CN1597499A - Phase selection in-situ synthesis method used for controlling boron nitride object phase - Google Patents
Phase selection in-situ synthesis method used for controlling boron nitride object phase Download PDFInfo
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Abstract
A phase-choosing process for in-situ synthesis of boron nitride with controlled phase incldues such steps as respectively dissolving boron source and nitrogen source in organic solvent, putting one solution in reactor, putting another in isolating container, hierarchically putting them in reaction system, reaction at 120-600 deg.C for 10-300 hr to generate boron nitride and drying by vacuum heating to obtain uniform BN microcrystals.
Description
(1) technical field
The present invention relates to select the phase in-situ synthetic method in a kind of solvent thermal reaction, be specifically related to a kind of be used to control boron nitride thing phase select the phase in-situ synthetic method, belong to chemical technology field.
(2) background technology
Modal in boron nitride (BN) material is hexagonal boron nitride (hBN), cubic boron nitride (cBN) and close heap hexagonal boron nitride (wBN).HBN wherein has high heat conductance, good chemical stability and excellent lubricating property and is used to nano lubricating, high-performance electron tube, high stability heating container, high heat conductance heat sink material or the like.CBN is the same with diamond, is the superhard material of excellent performance, its over-all properties even surpass diamond.WBN then has the character close with cBN, and they play a part very important in daily life and industrial production.Realize the synthetic of this superhard material of cBN, particularly low-cost in enormous quantities synthetic, once and always be the ideal that the mankind dream of.
Have excellent performance and purposes widely just because of hBN and cBN, people have carried out unremitting exploration aspect this two kinds of materials synthetic for many years, have developed various methods.For example, under high temperature (700～1100 ℃), make the method for urea and borax prepared in reaction hBN be applied to industrial production.By contrast, cBN prepares with high temperature and high pressure method.The preparation method of analysis-by-synthesis hBN and cBN is not difficult to find: there is the particle size uniformity difference of temperature of reaction height, powder in the method for preparing hBN and is difficult to obtain granularity is shortcomings such as nano level powder body material.The high temperature and high pressure method of synthetic cBN has again that apparatus expensive, temperature and pressure are too high, condition can't accurately be monitored, and poor repeatability and input/output compared high shortcoming.In order to overcome these shortcomings, applicant of the present invention had once been developed the novel method of utilizing structure inductive effect synthetic boron nitride under the solvent thermal condition, and (patent No.: ZL01115125.0), and academic at home and abroad and industrial community has produced bigger influence.But also there are some shortcomings in this method, and for example: the granularity of the boron nitride sample that reaction process is more restive, obtain and crystalline condition are difficult to regulation and control etc.In addition, this method is introduced xenogenesis crystal grain inevitably in the boron nitride sample, the performance of synthetic cubic boron nitride is under some influence.
We find through the method for deeply systematically analyzing above-mentioned synthetic cBN: raw materials used during the high temperature and high pressure method synthesizing cubic boron nitride is the very high hexagonal boron nitride of stability, make the change transitions on its recurring structure become another kind of thing to need to overcome very high potential barrier mutually.That is to say that in case formed stable solid matter, it is very difficult that its recurring structure is changed.Change an angle and consider,, can change the direction that this process is carried out with comparalive ease, thereby develop to the result that we wish if in the forming process of certain solid matter, it is intervened; Have, when utilizing solvent thermal process to prepare boron nitride, the raw materials all in the initial stage of reaction process just are in contact with one another again, and the reaction that generates boron nitride in the temperature elevation process is carried out gradually.Like this, when temperature and pressure was low, the thing phase (hBN) that thermostability is the highest will at first occur, and having only those just may be cubic boron nitride at the product that high-temperature and high-pressure conditions (stabilized zone of cubic boron nitride) occurs down.Said above that in case stable solid matter has occurred, it will be very difficult making it change another kind of structure type into again, the result that this phenomenon causes is that the productive rate of cubic boron nitride reduces significantly, and is difficult to grow up to big crystal.
Cubic boron nitride is very important 26S Proteasome Structure and Function material, and its shared critical role in our daily life and industrial production is known by people.But,, seriously limited its use range because the shortcoming of the low output of the high investment that existing synthetic method exists makes that its production cost and price are high always.
(3) technology contents
The present invention is directed to the shortcoming that the synthetic boron nitride method of existing solvent thermal exists, a kind of phase in-situ synthetic method that selects has been proposed, can control mutually the thing of final synthetic boron nitride well on the one hand, also can mix mutually and the speed of react is improved the crystalline quality of material and regulated and control crystallite size on the other hand by the control raw material.Utilize method of the present invention, can successfully control the thing phase in the boron nitride, and by controlling the mixing velocity of reaction raw materials, the cubic boron nitride micro crystal material that has obtained having the higher crystalline quality.
Of the present invention be used to control boron nitride thing phase select the phase in-situ synthetic method, comprise the steps that order is not limit:
(1) pre-treatment of organic solvent
In organic solvent, add siccative and leave standstill distillation after 10-72 hour according to the consumption of 0.01-1.0 grams per milliliter solvent, so that remove impurity such as the water that contains in desolvating, oxygen;
(2) preparation of boron source liquid
Under protection of inert gas, the boron source to be dissolved in the above-mentioned organic solvent, concentration is 0.005～20 mol, obtains boron source solution or suspension liquid after stirring fast;
(3) preparation of nitrogenous source liquid
Under protection of inert gas, nitrogenous source with stoichiometric ratio dissolves in the organic solvent while stirring, obtain the solution or the suspension liquid of nitrogenous source, used organic solvent can be same with the solvent phase in (2), also can be the another kind of organic solvent of handling through step (1);
(4) dress still
In the nitrogenous source liquid of preparing above or one of them immigration autoclave of boron source liquid, add organic solvent again through the deoxygenation that dewaters, making the filling ratio volume percent is 20～95%.
(5) dress sealing chamber
The boron source liquid of the autoclave of preparing above of not packing into or nitrogenous source liquid, in the sealing chamber of packing into, sealing chamber is packed in the reactor, and is fixing, gets rid of air in the still with rare gas element, the envelope still; Sealing chamber integral body is positioned at reactor, and its on-off mechanism is positioned at outside the reactor, so that in reaction process, open or close sealing chamber as required, and reinforced in reactor.
(6) reaction
The temperature of control reactor is heated to 120 ℃～600 ℃ reactions 10 hours～300 hours with 0.01 ℃/minute-60 ℃/minute speed.During this period, divide once, repeatedly or continuously boron source liquid in the sealing chamber or nitrogenous source liquid to be joined in the reactor, reaction generates boron nitride.
(7) sample aftertreatment
After reaction finishes, earlier the solvent suction filtration is fallen, use deionized water suction filtration product again, be neutral up to filtrate; Above-mentioned product is heated to 60～200 ℃ of dryings in a vacuum, just can obtain even-grained BN crystallite.
Temperature and pressure difference during according to the beginning reaction raw material, the boron nitride crystallite that obtains can be the mixture and the pure cubic boron nitride of hexagonal boron nitride, quadrature boron nitride, quadrature boron nitride and cubic boron nitride, and the temperature and pressure when beginning to mix is high more, and the content of cubic boron nitride is high more.
The organic solvent that uses in above-mentioned steps (1) is chosen one or more from benzene, alkylbenzene, halogeno-benzene, alkane and haloalkane, nitrile, pyridine, pyrroles, liquefied ammonia, organic amine, amide solvent.
The siccative that uses in above-mentioned steps (1) is then chosen one or more from basic metal, alkalimetal oxide, alkaline-earth metal, alkaline earth metal halide, alkaline earth metal oxide, alkaline earth metal sulphate, molecular sieve, activated alumina, Vanadium Pentoxide in FLAKES, lithium aluminum hydride and hydrolith.
The rare gas element that uses in above-mentioned steps (2) is selected from nitrogen, helium, neon or argon gas.
One or more are chosen in the boron source of using in above-mentioned steps (2) from halogenation boron, borine, metal borohydride, metal boride, halogen borate, borate ester, ammonium borate.
The nitrogenous source that uses in above-mentioned steps (3) is chosen one or more from metal nitride, trinitride, ammonia, inorganic ammonium salt, three halogenated nitrogens, organic amine, hydrazine class and title complex thereof.
Used sealing chamber is selected the structure shown in Figure 3 of ZL03218373.9 for use in above-mentioned steps (5).
In above-mentioned steps (6), when boron source and nitrogenous source when mixing continuously at a slow speed, can from organic solvent, grow granularity and reach micron order even bigger boron nitride crystal.
Method of the present invention is a kind of in-situ synthetic method mutually that selects that is used for controlling solvent thermal reaction process boron nitride thing phase and crystalline quality.Compare with existing method, significant improvement of the present invention is as follows: when temperature of reaction and pressure are low, each reaction raw materials is isolated mutually, after the question response temperature and pressure is elevated to preset value, make their mutual hybrid concurrencies give birth to reaction by controllable manner again, directly generate the cubic boron nitride that we need, avoided the phase transition process that needs severe condition to realize.And, utilize this method controls reaction speed, the nucleating process of modulation boron nitride, crystallite size and homogeneity, crystalline perfection as required arbitrarily.In addition, under the situation that reaction is carried out at a slow speed continuously, can also prepare large-sized cubic boron nitride crystal grain (body), this result almost is can not be getable with common solvent thermal reaction method.Have again, utilize this phase original position generation method of selecting, do not need to add other crystal grain and make the thing phase that structure inducer just can be controlled product, thereby eliminated " pollution " that structure inducer is brought, guaranteed the high purity of sample, for the practicability of this technology is laid a good foundation.
Utilize and select the phase in-situ synthetic method under the solvent thermal condition of the present invention, we have successfully controlled the mixing process and the speed of various raw materials in the solvent thermal reaction process, can make as required and generate hexagonal boron nitride or cubic boron nitride in the reaction system.Method of the present invention not only makes the reaction process controllability stronger, and is easy to amplify preparative-scale, realizes low-cost in enormous quantities synthesize of cubic boron nitride under mild conditions, therefore has important practical significance.On the other hand, method of the present invention is again to combine the relevant theoretical back development of chemical reaction thermodynamics, high-pressure physics and inorganic a plurality of subjects such as synthetic and come, and it will drive the development of related discipline.Have again, the phase in-situ synthetic method that selects of the present invention not only is applicable to the synthetic of cubic boron nitride, can be used for the controlled preparation of other 26S Proteasome Structure and Function materials equally, particularly synthesize some selectively and have the thing phase time of special property from the system of those heterogeneous coexistences, method of the present invention has unique advantages especially.
The cubic boron nitride crystallite range of application of the inventive method preparation is very extensive, for example can be applied to precision optical machinery process tool and the manufacturing of high stability high rigidity drill bit, superhard corrosion-resistant protective coating manufacturing etc., in addition, can also be used for the high temperature resistant heating container of high stability, high heat conductance insulating material, high-performance nano lubricating fluid, military extraordinary window material etc.
The invention will be further elaborated below in conjunction with description of drawings and embodiment.
(4) description of drawings
Fig. 1 is BBr
3With the XRD spectra of the boron nitride sample of NaN3 prepared in reaction, wherein,
(a) 120 ℃, once reinforced, (b) 240 ℃, once reinforced, (c) 280 ℃, five times reinforced.
Fig. 2 is at 280 ℃ of HRTEM photos of the BN sample of original position hybrid reaction preparation repeatedly.As can be seen, have more crystallizing field in Zhi Bei the boron nitride in this way, wherein indicating " oBN " is the quadrature boron nitride, and what indicate " cBN " is cubic boron nitride.
Fig. 3 uses BCl
3HRTEM photo with the boron nitride sample of magnesium nitride prepared in reaction.The little crystal grain that indicates " cBN " among the figure is cubic boron nitride.
Fig. 4 is the HRTEM photo of the boron nitride of preparation among the embodiment 22.The same front of implication of " oBN " and " cBN " among the figure.
Fig. 5 is the HRTEM photo of the boron nitride of preparation among the embodiment 31.Main thing is the quadrature boron nitride mutually in this sample.
Fig. 6 is the HRTEM photo of the boron nitride crystallite sample of preparation among the embodiment 34.
Fig. 7 is the HRTEM photo of the boron nitride crystallite sample of preparation among the embodiment 34.This photo is taken from another zone of sample.
Fig. 8 is the HRTEM photo of the boron nitride crystallite sample of preparation among the embodiment 35.This sample is by quadrature boron nitride and two kinds of thing phase composites of cubic boron nitride.
Fig. 9 is with the infrared absorption spectrum of usual vehicle by the use of thermal means with the BN that selects the preparation of in-situ method (embodiment 53) mutually.Wherein, (a) usual vehicle by the use of thermal means (b) selects the phase in-situ synthetic method.Wherein be positioned at 1049cm
-1The absorption peak at place derives from cubic boron nitride.
Figure 10 is the microscopic appearance picture of the cubic boron nitride crystal grain of embodiment 53 preparations.
(5) embodiment
Embodiment 1: at first in benzene, add the sodium Metal 99.5 sheet and leave standstill distillation after 24 hours, to remove water, the oxygen that contains in the benzene according to the consumption of 0.01 grams per milliliter.Then under nitrogen protection, boron tribromide is dissolved in 40 milliliters of benzene, stir fast and make it dissolving, obtain the solution that concentration is 0.005 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under nitrogen protection, the sodiumazide powder with stoichiometric ratio dissolves in the benzene while stirring, obtains the suspension liquid of nitrogenous source.The nitrogenous source suspension liquid is transferred in the autoclave, added the benzene through the deoxygenation that dewaters again, making filling ratio is 20% (volume percent).
The sealing chamber that boron tribromide solution is housed packed into to fix in the reactor, gets rid of in the still with nitrogen and seals still behind the air.The temperature of control reactor is heated to 120 ℃ of reactions 10 hours with 0.01 ℃/minute speed.During this period, when the temperature of reactor is elevated to 120 ℃, when pressure is normal pressure, join in the reactor the boron tribromide solution in the sealing chamber is disposable, make it and the nitrogenous source generation boron nitride that reacts.
Reaction is at first fallen the benzene suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 60 ℃ of dryings in a vacuum, just can obtain hexagonal boron nitride (hBN) nano microcrystalline, and its X-ray diffraction (XRD) spectrogram is seen accompanying drawing 1 (a).
Embodiment 2: all reaction raw materials of use and working method be with embodiment 1, and difference is that temperature of reaction brought up to 240 ℃.The XRD spectra of the sample that obtains is like this seen accompanying drawing 1 (b).
Embodiment 3: all reaction raw materials of use and working method be with embodiment 1, and difference is that temperature of reaction brought up to 280 ℃, and the reactor filling ratio has brought up to 65%, and boron tribromide solution divides five original positions to join in the reactor.The BN sample kind that obtains like this contains more quadrature boron nitride (oBN) and cubic boron nitride (cBN), and its XRD spectra is seen accompanying drawing 1 (c), and corresponding high resolution transmission electron microscopy (HRTEM) photo is seen accompanying drawing 2.
Embodiment 4: all reaction raw materials of use and working method are with embodiment 1, and unique difference is the position of the suspension liquid of the benzole soln of boron tribromide and sodiumazide is exchanged, and the properties of samples that obtains is identical with embodiment 1.
Embodiment 5: earlier in benzene, add potassium metal and leave standstill distillation after 10 hours, to remove water, the oxygen that contains in the benzene according to the consumption of 0.05 grams per milliliter.Then under nitrogen protection, boron trichloride is dissolved in 40 milliliters of benzene, stir fast and make it dissolving, obtain the solution that concentration is 0.005 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under nitrogen protection, the magnesium nitride powder with stoichiometric ratio dissolves in the benzene while stirring, obtains the suspension liquid of magnesium nitride.The magnesium nitride suspension liquid is transferred in the autoclave, added the benzene through the deoxygenation that dewaters again, making filling ratio is 45%.
The sealing chamber that boron trichloride solution is housed packed into to fix in the reactor, gets rid of in the still with nitrogen and seals still behind the air.The temperature of control reactor is heated to 120 ℃ of reactions 10 hours with 0.01 ℃/minute speed.During this period, when the temperature of reactor is elevated to 120 ℃, when pressure is 5 normal atmosphere, join in the reactor the boron trichloride solution in the sealing chamber is disposable, make it and the nitrogenous source generation boron nitride that reacts.
After reaction finishes, earlier the benzene suction filtration is fallen, use deionized water suction filtration product again, be neutral up to filtrate.The product that obtains is heated to 60 ℃ of dryings in a vacuum, just can obtain hexagonal boron nitride (hBN) nano microcrystalline.Major part is very little hBN nucleus in this sample, wherein also is being mingled with a spot of cBN, and its HRTEM photo is seen accompanying drawing 3.
Embodiment 6: all operations process and method are with embodiment 5, and difference is: the siccative potassium metal is replaced by metallic lithium, is replaced by boron trifluoride as the boron trichloride in boron source, is replaced by CaCl2 as the magnesium nitride of nitrogenous source.
Embodiment 7: in benzene and toluene, add sodium oxide respectively and leave standstill distillation after 16 hours, to remove water, the oxygen that wherein contains according to the consumption of 0.2 grams per milliliter.Then under the helium protection, be mol ratio that 1: 1 boron trifluoride and diborane dissolves in 40 milliliters of toluene, stir fast and make it dissolving, obtain the solution that concentration is 0.05 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under the helium protection, lithium nitride and the sodiumazide powder (mol ratio 1: 2) with stoichiometric ratio adds in the benzene while stirring, obtains the suspension liquid of sodiumazide.This suspension liquid is transferred in the autoclave, added the benzene through the deoxygenation that dewaters again, making filling ratio is 40%.
The sealing chamber that boron source solution is housed packed into to fix in the reactor, gets rid of in the still with helium and seals still behind the air.The temperature of control reactor is heated to 180 ℃ of reactions 20 hours with 0.1 ℃/minute speed.During this period,, when pressure is normal pressure, the boron source solution in the sealing chamber is joined (interval between adjacent twice 6 hours) in the reactor at twice, make it and the nitrogenous source generation boron nitride that reacts when the temperature of reactor is elevated to 180 ℃.
After reaction finishes, earlier the solvent suction filtration is fallen, use deionized water suction filtration product again, be neutral up to filtrate.The product that obtains is heated to 100 ℃ of dryings in a vacuum, just can obtain even-grained hexagonal boron nitride (hBN) nano microcrystalline.
Embodiment 8: all operations process and method are with embodiment 7, and difference is: the oxidized potassium of siccative sodium oxide replaces, and the toluene in the mixed solvent is replaced by dimethylbenzene.In addition, replaced by tetraborane, replaced by potassium azide as the sodiumazide of one of nitrogenous source as the diborane in one of boron source.
Embodiment 9: all operations process and method are with embodiment 7, and difference is: the oxidized lithium of siccative sodium oxide replaces, and the toluene in the mixed solvent is replaced by ethylbenzene.In addition, replaced by pentaborane, replaced by azide magnesium as the sodiumazide of one of nitrogenous source as the diborane in one of boron source.
Embodiment 10: in ethylbenzene and trimethylbenzene, add the mixture (mol ratio 2: 1, the total consumption of siccative is 0.5 grams per milliliter) of Lithium Oxide 98min and potassium oxide respectively and leave standstill distillation after 16 hours, to remove water, the oxygen that wherein contains.Then under the helium protection, be mol ratio that 1: 1 boron trichloride and tetraborane dissolves in 40 milliliters of trimethylbenzenes, stir fast and make it dissolving, obtain the solution that concentration is 0.05 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under the helium protection, lithium nitride and the azide magnesium dust (mol ratio 1: 2) with stoichiometric ratio adds in the ethylbenzene while stirring, obtains the suspension liquid of nitrogenous source.This suspension liquid is transferred in the autoclave, added the ethylbenzene through the deoxygenation that dewaters again, making filling ratio is 40%.
The sealing chamber that boron source solution is housed packed into to fix in the still, gets rid of in the still with helium and seals still behind the air.The temperature of control reactor is heated to 180 ℃ of reactions 20 hours with 0.1 ℃/minute speed.During this period,, when pressure is normal pressure, the boron source solution in the sealing chamber is joined (interval between adjacent twice 6 hours) in the reactor at twice, make it and the nitrogenous source generation boron nitride that reacts when the temperature of reactor is elevated to 180 ℃.
After reaction finishes, earlier the solvent suction filtration is fallen, use deionized water suction filtration product again, be neutral up to filtrate.The product that obtains is heated to 100 ℃ of dryings in a vacuum, just can obtain hexagonal boron nitride (hBN) nano microcrystalline.
Embodiment 11: operating process and method are with embodiment 10, and difference is: the lithium nitride in the mixed nitrogen is replaced by potassium azide, and the boron trichloride that mixes in the boron source is replaced by diborane.
Embodiment 12: the consumption according to 1.0 grams per milliliters in organic solvent chlorobenzene, benzene and the dimethylbenzene of selecting for use adds the metal magnesium sheet and leaves standstill 48 back distillations, to remove water, the oxygen that wherein contains.Then under the neon protection, sodium borohydride, tetraborane and boron tribromide (mol ratio is 3: 1: 2) are dissolved in successively in the mixed solvent of 60 milliliters of benzene and dimethylbenzene (volume ratio is 3: 1), stir after 30 minutes fast and obtain the suspension liquid that concentration is 0.1 mol, it is standby in the sealing chamber that this suspension liquid is packed into; In addition, under the neon protection, lithium nitride and potassium azide (mol ratio 1: the 3) powder with stoichiometric ratio adds in the chlorobenzene while stirring, obtains the suspension liquid of two kinds of nitrogenous source mixtures.Add liquefied ammonia (lithium nitride: the liquefied ammonia mol ratio is 1: 5) again in this suspension liquid, at last suspension liquid is transferred in the autoclave, add the chlorobenzene through the deoxygenation that dewaters again, making filling ratio is 60%.
The sealing chamber that boron source suspension liquid is housed packed into to fix in the reactor, gets rid of in the still with neon and seals still behind the air.The temperature that makes reactor is heated to 220 ℃ of reactions 36 hours with 0.5 ℃/minute speed.During this period, when the temperature of reactor is elevated to 220 ℃, when pressure is 20 normal atmosphere, the boron source suspension liquid in the sealing chamber divided join (interval between adjacent twice 4 hours) in the reactor for three times, make it and the nitrogenous source generation boron nitride that reacts.
Reaction is at first fallen the solvent suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 120 ℃ of dryings in a vacuum, just can obtain the mixture of even-grained hBN and quadrature boron nitride (oBN) nano microcrystalline.
Embodiment 13: the operating process of preparation sample is identical with embodiment 12 with method, and difference is: the solvent chlorobenzene is replaced by fluorobenzene, and benzene is replaced by bromobenzene; The siccative magnesium sheet replaces with calcium tablet; Sodium borohydride as one of boron source is replaced by POTASSIUM BOROHYDRIDE, and another boron source tetraborane is replaced by boron trichloride; Lithium nitride in the nitrogenous source is replaced by magnesium nitride, and potassium azide is then replaced by sodiumazide.
Embodiment 14: the operating process of preparation sample is identical with embodiment 12 with method, and difference is: the solvent chlorobenzene is replaced by fluorobenzene, and benzene is replaced by bromobenzene, and dimethylbenzene is replaced by trimethylbenzene; The siccative magnesium sheet replaces with calcium tablet; Sodium borohydride as one of boron source is replaced by lithium borohydride, and another boron source tetraborane is replaced by diborane, and boron tribromide is replaced by boron trichloride; Lithium nitride in the nitrogenous source is replaced by CaCl2.
Embodiment 15: at first in Skellysolve A, add calcium chloride and leave standstill distillation after 30 hours, to remove water, the oxygen that wherein contains according to the consumption of 1.0 grams per milliliters.Then under argon shield, magnesium diboride is joined in 40 milliliters of Skellysolve As, stir fast and obtain the suspension liquid that concentration is 0.4 mol, it is standby in the sealing chamber that this suspension liquid is packed into; In addition, under argon shield, the urea powder with stoichiometric ratio dissolves in the Skellysolve A while stirring, obtains the suspension liquid of nitrogenous source.The nitrogenous source suspension liquid is transferred in the autoclave, added the Skellysolve A through the deoxygenation that dewaters again, making filling ratio is 80%.
The sealing chamber that the magnesium diboride suspension liquid is housed packed into to fix in the still, gets rid of in the still with argon gas and seals still behind the air.The temperature of utilizing programmed temperature control instrument control reactor is heated to 220 ℃ of reactions 72 hours with 1.0 ℃/minute speed.During this period, when the temperature of reactor is elevated to 220 ℃, when pressure is 25 normal atmosphere, the boron source suspension liquid in the sealing chamber divided join (adjacent twice timed interval is 5 hours) in the reactor for five times, make it and the nitrogenous source generation boron nitride that reacts.
Reaction is at first fallen the Skellysolve A suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 160 ℃ of dryings in a vacuum, obtains the mixing nano microcrystalline of even-grained oBN and cubic boron nitride (cBN).
Embodiment 16: the preparation process of sample and working method are with embodiment 15, and different is: the solvent Skellysolve A has changed tetracol phenixin into, and siccative calcium chloride has then changed magnesium chloride into, and in addition, nitrogen source urea has changed volatile salt into.
Embodiment 17: the preparation process of sample and working method are with embodiment 15, and different is: the solvent Skellysolve A has changed heptane into, and nitrogen source urea has changed ammonium chloride into.
Embodiment 18: the preparation process of sample and working method are with embodiment 16, and different is: the solvent tetracol phenixin has changed methylene dichloride into.
Embodiment 19: the preparation process of sample and working method are with embodiment 16, and different is: the solvent tetracol phenixin has changed bromofom into.
Embodiment 20: the preparation process of sample and working method are with embodiment 15, and different is: the solvent Skellysolve A has changed hexachloroethane into.
Embodiment 21: in benzene, add calcium oxide and leave standstill distillation after 28 hours, to remove water, the oxygen that wherein contains according to the consumption of 0.6 grams per milliliter.Then under nitrogen protection, sodium borohydride is joined in 40 milliliters of benzene, stir fast and obtain the suspension liquid that concentration is 0.8 mol, it is standby in the sealing chamber that this suspension liquid is packed into; In addition, under nitrogen protection, the nitrogen trichloride with stoichiometric ratio when slowly stirring dissolves in the benzene, obtains nitrogenous source solution.Nitrogenous source solution is transferred in the autoclave, added the benzene through the deoxygenation that dewaters again, making filling ratio is 90%.
The sealing chamber that boron source suspension liquid is housed packed into to fix in the still, gets rid of in the still with nitrogen and seals still behind the air.The temperature of utilizing programmed temperature control instrument control reactor is heated to 350 ℃ of reactions 108 hours with 1.8 ℃/minute speed.During this period, when the temperature of reactor is elevated to 350 ℃, when pressure is 90 normal atmosphere, the boron source suspension liquid in the sealing chamber divided join (adjacent twice timed interval is 2 hours) in the reactor for eight times, make it and the nitrogenous source generation boron nitride that reacts.
Reaction is at first fallen the benzene suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 180 ℃ of dryings in a vacuum, obtains based on the cBN of cubic boron nitride (cBN) and the mixed microcrystalline of oBN.
Embodiment 22: the preparation process of sample and working method are with embodiment 21, and different is: the nitrogenous source nitrogen trichloride has changed sodiumazide into.The HRTEM photo of the sample that obtains is like this seen accompanying drawing 4.
Embodiment 23: the preparation process of sample and working method are with embodiment 21, and different is: the siccative calcium oxide has changed strontium oxide into, and the nitrogenous source nitrogen trichloride has changed nitrogen trifluoride into.
Embodiment 24: in benzene, add calcium sulfate and leave standstill distillation after 18 hours, to remove the water that wherein contains according to the consumption of 0.6 grams per milliliter.Then under nitrogen protection, the tetrachloro potassium borate is joined in 60 milliliters of benzene, stir fast and obtain the suspension liquid that concentration is 1.6 mol, it is standby in the sealing chamber that this suspension liquid is packed into; In addition, under nitrogen protection, the Trimethylamine 99 with stoichiometric ratio when stirring fast dissolves in the benzene, obtains nitrogenous source solution.Nitrogenous source solution is transferred in the autoclave, added the benzene through the deoxygenation that dewaters again, making filling ratio is 95%.
The sealing chamber that boron source suspension liquid is housed packed into to fix in the still, gets rid of in the still with nitrogen and seals still behind the air.The temperature of utilizing programmed temperature control instrument control reactor is heated to 480 ℃ of reactions 200 hours with 5 ℃/minute speed.During this period,, when pressure is 400 normal atmosphere, the boron source suspension liquid in the sealing chamber is joined (adjacent twice timed interval is 24 hours) in the reactor at twice, make it and the nitrogenous source generation boron nitride that reacts when the temperature of reactor is elevated to 480 ℃.
Reaction is at first fallen the benzene suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 200 ℃ of dryings in a vacuum, obtains pure cubic boron nitride (cBN) crystallite.
Embodiment 25: all operations process and method are with embodiment 24, difference is: siccative calcium sulfate is replaced by sal epsom, boron source tetrachloro potassium borate is replaced by ammonium tetrafluoroborate, and boron source concentration become 3.6 mol by 1.6 mol, and the nitrogenous source Trimethylamine 99 is then replaced by diethylamine.In addition, heat-up rate rises to 10 ℃/minute by 5 ℃/minute, and the reaction times has extended to 240 hours
Embodiment 26: in pyridine, add the 3A molecular sieve and leave standstill distillation after 36 hours, to remove water, the oxygen that wherein contains according to the consumption of 0.2 grams per milliliter.Then under argon shield, trimethyl borate and boron tribromide (mol ratio is 1: 3) are joined in 50 milliliters of pyridines, stir fast and obtain the solution that concentration is 3.6 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under argon shield, the aniline with stoichiometric ratio when stirring fast dissolves in the pyridine, obtains nitrogenous source solution.Nitrogenous source solution is transferred in the autoclave, added the pyridine through the deoxygenation that dewaters again, making filling ratio is 90%.
The sealing chamber that boron source solution is housed packed into to fix in the still, gets rid of in the still with argon gas and seals still behind the air.The temperature of utilizing programmed temperature control instrument control reactor is heated to 480 ℃ of reactions 240 hours with 10 ℃/minute speed.During this period,, when pressure is 350 normal atmosphere, the boron source suspension liquid in the sealing chamber is joined (adjacent twice timed interval is 20 hours) in the reactor at twice, make it and the nitrogenous source generation boron nitride that reacts when the temperature of reactor is elevated to 480 ℃.
Reaction is at first fallen the pyridine suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 180 ℃ of dryings in a vacuum, obtains pure cubic boron nitride (cBN) crystallite.
Embodiment 27: in benzene and pyridine, add 4A type molecular sieve and leave standstill distillation after 20 hours, to remove water, the oxygen that wherein contains according to the consumption of 0.5 grams per milliliter.Then under argon shield, tripropoxy-boron is joined in 80 milliliters of pyridines, stir fast and obtain the solution that concentration is 12 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under argon shield, the hydrazine with stoichiometric ratio when stirring fast dissolves in the pyridine, obtains nitrogenous source solution.Nitrogenous source solution is transferred in the autoclave, added the benzene through the deoxygenation that dewaters again, making filling ratio is 90%.
The sealing chamber that boron source solution is housed packed into to fix in the reactor, gets rid of in the still with argon gas and seals still behind the air.The temperature of utilizing programmed temperature control instrument control reactor is heated to 600 ℃ of reactions 300 hours with 40 ℃/minute speed.During this period, when the temperature of reactor is elevated to 600 ℃, when pressure is 1800 normal atmosphere,, make it and the nitrogenous source generation boron nitride that reacts disposable the joining in the reactor of boron source suspension liquid in the sealing chamber.
Reaction is at first fallen the solvent suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 200 ℃ of dryings in a vacuum, obtains pure cubic boron nitride (cBN) crystallite.
Embodiment 28: all operations process and method are with embodiment 27, and difference is: solvent benzol is replaced by liquefied ammonia.
Embodiment 29: all operations process and method are with embodiment 27, and difference is: the nitrogenous source hydrazine is replaced by the hydrazine dihydrochloride.
Embodiment 30: all operations process and method are with embodiment 27, and difference is: the nitrogenous source hydrazine is replaced by methyl hydrazine.
Embodiment 31: in acetonitrile, add activated alumina and leave standstill distillation after 18 hours, to remove the water that wherein contains according to the consumption of 0.6 grams per milliliter.Then under the helium protection, ammonium borate is joined in 60 milliliters of acetonitriles, stir fast and obtain the solution that concentration is 0.4 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under helium protection, when stirring fast with the Zn (N of stoichiometric ratio
2H
4)
2Cl
2Dissolve in the acetonitrile, obtain nitrogenous source solution.Nitrogenous source solution is transferred in the autoclave, added the acetonitrile through the deoxygenation that dewaters again, making filling ratio is 90%.
The sealing chamber that boron source solution is housed packed into to fix in the still, gets rid of in the still with helium and seals still behind the air.The temperature of utilizing programmed temperature control instrument control reactor is heated to 350 ℃ of reactions 72 hours with 40 ℃/minute speed.In reaction process, when the temperature of reactor is elevated to 350 ℃, when pressure is 100 normal atmosphere, the boron source solution in the sealing chamber is joined in the reactor, make it and the nitrogenous source generation boron nitride that reacts.
Reaction is at first fallen the acetonitrile suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 60 ℃ of dryings in a vacuum, obtains cBN and oBN blended nano microcrystalline sample based on oBN.The HRTEM photo of this sample is seen accompanying drawing 5.
Embodiment 32: in propionitrile, add the 4A molecular sieve and leave standstill distillation after 36 hours, to remove water, the oxygen that wherein contains according to the consumption of 0.3 grams per milliliter.Then under the helium protection, boron tribromide is joined in 50 milliliters of propionitrile, stir fast and obtain the solution that concentration is 20 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under the helium protection, the potassium azide with stoichiometric ratio when stirring fast dissolves in the propionitrile, obtains the nitrogenous source suspension liquid.The nitrogenous source suspension liquid is transferred in the autoclave, added the propionitrile through the deoxygenation that dewaters again, making filling ratio is 80%.
The sealing chamber that boron source solution is housed packed into to fix in the reactor, gets rid of in the still with helium and seals still behind the air.The temperature of control reactor is heated to 220 ℃ of reactions 36 hours with 60 ℃/minute speed.During this period,, when pressure is 18 normal atmosphere, the boron source solution in the sealing chamber is joined in the reactor, make it and the nitrogenous source generation boron nitride that reacts when the temperature of reactor is elevated to 220 ℃.
Reaction is at first fallen the propionitrile suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 200 ℃ of dryings in a vacuum, obtains hBN and oBN blended nano microcrystalline sample.
Embodiment 33: in benzonitrile, add activated alumina and leave standstill distillation after 32 hours, to remove water, the oxygen that wherein contains according to the consumption of 0.6 grams per milliliter.Then under argon shield, tetraborane is joined in 45 milliliters of benzonitriles, stir fast and obtain the solution that concentration is 12 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under argon shield, when stirring fast with the Zn (N of stoichiometric ratio
2H
4)
2Cl
2Dissolve in the benzonitrile, obtain the nitrogenous source suspension liquid.The nitrogenous source suspension liquid is transferred in the autoclave, added the benzonitrile through the deoxygenation that dewaters again, making filling ratio is 95%.
The sealing chamber that boron source solution is housed packed into to fix in the reactor, gets rid of in the still with argon gas and seals still behind the air.The temperature of control reactor is heated to 300 ℃ of reactions 32 hours with 1.8 ℃/minute speed.During this period,, when pressure is 280 normal atmosphere, the boron source solution in the sealing chamber is joined in the reactor, make it and the nitrogenous source generation boron nitride that reacts when the temperature of reactor is elevated to 300 ℃.
Reaction is at first fallen the benzonitrile suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 80 ℃ of dryings in a vacuum, obtains cBN and oBN blended nano microcrystalline sample based on cBN.
Embodiment 34: in acetonitrile, add the 3A molecular sieve and leave standstill distillation after 20 hours, remove the water, the oxygen that wherein contain according to the consumption of 0.2 grams per milliliter.Then under argon shield, ammonium borate is joined in 50 milliliters of acetonitriles, stir fast and obtain the solution that concentration is 1.6 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under argon shield, the methyl hydrazine with stoichiometric ratio when stirring fast dissolves in the acetonitrile, obtains nitrogenous source solution.Nitrogenous source solution is transferred in the autoclave, added the acetonitrile through the deoxygenation that dewaters again, making filling ratio is 60%.
The sealing chamber that boron source solution is housed packed into to fix in the reactor, gets rid of in the still with argon gas and seals still behind the air.The temperature of control reactor is heated to 350 ℃ of reactions 20 hours with 1.2 ℃/minute speed.During this period,, when pressure is 30 normal atmosphere, the boron source solution in the sealing chamber is joined (twice reinforced timed interval is 5 hours) in the reactor at twice, make it and the nitrogenous source generation boron nitride that reacts when the temperature of reactor is elevated to 350 ℃.
Reaction is at first fallen the acetonitrile suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 200 ℃ of dryings in a vacuum, and obtaining oBN is the cBN and the oBN blended nano microcrystalline sample of advantage thing phase, and its HRTEM photo is seen accompanying drawing 6 and 7.
Embodiment 35: in acetonitrile and pyridine, add activated alumina and leave standstill distillation after 25 hours, to remove water, the oxygen that wherein contains according to the consumption of 0.4 grams per milliliter.Then under nitrogen protection, trimethyl borate is joined in 60 milliliters of acetonitriles, stir fast and obtain the solution that concentration is 5 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under nitrogen protection, the hydrazine with stoichiometric ratio when stirring fast dissolves in the pyridine, obtains nitrogenous source solution.Nitrogenous source solution is transferred in the autoclave, added the pyridine through the deoxygenation that dewaters again, making filling ratio is 90%.
The sealing chamber that boron source solution is housed packed into to fix in the reactor, gets rid of in the still with nitrogen and seals still behind the air.The temperature of control reactor is heated to 350 ℃ of reactions 36 hours with 5 ℃/minute speed.During this period,, when pressure is 80 normal atmosphere, the boron source solution in the sealing chamber is joined in the reactor, make it and the nitrogenous source generation boron nitride that reacts when the temperature of reactor is elevated to 350 ℃.
Reaction is at first fallen the solvent suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 180 ℃ of dryings in a vacuum, obtains the mixture nano microcrystalline of cBN and oBN.The HRTEM photo of sample is seen accompanying drawing 8.
Embodiment 36: operating process and method just change benzonitrile into pyrroles with embodiment 33.
Embodiment 37: operating process and method just change pyridine into pyrroles with embodiment 35.
Embodiment 38: in the pyrroles, add the 3A molecular sieve and leave standstill distillation after 22 hours, remove the water, the oxygen that wherein contain according to the consumption of 0.3 grams per milliliter.Then under nitrogen protection, diborane is added among 50 milliliters of pyrroles, stirs fast and obtain the solution that concentration is 0.4 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under nitrogen protection, the sodiumazide with stoichiometric ratio when stirring fast joins among the pyrroles, obtains the nitrogenous source suspension liquid.The nitrogenous source suspension liquid is transferred in the autoclave, added the pyrroles through the deoxygenation that dewaters again, making filling ratio is 60%.
The sealing chamber that boron source solution is housed packed into to fix in the reactor, gets rid of in the still with nitrogen and seals still behind the air.The temperature of control reactor is heated to 180 ℃ of reactions 48 hours with 0.5 ℃/minute speed.During this period,, when pressure is normal pressure, the boron source solution in the sealing chamber is joined in the reactor, make it and the nitrogenous source generation boron nitride that reacts when the temperature of reactor is elevated to 180 ℃.
Reaction is at first fallen pyrroles's suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 60 ℃ of dryings in a vacuum, obtains hBN nano microcrystalline sample.
Embodiment 39: in triethylamine, add calcium chloride and leave standstill distillation after 36 hours, remove the water, the oxygen that wherein contain according to the consumption of 0.2 grams per milliliter.Then under nitrogen protection, boron trichloride is added in 45 milliliters of triethylamines, stirs fast and obtain the solution that concentration is 3.6 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under nitrogen protection, the sodiumazide with stoichiometric ratio when stirring fast joins in the triethylamine, obtains the nitrogenous source suspension liquid.The nitrogenous source suspension liquid is transferred in the autoclave, added the triethylamine through the deoxygenation that dewaters again, making filling ratio is 40%.
The sealing chamber that boron source solution is housed packed into to fix in the reactor, gets rid of in the still with nitrogen and seals still behind the air.The temperature of control reactor is heated to 220 ℃ of reactions 36 hours with 0.5 ℃/minute speed.During this period,, when pressure is 6 normal atmosphere, the boron source solution in the sealing chamber is joined in the reactor, make it and the nitrogenous source generation boron nitride that reacts when the temperature of reactor is elevated to 220 ℃.
Reaction is at first fallen the triethylamine suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 60 ℃ of dryings in a vacuum, obtains the hBN nano microcrystalline.
Embodiment 40: all operations process and method are with embodiment 39, and difference is: the solvent triethylamine is replaced by quadrol, and the oxidized calcium of siccative calcium chloride replaces, and boron source boron trichloride has changed boron tribromide into, and the nitrogenous source sodiumazide has changed potassium azide into.
Embodiment 41: all operations process and method are with embodiment 39, and difference is: the solvent triethylamine is replaced by aniline.
Embodiment 42: all operations process and method are with embodiment 38, and difference is: solvent the pyrroles replaced by Ortho-Chloro aniline.
Embodiment 43: in methane amide, add activated alumina and leave standstill distillation after 32 hours, remove wherein water, oxygen according to the consumption of 0.3 grams per milliliter.Then under nitrogen protection, ammonium borate is joined in 45 milliliters of methane amides, stir fast and obtain the suspension liquid that concentration is 0.6 mol, it is standby in the sealing chamber that this suspension liquid is packed into; In addition, under nitrogen protection, the methyl hydrazine with stoichiometric ratio when stirring fast dissolves in the methane amide, obtains nitrogenous source solution.Nitrogenous source solution is transferred in the autoclave, added the methane amide through the deoxygenation that dewaters again, making filling ratio is 80%.
The sealing chamber that boron source suspension liquid is housed packed into to fix in the reactor, gets rid of in the still with nitrogen and seals still behind the air.The temperature of control reactor is elevated to 350 ℃ of reactions 72 hours with 2.0 ℃/minute speed.During this period,, when pressure is 48 normal atmosphere, the boron source suspension liquid in the sealing chamber is joined in the reactor, make it and the nitrogenous source reaction generates boron nitride when the temperature of reactor reaches 350 ℃.
Reaction is at first fallen the methane amide suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 140 ℃ of dryings in a vacuum, obtains hBN and oBN blended nano microcrystalline sample.
Embodiment 44: all operations process and method are with embodiment 43, and difference is: the solvent methane amide is by N, and dinethylformamide replaces.
Embodiment 45: in benzene, add Vanadium Pentoxide in FLAKES and leave standstill distillation after 24 hours, remove the water, the oxygen that wherein contain according to the consumption of 0.1 grams per milliliter.Then under the helium protection, boron trifluoride is added in 40 milliliters of benzene, stirs fast and obtain the solution that concentration is 1.6 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under the helium protection, the lithium nitride with stoichiometric ratio when stirring fast joins in the benzene, obtains the nitrogenous source suspension liquid.The nitrogenous source suspension liquid is transferred in the autoclave, added the benzene through the deoxygenation that dewaters again, making filling ratio is 90%.
The sealing chamber that boron source solution is housed packed into to fix in the reactor, gets rid of in the still with helium and seals still behind the air.The temperature of control reactor is heated to 480 ℃ of reactions 68 hours with 20 ℃/minute speed.During this period,, when pressure is 200 normal atmosphere, the boron source solution in the sealing chamber is joined in the reactor, make it and the nitrogenous source reaction generates boron nitride when the temperature of reactor is elevated to 480 ℃.
Reaction is at first fallen the benzene suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 150 ℃ of dryings in a vacuum, and obtaining with cBN is the BN crystallite of advantage thing phase.
Embodiment 46: all operations process and method are with embodiment 45, and difference is: the siccative Vanadium Pentoxide in FLAKES has changed lithium aluminum hydride into, and the nitrogenous source lithium nitride has changed quadrol into.
Embodiment 47: all operations process and method are with embodiment 45, and difference is: the siccative Vanadium Pentoxide in FLAKES has changed hydrolith into, and boron source boron trifluoride has changed POTASSIUM BOROHYDRIDE into.
Embodiment 48: all operations process and method are with embodiment 7, and difference is: solvent toluene is replaced by pyridine, and the nitrogenous source lithium nitride is by Zn (N
2H
4)
2Cl
2Replace.
Embodiment 49: all operations process and method are with embodiment 10, and difference is: solvent ethylbenzene is replaced by methane amide.
Embodiment 50: all operations process and method are with embodiment 12, and difference is: solvent xylene is replaced by pyridine, and the solvent chlorobenzene is replaced by aniline.
Embodiment 51: all operations process and method are with embodiment 27, and difference is: boron source tripropoxy-boron is replaced by ammonium borate, and diamine is replaced by methyl hydrazine.
Embodiment 52: in benzene, add sodium Metal 99.5 and leave standstill distillation after 24 hours, remove the water and the oxygen that wherein contain according to the consumption of 0.1 grams per milliliter.Then under argon shield, boron trichloride is added in 45 milliliters of benzene, stirs fast and obtain the solution that concentration is 0.6 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under argon shield, the lithium nitride with stoichiometric ratio when stirring fast joins in the benzene, obtains the nitrogenous source suspension liquid.The nitrogenous source suspension liquid is transferred in the autoclave, added the benzene through the deoxygenation that dewaters again, making filling ratio is 90%.
The sealing chamber that boron source solution is housed packed into to fix in the reactor, gets rid of in the still with argon gas and seals still behind the air.The temperature of control reactor is heated to 500 ℃ of reactions 210 hours with 0.5 ℃/minute speed.During this period,, when pressure is 320 normal atmosphere, open sealing chamber slightly, boron source solution is wherein joined in the reactor continuously, and generate boron nitride with the nitrogenous source deferred reaction when the temperature of reactor is elevated to 500 ℃.
Reaction is at first fallen the benzene suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 180 ℃ of dryings in a vacuum, obtains the cBN micro crystal material that granularity reaches tens of microns.
Embodiment 53: all operations process and method are with embodiment 52, different is: filling ratio is reduced to 60% by 90%, temperature of reaction is reduced to 300 ℃, and the nitrogenous source lithium nitride is replaced by sodiumazide, and (being spaced apart 10 hour between adjacent twice) divided in eight adding reactors in the boron source.The infrared absorption spectrum of the boron nitride sample that obtains is like this seen accompanying drawing 9, and its microscopic appearance is seen accompanying drawing 10.
Embodiment 54: in pyridine, add sodium oxide and leave standstill distillation after 20 hours, remove the water, the oxygen that wherein contain according to the consumption of 0.2 grams per milliliter.Then under nitrogen protection, diborane is added in 60 milliliters of pyridines, stirs fast and obtain the solution that concentration is 0.8 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under nitrogen protection, the Trimethylamine 99 with stoichiometric ratio when stirring fast is dissolved in the pyridine, obtains nitrogenous source solution.Nitrogenous source solution is transferred in the autoclave, added the pyridine through the deoxygenation that dewaters again, making filling ratio is 95%.
The sealing chamber that boron source solution is housed packed into to fix in the reactor, gets rid of in the still with nitrogen and seals still behind the air.The temperature of control reactor is heated to 600 ℃ of reactions 220 hours with 1.8 ℃/minute speed.During this period,, when pressure is 1600 normal atmosphere, open sealing chamber slightly, boron source solution is wherein joined in the reactor continuously, make it and the nitrogenous source deferred reaction generates boron nitride when the temperature of reactor is elevated to 600 ℃.
Reaction is at first fallen the pyridine suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 180 ℃ of dryings in a vacuum, obtains the cBN micro crystal material that granularity reaches tens of microns.
Embodiment 55: in pyridine and acetonitrile, add calcium chloride and leave standstill distillation after 48 hours, remove the water, the oxygen that wherein contain according to the consumption of 0.6 grams per milliliter.Then under argon shield, POTASSIUM BOROHYDRIDE is added in 60 milliliters of acetonitriles, stirs fast and obtain the solution that concentration is 0.1 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under argon shield, the methyl hydrazine with stoichiometric ratio when stirring fast is dissolved in the pyridine, obtains nitrogenous source solution.Nitrogenous source solution is transferred in the autoclave, added the pyridine through the deoxygenation that dewaters again, making filling ratio is 80%.
The sealing chamber that boron source solution is housed packed into to fix in the reactor, gets rid of in the still with argon gas and seals still behind the air.The temperature of control reactor is heated to 360 ℃ of reactions 280 hours with 0.6 ℃/minute speed.During this period,, when pressure is 60 normal atmosphere, open sealing chamber slightly, boron source solution is wherein joined in the reactor continuously, make it and the nitrogenous source deferred reaction generates boron nitride when the temperature of reactor is elevated to 360 ℃.
Reaction is at first fallen the solvent suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.Product is heated to 120 ℃ of dryings in a vacuum, obtains cBN and oBN mixed microcrystalline material that granularity reaches tens of microns.
Embodiment 56: in benzene and acetonitrile, add hydrolith and leave standstill distillation after 36 hours, remove the water oxygen that wherein contains according to the consumption of 0.15 grams per milliliter.Then under nitrogen protection, boron trifluoride is added in 60 milliliters of acetonitriles, add sodium borohydride (boron trifluoride: the sodium borohydride mol ratio is 3: 1) again when stirring fast and obtain the suspension liquid that concentration is 1.2 mol, it is standby in the sealing chamber that this suspension liquid is packed into; In addition, under nitrogen protection, when stirring fast the lithium nitride of stoichiometric ratio and the mixture of potassium azide (mol ratio 1: 4) are joined in the benzene, obtain the nitrogenous source suspension liquid.The nitrogenous source suspension liquid is transferred in the autoclave, added the benzene through the deoxygenation that dewaters again, making filling ratio is 90%.
The sealing chamber that boron source suspension liquid is housed packed into to fix in the reactor, gets rid of in the still with nitrogen and seals still behind the air.The temperature of control reactor is heated to 450 ℃ of reactions 240 hours with 1.2 ℃/minute speed.During this period,, when pressure is 180 normal atmosphere, open sealing chamber slightly, boron source suspension liquid is wherein joined in the reactor continuously, and generate boron nitride with the nitrogenous source deferred reaction when the temperature of reactor is elevated to 450 ℃.
Reaction is at first fallen the solvent suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 160 ℃ of dryings in a vacuum, obtains the granularity that cBN occupies absolute predominance and reaches tens of microns cBN and oBN mixed microcrystalline material.
Embodiment 57: operating process and method are with embodiment 52, and different is: the siccative sodium Metal 99.5 is replaced by magnesium sheet, and the nitrogenous source lithium nitride is replaced by Trimethylamine 99.
Embodiment 58: operating process and method are with embodiment 55, and different is: the acetonitrile as one of solvent is replaced by benzene, is replaced by urea as the methyl hydrazine of nitrogenous source.
Embodiment 59: operating process and method are with embodiment 56, and different is: the acetonitrile as one of solvent is replaced by aniline, replaced by ammonium borate as the sodium borohydride in one of boron source, simultaneously, as the potassium azide of one of nitrogenous source by Zn (N
2H
4)
2Cl
2Replace.
Embodiment 60: in acetonitrile, add potassium oxide and leave standstill distillation after 72 hours, remove the water and the oxygen that wherein contain according to the consumption of 0.08 grams per milliliter.Then under nitrogen protection, trimethyl borate is added in 45 milliliters of acetonitriles, stirs fast and obtain the solution that concentration is 0.2 mol, it is standby in the sealing chamber that this solution is packed into; In addition, under nitrogen protection, the methyl hydrazine with stoichiometric ratio when stirring fast is dissolved in the acetonitrile, then lithium nitride (methyl hydrazine: the lithium nitride mol ratio is 4: 2) powder is added wherein under the continuation stirring state again, obtains the nitrogenous source suspension liquid.The nitrogenous source suspension liquid is transferred in the autoclave, added the acetonitrile through the deoxygenation that dewaters again, making filling ratio is 95%.
The sealing chamber that boron source solution is housed packed into to fix in the reactor, gets rid of in the still with nitrogen and seals still behind the air.The temperature of control reactor is heated to 460 ℃ of reactions 250 hours with 1.0 ℃/minute speed.During this period,, when pressure is 580 normal atmosphere, open sealing chamber slightly, boron source solution is wherein joined in the reactor continuously, and generate boron nitride with the nitrogenous source deferred reaction when the temperature of reactor is elevated to 460 ℃.
Reaction is at first fallen the acetonitrile suction filtration after finishing, and uses deionized water suction filtration product again, is neutral up to filtrate.The product that obtains is heated to 160 ℃ of dryings in a vacuum, obtains the cBN micro crystal material that granularity reaches tens of microns.
Claims (6)
- What 1, be used to control boron nitride thing phase selects the phase in-situ synthetic method, comprises the steps that order is not limit:(1) pre-treatment of organic solventIn organic solvent, add siccative and leave standstill distillation after 10-72 hour according to the consumption of 0.01-1.0 grams per milliliter solvent, so that remove impurity such as the water that contains in desolvating, oxygen;(2) preparation of boron source liquidUnder protection of inert gas, the boron source to be dissolved in the above-mentioned organic solvent, concentration is 0.005～20 mol, obtains boron source solution or suspension liquid after stirring fast;(3) preparation of nitrogenous source liquidUnder protection of inert gas, nitrogenous source with stoichiometric ratio dissolves in the organic solvent while stirring, obtain the solution or the suspension liquid of nitrogenous source, used organic solvent can be same with the solvent phase in (2), also can be the another kind of organic solvent of handling through step (1);(4) dress stillIn the nitrogenous source liquid of preparing above or one of them immigration autoclave of boron source liquid, add organic solvent again through the deoxygenation that dewaters, making the filling ratio volume percent is 20～95%;(5) dress sealing chamberThe boron source liquid of the autoclave of preparing above of not packing into or nitrogenous source liquid, in the sealing chamber of packing into, sealing chamber is packed in the reactor, and is fixing, gets rid of air in the still with rare gas element, the envelope still; Sealing chamber integral body is positioned at reactor, and its on-off mechanism is positioned at outside the reactor, so that in reaction process, open or close sealing chamber as required, and reinforced in reactor;(6) reactionThe temperature of control reactor is heated to 120 ℃～600 ℃ reactions 10 hours～300 hours with 0.01 ℃/minute-60 ℃/minute speed.During this period, divide once, repeatedly or continuously boron source liquid in the sealing chamber or nitrogenous source liquid to be joined in the reactor, reaction generates boron nitride;(7) sample aftertreatmentAfter reaction finishes, earlier the solvent suction filtration is fallen, use deionized water suction filtration product again, be neutral up to filtrate; Above-mentioned product is heated to 60～200 ℃ of dryings in a vacuum, just can obtain even-grained BN crystallite.
- 2, as claimed in claim 1 be used to control boron nitride thing phase select the phase in-situ synthetic method, it is characterized in that the organic solvent that uses is chosen one or more from benzene, alkylbenzene, halogeno-benzene, alkane and haloalkane, nitrile, pyridine, pyrroles, liquefied ammonia, organic amine, amide solvent in step (1).
- 3, as claimed in claim 1 be used to control boron nitride thing phase select the phase in-situ synthetic method, it is characterized in that the siccative that uses is then chosen one or more from basic metal, alkalimetal oxide, alkaline-earth metal, alkaline earth metal halide, alkaline earth metal oxide, alkaline earth metal sulphate, molecular sieve, activated alumina, Vanadium Pentoxide in FLAKES, lithium aluminum hydride and hydrolith in step (1).
- 4, as claimed in claim 1 be used to control boron nitride thing phase select the phase in-situ synthetic method, it is characterized in that the rare gas element that uses is selected from nitrogen, helium, neon or argon gas in step (2).
- 5, as claimed in claim 1 be used to control boron nitride thing phase select the phase in-situ synthetic method, it is characterized in that one or more are chosen in the boron source of using from halogenation boron, borine, metal borohydride, metal boride, halogen borate, borate ester, ammonium borate in step (2).
- 6, as claimed in claim 1 be used to control boron nitride thing phase select the phase in-situ synthetic method, it is characterized in that the nitrogenous source that uses is chosen one or more from metal nitride, trinitride, ammonia, inorganic ammonium salt, three halogenated nitrogens, organic amine, hydrazine class and title complex thereof in step (3).
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Cited By (7)
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| CN100430313C (en) * | 2006-01-20 | 2008-11-05 | 山东大学 | Controllable hydrothermal constant pressure synthesis method for preparation of boron-carbon-nitrogen material |
| CN100430314C (en) * | 2006-01-04 | 2008-11-05 | 山东大学 | Boron-carbon-nitrogen material phase regulated dissolvent heat constant pressure synthesis method |
| 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 |
| CN106414311A (en) * | 2013-11-27 | 2017-02-15 | 北伊利诺斯大学董事会 | Boron nitride and method of producing boron nitride |
| CN106744736A (en) * | 2016-12-26 | 2017-05-31 | 湖北第二师范学院 | A kind of synthetic method of the active porous boron nitride nanosheet for water process |
| CN110116995A (en) * | 2018-02-06 | 2019-08-13 | 中国科学院深圳先进技术研究院 | The preparation method of boron nitride nanometer stick |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05310404A (en) * | 1992-05-07 | 1993-11-22 | Tokuyama Soda Co Ltd | Boron nitride precursor and production of boron nitride |
| FR2724645B1 (en) * | 1994-09-19 | 1997-01-24 | Centre Nat Rech Scient | PROCESS FOR OBTAINING CUBIC BN BY A SOLVOTHERMAL METHOD WITH THE USE OF HYDRAZINE AS A SOLVENT |
| CN1101337C (en) * | 2001-07-10 | 2003-02-12 | 山东大学 | Prepn. of nanometer boron nitride micro powder |
| CN1173879C (en) * | 2002-02-07 | 2004-11-03 | 山东大学 | Process for preparing nitride ultromicro powder and nitride crystal wunder hydrothermal condition |
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| CN100430314C (en) * | 2006-01-04 | 2008-11-05 | 山东大学 | Boron-carbon-nitrogen material phase regulated dissolvent heat constant pressure synthesis method |
| CN100430313C (en) * | 2006-01-20 | 2008-11-05 | 山东大学 | Controllable hydrothermal constant pressure synthesis method for preparation of boron-carbon-nitrogen material |
| 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 |
| CN106414311A (en) * | 2013-11-27 | 2017-02-15 | 北伊利诺斯大学董事会 | Boron nitride and method of producing boron nitride |
| US10236122B2 (en) | 2013-11-27 | 2019-03-19 | The Board Of Trustees Of Northern Illinois University | Boron nitride and method of producing boron nitride |
| US10892094B2 (en) | 2013-11-27 | 2021-01-12 | Board Of Trustees Of Northern Illinois University | Boron nitride and method of producing boron nitride |
| CN106744736A (en) * | 2016-12-26 | 2017-05-31 | 湖北第二师范学院 | A kind of synthetic method of the active porous boron nitride nanosheet for water process |
| CN110116995A (en) * | 2018-02-06 | 2019-08-13 | 中国科学院深圳先进技术研究院 | The preparation method of boron nitride nanometer stick |
| CN110116995B (en) * | 2018-02-06 | 2021-12-17 | 中国科学院深圳先进技术研究院 | Preparation method of boron nitride nanorod |
| CN111204720A (en) * | 2020-02-10 | 2020-05-29 | 浙江硼矩新材料科技有限公司 | Batch preparation method of boron nitride nanotubes |
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| CN1329290C (en) | 2007-08-01 |
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