grains are used for inducing the growth of the cubic boron nitride, the small crystal grains have stronger inducing effect, the cubic boron nitride nanometer micro powder can be more easily obtained under the conditions of low temperature and low pressure, and the inducing effect is obviously weakened when the grain size is increased.
The organic solvent includes aromatic compounds, alkanes, pyridines, ethers and esters with higher boiling point and better chemical stability.
Such boron sources include boron halides, boranes and other organoboron compounds that have moderate stability and are soluble in such organic solvents.
The nitrogen source includes metal nitrides, ammonia, organic amines and nitrogen-containing organic substances, and the nitrogen source may be soluble in an organic solvent or may be a solid powder. It is required to be relatively active in that the nitrogen atom readily participates in the reaction.
In the preparation method, the higher the concentration of the boron source is, the larger the obtained boron nitride nanometer micro powder particles are, the worse the uniformity of crystal grains is, and the lower the actual yield is. But at the same time, the reaction speed is accelerated, and the required reaction temperature is reduced; on the contrary, when the concentration of the boron source is reduced, the obtained boron nitride nanometer micro powder has fine and uniform crystal grains, the reaction process is easy to control, and the actual yield isimproved. However, the reaction rate is slow and the reaction temperature required is correspondingly increased. In addition, the longer the preparation reaction time, the larger the particle size of the obtained boron nitride nanopowder, and the higher the yield.
The method is characterized in that the reaction process is completed under the conditions of normal pressure and low pressure, the low-cost mass preparation is easy to realize, and the preparation cost of the cubic boron nitride nano micro powder is only one fourth to one fifth of the cost of the existing solid-state high-pressure phase change method. Not only the reaction temperature is reduced to be about 100 ℃, but also the powder uniformity is good, and the granularity can be controlled within the range of a few nanometers to hundreds of nanometers. The invention carries out systematic research on key influencing factors of the preparation process, such as the crystal structure and the size of the substrate, the reaction temperature, the pressure and the like. The boron nitride nanometer micro powder with uniform and fine granularity is prepared, and the melting point of the boron nitride nanometer micro powder is reduced from 2967 ℃ of large particles to about 1200 ℃; in addition, under the crystal grain inducing effect (substrate induced growth) with a cubic crystal structure, pure cubic boron nitride nanometer micro powder can be prepared at one atmosphere and 120 ℃; the hexagonal boron nitride nanometer micro powder prepared by the method can be used for manufacturing high-efficiency lubricating liquid, and the cubic boron nitride nanometer micro powder has complete crystal form and uniform granularity. They can be used for manufacturing precision machining tools, high-stability high-temperature-resistant heating containers, high-thermal-conductivity insulating materials, grinding tools, high-stability high-hardness drill bits, high-performance nano lubricating liquid, military special window materialsand the like.
The invention is further illustrated by the following description and examples in conjunction with the accompanying drawings.
Description of the drawings:
FIG. 1 is an X-ray diffraction diagram of hexagonal boron nitride nanopowder of example 1, with diffraction angles (2 θ/°) on the abscissa and intensity (arbitrary units) on the ordinate.
FIG. 2 is a transmission electron micrograph (magnification 15 ten thousand times) of a sample of example 1.
FIG. 3 is a high temperature differential thermal curve of hexagonal boron nitride nanopowder. The abscissa is temperature (. degree. C.) and the ordinate is temperature difference (. degree. C.).
FIG. 4 is an X-ray diffraction spectrum of a sample obtained in example 3, with diffraction angles (2. theta./°) on the abscissa and intensities (arbitrary units) on the ordinate.
FIG. 5 is an infrared spectrum of a sample obtained in example 3, with the abscissa being the wave number (cm)-1) And the ordinate represents the transmittance (%).
FIG. 6 is an X-ray diffraction spectrum of a sample obtained in example 4, with diffraction angles (2. theta./°) on the abscissa and intensities (arbitrary units) on the ordinate.
FIG. 7 is an infrared absorption spectrum of a sample obtained in example 4, with wavenumber (cm) on the abscissa-1) And the ordinate represents the transmittance (%).
The specific embodiment is as follows:
example 1 preparation of hexagonal boron nitride nanopowder
Xylene is usedas solvent, boron tribromide is selected as boron source, and lithium nitride is used as nitrogen source. The total reaction for synthesizing the boron nitride nanometer micro powder is as follows:
FIG. 1 is an X-ray diffraction pattern of a hexagonal boron nitride nanopowder of example 1, in which a protrusion in the form of a bag appears at the main diffraction peak position of hexagonal boron nitride, illustrating that the hexagonal boron nitride particle size obtained in this case is small; FIG. 2 shows a TEM image of the sample (magnification 15 ten thousand) taken from different areas of the sample, indicating that the sample has good overall uniformity, and that the sample has a very small average particle size (about 5 nm) and is very uniform. The results of the thermal analysis performed on this sample show that: it melts at 1240 ℃ which is approximately two thirds lower than the 2967 ℃ temperature of the boron nitride micro-particles, and figure 3 is the high temperature differential thermal curve of the hexagonal boron nitride nanopowder.
Example 2 preparation of hexagonal boron nitride nanopowder
The reaction was carried out at one atmosphere, as described in example 1, except that. After the addition of the lithium nitride powder was completed, the mixture was stirred for another 30 minutes, and then the temperature of the solution was increased to 120 ℃ and maintained for 10 to 14 hours while stirring was continued. After the reaction is finished, the obtained powder is also filtered by xylene at 70 ℃ for three times, then sufficient deionized water is used for filtering until the filtrate is neutral, and the powder is dried in vacuum.
Example 3 preparation of cubic boron nitride nanopowder under the action of Large grain Induction
Benzene is used as solvent, boron tribromide is selected as boron source, and lithium nitride is used as nitrogen source. The operation steps are as follows: benzene was distilled and a sodium sheet was added to remove water and oxygen, and then 100 ml of benzene was taken in a high-purity nitrogen atmosphere and placed in a Erlenmeyer flask having a capacity of 250 ml. About 15 grams of boron tribromide was then dissolved in benzene and, after rapid stirring for 20-30 minutes, 2.1 grams of finely ground lithium nitride powder was added to it. After stirring for 1 hour, the uniformly stirred mixed solution was transferred to a reaction vessel. Then 5g of sliced metallic nickel is added, finally the benzene which is dehydrated and deoxidized is used to make the filling rate reach 80%, the nitrogen is used for bubbling to remove the air in the kettle, and then the kettle is sealed. Heating the reaction kettle to 480 ℃, preserving heat for 8-10 hours, after the reaction is finished, performing suction filtration for three times by using three parts of benzene with the volume of 100 ml and the temperature of 70 ℃, and performing suction filtration by using a large amount of deionized water until the filtrate is neutral. And drying the powder obtained by suction filtration in a vacuum state to obtain a powder sample mainly containing the cubic boron nitride nano micro powder.
Fig. 4 shows an X-ray diffraction spectrum of the sample obtained above, in which the peaks marked with dots belong to cubic boron nitride and the peaks marked with squares belong to hexagonal boron nitride. It can be seen that cubic boron nitride has become the predominant phase in the sample; this conclusion is also confirmed by the IR spectrum, FIG. 5 is the IR spectrum of the boron nitride nanopowder synthesized at 480 ℃ wherein the strongest absorption peak at the wavenumber of 1134cm-1 belongs to cubic boron nitride, the IR absorption peak labeled "hBN" at 1409 belongs to hexagonal boron nitride, whose intensity is greatly reduced with respect to cubic boron nitride, and the absorption peak labeled "-OH" is caused by surface adsorbed hydroxyl groups. At temperatures below 480 c no cubic boron nitride phase was detected because the large grain size significantly reduced the reactivity of these grains with a consequent reduction in induction.
Example 4 preparation of cubic boron nitride nanopowder at Low temperature and Low pressure under the Induction of gallium phosphide nanocrystals
Xylene is used as a solvent, boron trichloride is selected as a boron source, and lithium nitride is used as a nitrogen source. The operation steps are as follows: xylene was distilled and added to a sodium sheet to remove water and oxygen, and then 100 ml of xylene was taken in a high-purity nitrogen atmosphere and placed in a Erlenmeyer flask having a capacity of 250 ml. Then, 10 g of boron trichloride was dissolved in xylene, and after stirring rapidly for 20 to 30 minutes, 2.1 g of finely ground lithium nitride powder was added thereto. After stirring for 1 hour, the uniformly stirred mixed solution was transferred to a reaction vessel. Then 0.5g of gallium phosphide nano-crystalline grains are added, finally, the filling rate is up to 80% by using dimethylbenzene which is subjected to water removal and oxygen removal, and after air in the kettle is removed by bubbling nitrogen, the kettle is sealed. Heating the reaction kettle to 200 ℃ and 3 atmospheres, preserving heat for 10 hours, carrying out suction filtration three times by using three portions of xylene with the volume of 100 ml and the temperature of 70 ℃ after the reaction is finished, and then carrying out suction filtration by using a large amount of deionized water until the filtrate is neutral. And drying the powder obtained by suction filtration in a vacuum state to obtain a nearly pure cubic boron nitride nano micro powder sample.
FIG. 6 shows the X-ray diffraction spectrum of the sample obtained above, in which the peak labeled with cBN is the main peak of cubic boron nitride, and the apparent broadening of the peak demonstrates that the cubic boron nitride obtained has a particle size of 4 to 10 nm. The remaining diffraction peaks in the figure belong to gallium phosphide and these peaks can be removed by chemical etching. FIG. 7 is an infrared absorption spectrum of cubic boron nitride nanopowder, wherein the strongest absorption peak labeled "cBN" is the absorption peak of cubic boron nitride nanopowder, the absorption peak labeled "hBN" belongs to hexagonal boron nitride, which has nearly disappeared, and the absorption peak labeled "-OH" is due to hydroxyl groups adsorbed on the surface.
Example 5 preparation of boron nitride nanopowder by reaction of boron trichloride and trimethylamine
As described in example 4, except that the nitrogen source was trimethylamine. Xylene was first distilled and added to a sodium tablet to remove water and oxygen, and then 100 ml of xylene was taken in a high-purity nitrogen atmosphere and placed in a Erlenmeyer flask having a capacity of 250 ml. 10 g of boron trichloride were then dissolved in xylene. After stirring rapidly for 20-30 minutes, 5 grams of trimethylamine are added to the boron trichloride solution. After stirring for 1 hour, the mixed solution was transferred to a reaction vessel, and 3 g of nano nickel powder having an average particle size of 12 nm was added. Adding dimethylbenzene which is subjected to water removal and oxygen removal to enable the filling rate to be 80%, removing air in the kettle by using high-purity nitrogen, and sealing the kettle. The reaction kettle is heated to 300 ℃ for reaction for 6 hours. After the reaction is finished, xylene with the temperature of 70 ℃ and the volume of 100 ml is used for suction filtration for 3-4 times, and then sufficient deionized water is used for suction filtration until the filtrate is neutral. The powder is dried in vacuum state to obtain the boron nitride nanometer micro powder.
Example 6 as in example 1, except that the organic solvent was pyridine, the reaction temperature was 280 ℃. Calcium hydride powder is used for removing water by pyridine.
Example 7. As described in example 1, except that the organic solvent was n-pentane and the reaction temperature was 150 ℃.
Example 8. As described in example 1, except that the boron source was diborane, the nitrogen source was ammonia, and the reaction temperature was 300 deg.C
Example 9. as described in example 3, except that the grains used to induce cubic boronnitride growth were cubic zinc sulfide nanocrystals having a particle size of 5-8 nm.
Example 10. as described in example 3, except that the organic solvent is pyridine, the water scavenger is calcium hydride, the boron source is tributylboron, the nitrogen source is ammonia, and the crystal grains inducing the growth of cubic boron nitride are zirconia nanopowder with an average particle size of 10 nm.
Claims (7)
1. A method for preparing boron nitride nanometer micropowder by utilizing organic solvent liquid phase chemical reaction comprises the following steps:
(1) under the protection of inert atmosphere, dissolving a soluble boron source in an organic solvent subjected to oxygen removal and water removal, stirring while dissolving, and continuously stirring for 10-80 minutes to obtain a solution with the concentration of 0.01-10 mol/L;
(2) slowly adding a stoichiometric ratio of a nitrogen source to the previously obtained boron source solution with stirring;
(3) stirring the solution for 0.5-5 hours, putting the solution into a closed reaction container, heating the solution to 50-600 ℃ at a filling rate of 30-95 percent, and reacting the solution for 3-120 hours under a shaking condition; or heating the uniformly stirred mixed solution to 50-300 ℃ in an open container under the protection of inert atmosphere, and reacting for 5-120 hours under the condition of continuous and rapid stirring;
(4) after the reaction is finished, the product is filtered by an organic solvent with the temperature of 30-200 ℃ for 1-8 times, and then is filtered by deionized water for several times until the filtrate is neutral;
(5) the obtained powder is dried in vacuum or inert atmosphere toobtain the boron nitride nanometer micro powder with uniform particles.
2. The method for producing a boron nitride nanopowder according to claim 1, wherein the crystal grains for inducing cubic boron nitride growth are added in the reaction vessel in the step (3) in an amount of 0.01 to 200 g/l solution.
3. The method for producing boron nitride nanopowder according to claim 2, wherein the inducing crystal grains are removed using an inorganic acid or alkali in step (4), followed by suction filtration with deionized water.
4. The method for producing a boron nitride nanopowder according to claim 2 or 3 wherein the crystal grains inducing the growth of cubic boron nitride are a metal, a II-VI semiconductor, a III-V semiconductor, an oxide semiconductor, and a salt having a cubic crystal structure and good stability and having a lattice parameter similar to that of cubic boron nitride.
5. The method for preparing boron nitride nanopowder according to claim 1 or 2, wherein the organic solvent comprises aromatic, alkane, pyridine, ether, ester with high boiling point and good chemical stability.
6. A process for the preparation of boron nitride nanopowders according to claim 1 or 2, wherein the boron source comprises boron halides, boranes and other organoboron compounds having moderate stability and soluble in the above organic solvents.
7. The method for producing a boron nitride nanopowder according to claim 1 or 2, wherein the nitrogen source comprises a metal nitride, ammonia, an organic amine and a nitrogen-containing organic substance, and the nitrogen source may be soluble in an organic solvent or may be a solid powder.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329290C (en) * | 2004-09-01 | 2007-08-01 | 山东大学 | Phase selection in-situ synthesis method used for controlling boron nitride object phase |
| CN100493691C (en) * | 2006-08-07 | 2009-06-03 | 山东大学 | Dissolvent hot liquid state phase-change method for synthesizing superhard micro nano material |
| CN101550599B (en) * | 2009-04-16 | 2011-05-11 | 山东大学 | Preparation method of boron nitride crystal whisker |
| CN104507862A (en) * | 2012-07-27 | 2015-04-08 | 韩化石油化学株式会社 | Porous boron nitride and method for manufacturing same |
| CN104507862B (en) * | 2012-07-27 | 2016-11-30 | 韩华化学株式会社 | Porous boron nitride and the preparation method of this porous boron nitride |
| CN107029773A (en) * | 2017-03-14 | 2017-08-11 | 沃邦环保有限公司 | Boron nitride bismuth tungstate composite photocatalyst of degradating organic dye and preparation method thereof |
| CN110902661A (en) * | 2019-12-23 | 2020-03-24 | 潍坊春丰新材料科技有限公司 | Nanoscale boron nitride powder for spraying field and manufacturing process thereof |
| CN112875716A (en) * | 2021-03-19 | 2021-06-01 | 中建材飞渡航天科技有限公司 | Gas-phase synthesis method of boron nitride ceramic precursor |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2633279A1 (en) * | 1988-06-27 | 1989-12-29 | Rhone Poulenc Chimie | NEW BORON NITRIDE MATERIAL, PROCESS FOR PREPARING THE SAME AND USE THEREOF AS REINFORCING AGENT |
| FR2684366A1 (en) * | 1991-11-28 | 1993-06-04 | Atochem | NEW PROCESS FOR PREPARING BORON NITRIDE AND BORON NITRIDE THUS OBTAINED |
| EP0918039A4 (en) * | 1996-08-06 | 1999-10-27 | Otsuka Kagaku Kk | Boron nitride and process for preparing the same |
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2001
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329290C (en) * | 2004-09-01 | 2007-08-01 | 山东大学 | Phase selection in-situ synthesis method used for controlling boron nitride object phase |
| CN100493691C (en) * | 2006-08-07 | 2009-06-03 | 山东大学 | Dissolvent hot liquid state phase-change method for synthesizing superhard micro nano material |
| CN101550599B (en) * | 2009-04-16 | 2011-05-11 | 山东大学 | Preparation method of boron nitride crystal whisker |
| CN104507862A (en) * | 2012-07-27 | 2015-04-08 | 韩化石油化学株式会社 | Porous boron nitride and method for manufacturing same |
| CN104507862B (en) * | 2012-07-27 | 2016-11-30 | 韩华化学株式会社 | Porous boron nitride and the preparation method of this porous boron nitride |
| US9796595B2 (en) | 2012-07-27 | 2017-10-24 | Hanwha Chemical Corporation | Porous boron nitride and method of preparing the same |
| CN107029773A (en) * | 2017-03-14 | 2017-08-11 | 沃邦环保有限公司 | Boron nitride bismuth tungstate composite photocatalyst of degradating organic dye and preparation method thereof |
| CN107029773B (en) * | 2017-03-14 | 2019-11-19 | 沃邦环保有限公司 | Boron nitride-bismuth tungstate composite photocatalyst of degradating organic dye and preparation method thereof |
| CN110902661A (en) * | 2019-12-23 | 2020-03-24 | 潍坊春丰新材料科技有限公司 | Nanoscale boron nitride powder for spraying field and manufacturing process thereof |
| CN112875716A (en) * | 2021-03-19 | 2021-06-01 | 中建材飞渡航天科技有限公司 | Gas-phase synthesis method of boron nitride ceramic precursor |
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| Publication number | Publication date |
|---|---|
| CN1101337C (en) | 2003-02-12 |
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