CN1803597A - Boron-carbon-nitrogen material phase regulated dissolvent heat constant pressure synthesis method - Google Patents
Boron-carbon-nitrogen material phase regulated dissolvent heat constant pressure synthesis method Download PDFInfo
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Abstract
The solvent thermal constant-pressure synthesis method to adjust and control phase of boron carbonitride material comprises: preparing liquids for boron resource, carbon source and nitrogen source respectively; putting into the kettle; forcing 40~2000MPa constant pressure then heating the kettle to 220~1000Deg with 0.01~60Deg/min speed; after reaction, cooling to room temperature, and taking post-treatment to the product. Wherein, it can adjust and control the system temperature and pressure independently as well as the reaction speed and direction, and obtains large-size diamond, cubic boron nitride and carbonitride crystal block.
Description
One, technical field
The present invention relates to a kind of solvent thermal constant-pressure synthesis method of regulating and control boron-carbon-nitrogen material thing phase, belong to the new chemical materials field.
Two, background technology
Cubic boron nitride, diamond, carbonitride (being referred to as boron carbon nitrogen) are as the superhard material of excellent performance, in daily life and industrial production and be about to play a part very important, realize the synthetic of these materials, particularly low-cost in enormous quantities synthetic, be that the mankind dream of always.In order to realize this ideal, people's development has also improved various preparation methods, and wherein high temperature and high pressure method is the most ripe.Up to the present, utilize this method, realized cubic boron nitride and adamantine industrialization.But, this method of analysis-by-synthesis is not difficult to find out, preparation process still needs to use (for example 1200～2000 ℃ of extreme conditions, 3～200,000 normal atmosphere), thereby very harsh requirement has been proposed equipment, this directly causes input-output ratio to increase substantially, and product price is high, has seriously limited the range of application of these materials.In addition, utilize the diamond and the cubic boron nitride defective of high temperature and high pressure method preparation more, the crystallite size variable range is narrow, and the body piece crystal that can't grow big in this way.
For preparation diamond and cubic boron nitride under the condition of gentleness, people have been developed a series of new synthetic methods, and wherein softening synthetic method is development in recent years one of method faster.For example, Chinese University of Science and Technology utilizes the catalytic reduction pyrolytic reaction method in the airtight autoclave to prepare the diamond with larger particles degree, and Shandong University then utilizes solvent process for thermosynthesizing to prepare the very high nm-class boron nitride of cube phase content.Yet, all there is limitation separately in these methods: for example, except control reaction temperature, we may regulate and control other influence factor in the reactor hardly, also just be difficult to the rapid Optimum preparation condition, realize the low-cost in enormous quantities synthetic of these two kinds of materials.In light of this situation, we have developed again and have selected the phase in-situ synthetic method, realized controlling artificially as required the beginning and the termination of reaction process, and can regulate and control speed of response in quite on a large scale.Utilize the thing phase purity and the crystalline quality of the boron nitride nanometer material of this method preparation all to be significantly improved.But in selecting the phase in-situ synthetic method, solvent thermal reaction carries out in airtight high pressure vessel, in case the composition of reaction raw materials and consumption are determined, under specific filling ratio, the temperature and pressure of reaction system is interrelated by certain mode, can't independently regulate and control, particularly the chemical reaction that takes place in the temperature-fall period in the temperature-rise period at restive initial stage and later stage; Therefore, the accurate regulation and control to building-up process still are subjected to more restriction.
We find in depth to analyze existing method by system: for the chemical reaction that relates in the material preparation process, although each reaction all has certain threshold temperature or pressure, but because the residing energy state difference of reactant molecule reacts even also have small number of molecules when being lower than this threshold condition.For the material system of those heterogeneous coexistences, the thing that generates under lower pressure condition mainly is thermodynamically stable phase mutually, for example hexagonal boron nitride, graphite and graphite mould carbonitride.In case these stable things generate mutually and settle out, make them be transformed into cubic structure (as cubic boron nitride, diamond or cube carbonitride) and will become very difficult.In addition, when reaction process was finished and begin to lower the temperature, thing also might take place and reverse mutually in original cubic structure thing that generates mutually, made that multiple thing coexists mutually in the product, and the selectivity of grievous injury reaction process has also reduced the using value of product.
Three, summary of the invention
The present invention is directed to the shortcoming that existing boron-carbon-nitrogen material synthetic method exists, a kind of solvent thermal constant-pressure synthesis method of regulating and control boron-carbon-nitrogen material thing phase has been proposed, can regulate and control the temperature and pressure of reaction system on the one hand relatively independently, make the reaction process controllability of synthetic boron carboritride stronger, thereby can control mutually the thing of final product better.Can make the controlled range of temperature of reaction and pressure bigger on the other hand, the material category that this method is suitable for is more.Moreover, to pressure-sensitive reaction, utilize this method can control speed and direction that reaction is carried out for those, thereby improve the granularity and the crystalline quality of synthetic materials.
The solvent thermal constant-pressure synthesis method of regulation and control boron-carbon-nitrogen material thing phase of the present invention may further comprise the steps, and wherein the preparation steps of boron source liquid, carbon source liquid and nitrogenous source liquid is in no particular order:
1. the preparation of boron source liquid or carbon source liquid
In shielding gas, boron source or carbon source to be dissolved in the organic solvent of removing water and oxygen, concentration is 0.005～18 mol, obtains the solution or the suspension liquid of boron source or carbon source after stirring fast.
2. the preparation of nitrogenous source liquid
In shielding gas, the nitrogenous source with stoichiometric ratio dissolves in the organic solvent while stirring, obtains the solution or the suspension liquid of nitrogenous source.
3. dress still
(1) during diamond synthesis, only above-mentioned carbon source solution or suspension liquid are joined in the autoclave, then add the reductive agent of stoichiometric ratio again.Use shielding gas packaged autoclave behind the bubbling in solution then.
When (2) synthesizing boron nitride, above-mentioned boron source liquid and nitrogenous source liquid are mixed by stoichiometric ratio, in the autoclave of packing into after stirring.With shielding gas in mixing solutions bubbling to get rid of air wherein, packaged autoclave then.
When (3) synthesizing carbonitride, above-mentioned carbon source liquid and nitrogenous source liquid are mixed by stoichiometric ratio, in the autoclave of packing into after stirring.With shielding gas in mixing solutions bubbling to get rid of air wherein, packaged autoclave then.
4. reaction
To before the autoclave heating, at first apply the pressure of a 40～2000MPa to it, the temperature of then controlling autoclave is heated to 220～1000 ℃ with 0.01～60 ℃/minute speed, and constant temperature and pressure reaction 8～480 hours naturally cools to room temperature then.
5. product aftertreatment
Reaction is at first fallen the solvent suction filtration after finishing, and successively with acetone, ethanol, dilute hydrochloric acid washing, to remove organic by-products and other impurity in the product, uses deionized water repetitive scrubbing product more then, is neutral up to filtrate; Above-mentioned product is heated to 60～200 ℃ of dryings in a vacuum, just can obtain even-grained boron-carbon-nitrogen material.
According to the autoclave temperature with exerted pressure different, the boron-carbon-nitrogen material that obtains can be hexagonal boron nitride, quadrature boron nitride, cubic boron nitride, graphite, lonsdaleite, diamond, graphite mould carbonitride, class cube carbonitride, cube carbonitride and six side's carbonitrides etc.Along with the raising of autoclave temperature and pressure, the content with boron carboritride of cubic structure constantly increases.For the reaction that has gas to participate in, all right controls reaction speed of the pressure of regulation and control autoclave, thereby the granularity and the crystalline quality of control gained material.
Organic solvent used in the above-mentioned steps 1 and 2 can be identical, also can be different.
The pre-treatment of organic solvent is as follows:
In organic solvent, add siccative and leave standstill distillation after 10～72 hours 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 and oxygen.
Above-mentioned organic solvent is selected from one or more in benzene, alkylbenzene, halogeno-benzene, alkane and haloalkane, nitrile, pyridine, pyrroles, liquefied ammonia, organic amine, amides, tetraline, naphthane, dimethyl sulfoxide (DMSO) (DMSO), dithiocarbonic anhydride, tetrahydrofuran (THF) (DHF), hexahydropyridine, aminopyridine, hydrazine class and the ion liquid solvent.
Above-mentioned siccative is selected from one or more in basic metal, alkalimetal oxide, alkalimetal hydride, alkali metal hydroxide, alkali metal sulfates, alkaline-earth metal, alkaline earth metal hydride, alkaline earth metal halide, alkaline earth metal oxide, alkaline earth metal sulphate, molecular sieve, activated alumina, Vanadium Pentoxide in FLAKES, lithium aluminum hydride, paraffin sheet, soda-lime, metal bromide, salt of wormwood and the silica gel.
Employed shielding gas is selected from nitrogen, helium, neon or argon gas in the inventive method.
One or more are chosen in the boron source of using in above-mentioned steps 1 from halogenation boron, borine, alkali metal borohydride, metal boride, boric acid, borate, halogen borate, boric acid ester compound, ammonium borate.Carbon source is chosen one or more from sulfide, carbon oxides, carbonate, halo piperazine and the organic amine of the halogenide of carbon, haloalkane, carbon.
The nitrogenous source that uses in above-mentioned steps 2 is chosen one or more from metal nitride, trinitride, ammonia and ammonium salt, three halogenated nitrogens, organic amine, sodium amide, amino ester, hydrazine class or hydrazine class title complex.
The reductive agent that uses in above-mentioned steps 3 (1) is chosen one or more from basic metal, alkaline-earth metal, basic metal phosphide, basic metal aminocompound, alkalimetal hydride, metal borohydride.
In above-mentioned steps 4, when the temperature of autoclave so that 20～60 ℃ of fast speeds/when min was elevated to preset value, the sample that obtains was the very little boron carbon nitrogen nanocrystal of granularity; Otherwise, when the temperature of autoclave being elevated to preset value, just can in the solvent thermal environment, obtaining granularity and reach micron order or the boron carbon nitrogen crystalline material more than the micron order with 0.01～10 ℃/min of slower speed.
Method of the present invention is a kind of solvent thermal constant-pressure synthesis method of regulating and control boron-carbon-nitrogen material thing phase, compare with existing method, significant improvement of the present invention is as follows: can relatively independently regulate and control respectively the temperature and pressure of reaction system on the one hand, and can control those speed and directions as required to pressure-sensitive solvent thermal reaction process, realized that the selectivity of superhard material is synthetic.On the other hand, utilize method of the present invention can also prevent that the thing that occurs in the temperature-fall period after reaction is finished from reversing phenomenon mutually.Compare with the in-situ synthetic method that selects mutually of front, this method can make the reaction process of synthetic boron carbon nitrogen carry out under higher temperature and pressure, this for more effectively control the product thing mutually and crystalline quality and the range of application of expanding this method be very favourable.This method has above-mentioned advantage just, and it is mutually identical with the product thing that generates more than the threshold temperature to utilize it can make at the product thing that generates below the threshold temperature, thereby has guaranteed the high thing phase purity of product.The 3rd, can make the reaction process controllability stronger, and be easy to amplify preparative-scale, realize low-cost in enormous quantities synthesize of boron-carbon-nitrogen material under relative mild conditions, therefore have important practical significance; In addition, this method is again to combine the relevant theoretical back development of chemical reaction thermodynamics, kinetics, high-pressure physics and inorganic a plurality of subjects such as synthetic and come, and it also has very high using value to the fundamental research of related discipline.
Method of the present invention is not only applicable to the synthetic of boron-carbon-nitrogen material, and be applicable to the controlledly synthesis of other 26S Proteasome Structure and Function materials, especially synthesize some selectively and have the thing phase time of special property from the system of those heterogeneous coexistences, this method has unique advantages especially.
Utilize method of the present invention, we have successfully controlled the thing phase and the crystallisation process of materials such as boron nitride, carbonitride, the boron-carbon-nitrogen material that has obtained having the higher crystalline quality; Simultaneously, this method is adjusting solvent thermal response speed significantly, prepares the super hard nano material according to actual needs or grow larger sized boron carbon nitrogen crystalline material.These superhard materials all have important application in precision optical machinery processing, national defense industry, oil drilling and exploitation and our daily life.
The invention will be further elaborated below in conjunction with description of drawings and embodiment.
Four, description of drawings
The infrared absorpting light spectra of the carbonitride of preparation is positioned at 1345cm among Fig. 1 embodiment 1 among the figure
-1The absorption peak ownership at place is C-N key, 1555cm
-1Ownership is C=N key, 2142cm
-1Ownership is C ≡ N key.
X-ray diffraction (XRD) spectrogram of the carbonitride of preparation among Fig. 2 embodiment 9, what indicate " * " among the figure is the graphite mould carbonitride, what indicate " " is β type carbonitride.
The TEM microscopic appearance figure of the carbonitride of preparation among Fig. 3 embodiment 10, (a) is the light field shape appearance figure among the figure, (b) is the details in a play not acted out on stage, but told through dialogues shape appearance figure.
The selected area electron diffraction figure of the carbonitride of preparation among Fig. 4 embodiment 10, diffraction ring can belong to class cube carbonitride among the figure, and the crystal indices are followed successively by (111), (200), (211), (310).
The TEM microscopic appearance figure of the carbonitride of preparation among Fig. 5 embodiment 16
The selected area electron diffraction figure of the carbonitride of preparation among Fig. 6 embodiment 16, diffraction ring is that electron beam obtains along graphite mould carbonitride [112] zone axis incident among the figure.
Five, embodiment
Embodiment 1: at first add the sodium Metal 99.5 sheet in benzene, leave standstill distillation after 24 hours, remove wherein water and oxygen.Under nitrogen protection, take by weighing the sodiumazide (NaN of stoichiometric ratio then
3) and three chloro piperazine (C
3N
3Cl
3) put into autoclave, add 8ml again and seal through behind the benzene of drying treatment.Apply the pressure of 40MPa on autoclave, the temperature of controlling autoclave again is elevated to 220 ℃ with 0.01 ℃/minute speed, and the constant temperature and pressure reaction naturally cooled to room temperature after 8 hours.
Reaction is at first fallen the benzene suction filtration after finishing, and uses acetone, ethanol, dilute hydrochloric acid washed product then successively, removes wherein organic by-products and other impurity, uses deionized water repetitive scrubbing product again, is neutral up to filtrate.Heat product to 60 in a vacuum and ℃ carry out drying, just can obtain graphite mould carbonitride (g-C
3N
4), its infrared absorption spectrum is seen accompanying drawing 1.
Embodiment 2: as described in embodiment 1, different is that temperature of reaction is brought up to 260 ℃.
Embodiment 3: as described in embodiment 1, the temperature of reaction of autoclave that different is is brought up to 300 ℃, and three chloro piperazines substitute with Trimethylamine 99, and sodiumazide substitutes with nitrogen trichloride.
Embodiment 4: as described in embodiment 1, different is that pressure is brought up to 80MPa.
Embodiment 5: as described in embodiment 1, different is that pressure is brought up to 120MPa.
Embodiment 6: as described in embodiment 1, different is that reaction pressure is brought up to 80MPa, and temperature is brought up to 260 ℃, and the reaction times is increased to 12 hours.
Embodiment 7: as described in embodiment 1, different is that reaction pressure is brought up to 80MPa, and temperature is brought up to 300 ℃, and the reaction times is increased to 24 hours.
Embodiment 8: as described in embodiment 1, different is that reaction pressure is brought up to 120MPa, and temperature is brought up to 260 ℃, and the reaction times is increased to 36 hours.
Embodiment 9: as described in embodiment 1, different is that reaction pressure is brought up to 120MPa, and temperature is brought up to 300 ℃, and the reaction times is increased to 48 hours.The X-ray diffraction of gained sample (XRD) spectrogram is seen accompanying drawing 2.
Embodiment 10: as described in embodiment 1, different is that benzene is changed into N, dinethylformamide (DMF), and siccative sodium sheet changes potassium hydroxide into.The microscopic appearance of gained sample and polycrystalline diffractogram are seen accompanying drawing 3,4.
Embodiment 11: as described in embodiment 1, different is to substitute sodiumazide (NaN with sodium Metal 99.5
3), three chloro piperazines substitute with Monomethylamine.
Embodiment 12: as described in embodiment 1, different is to substitute sodiumazide (NaN with potassium metal
3).
Embodiment 13: as described in embodiment 1, different is that benzene is changed into hexahydropyridine.
Embodiment 14: as described in embodiment 1, different is that benzene is changed into liquefied ammonia, and dry sodium tablet changes calcium hydroxide into.
Embodiment 15: as described in embodiment 1, different is that benzene is changed into dimethyl sulfoxide (DMSO) (DMSO), and siccative sodium sheet changes hydrolith into.
Embodiment 16: at first add potassium metal in benzene, leave standstill distillation after 48 hours, remove wherein water and oxygen.Under the helium protection, take by weighing the sodiumazide (NaN of stoichiometric ratio
3) and carbon tetrabromide (CBr
4) put into autoclave, make sodiumazide (NaN
3) content in benzole soln is 6 mol, add 8ml again and seal through behind the benzene of drying treatment.Apply the pressure of 160MPa on autoclave, the temperature of controlling autoclave again is raised to 300 ℃ with 0.5 ℃/minute speed, and the constant temperature and pressure reaction naturally cooled to room temperature after 16 hours.
After reaction finishes, at first the benzene suction filtration is fallen, remove organic by-products and other impurity in the product with acetone, ethanol, dilute hydrochloric acid successively then, use deionized water repetitive scrubbing product at last, be neutrality up to filtrate.Heat product to 80 in a vacuum and ℃ carry out drying, the graphite mould carbonitride (g-C that obtains
3N
4) microscopic appearance figure and selected area electron diffraction figure see accompanying drawing 5,6.
Embodiment 17: as described in embodiment 16, different is that siccative potassium substitutes sodiumazide (NaN with metallic lithium
3) substitute with sodium amide, and to make its content in benzene be 8 mol.
Embodiment 18: as described in embodiment 16, different is that benzene substitutes with toluene, and siccative potassium substitutes with sodium oxide, and the shielding gas helium substitutes with neon.
Embodiment 19: as described in embodiment 16, different is that benzene substitutes with Skellysolve A, and siccative potassium substitutes with calcium chloride, and carbon tetrabromide substitutes with quadrol, and sodiumazide substitutes with the mixture (mol ratio 3: 1) of sodiumazide and nitrogen trichloride.
Embodiment 20: as described in embodiment 16, different is that benzene substitutes with pyridine, and siccative potassium substitutes sodiumazide (NaN with 4A type molecular sieve
3) usefulness potassium azide (KN
3) substitute, and to make its content in benzene be 10 mol.
Embodiment 21: as described in embodiment 16, different is that benzene substitutes with acetonitrile, and siccative potassium substitutes with activated alumina, sodiumazide (NaN
3) usefulness lithium nitride (Li
3N) substitute, and to make its content in benzene be 12 mol.
Embodiment 22: as described in embodiment 16, different is that benzene substitutes with Pyrrolidine, and siccative potassium substitutes sodiumazide (NaN with 3A type molecular sieve
3) usefulness lithium nitride (Li
3N) and ammonium chloride (NH
4Cl) mixture (mol ratio 3: 1) substitutes, and to make the concentration of its benzole soln be 14 mol.
Embodiment 23: as described in embodiment 16, different is that pressure is brought up to 180MPa, and temperature is brought up to 350 ℃, and the reaction times is increased to 20 hours.
Embodiment 24: as described in embodiment 16, different is to be warmed up to 220 ℃ earlier, adds the pressure of 200MPa then to reaction system.
Embodiment 25: as described in embodiment 16, different is adds the pressure of 60MPa earlier to reaction system, be warmed up to 220 ℃ then after, pressure is brought up to 300MPa, continues the constant temperature and pressure reaction.
Embodiment 26: at first add calcium sulfate and vitriolate of tartar in benzene, leave standstill distillation after 72 hours, remove wherein water and oxygen.In tetracol phenixin, add strontium oxide, leave standstill and carried out drying in 10 hours; Under argon shield, take by weighing the sodium amide (NaNH of stoichiometric ratio
2) put into autoclave, prepare the benzole soln of the tetracol phenixin of 16 mol then, and seal after getting this solution 8ml immigration autoclave.Apply the pressure of 1800MPa on autoclave, control reaction temperature is elevated to 800 ℃ with 1 ℃/minute speed again, and the constant temperature and pressure reaction naturally cooled to room temperature after 24 hours.
After reaction finishes, at first the benzene suction filtration is fallen, remove organic by-products and other impurity in the product with acetone, ethanol, dilute hydrochloric acid successively then, use deionized water repetitive scrubbing product again, be neutrality up to filtrate.Heat product to 100 in a vacuum and ℃ carry out drying, just can obtain the nanocrystalline of cube carbonitride.
Embodiment 27: as described in embodiment 26, different is that benzene substitutes with aniline, and siccative calcium sulfate and vitriolate of tartar substitute with the paraffin sheet, sodium amide (NaNH
2) usefulness ammonium chloride (NH
4Cl) substitute.
Embodiment 28: as described in embodiment 26, that different is sodium amide (NaNH
2) usefulness potassium azide (KN
3) substitute.
Embodiment 29: as described in embodiment 26, that different is sodium amide (NaNH
2) usefulness sodiumazide (NaN
3) substitute.
Embodiment 30: as described in embodiment 26, different is, and the carbon source tetracol phenixin substitutes with dithiocarbonic anhydride, and to make the concentration of its benzole soln be 18 mol, and siccative calcium sulfate and vitriolate of tartar substitute with magnesium chloride.
Embodiment 31: as described in embodiment 26, different is, and the carbon source tetracol phenixin substitutes with methylene dichloride, and to make the concentration of its benzole soln be 20 mol, and siccative calcium sulfate and vitriolate of tartar substitute with potassium hydroxide.
Embodiment 32: as described in embodiment 26, different is that the carbon source tetracol phenixin substitutes with trichloromethane.
Embodiment 33: as described in embodiment 26, different is that benzene substitutes with bromobenzene, siccative calcium sulfate, vitriolate of tartar and the strontium oxide mixture replacing of calcium tablet and magnesium sheet.
Embodiment 34: at first add the paraffin sheet in the pyrroles, leave standstill distillation after 40 hours, remove wherein water and oxygen.Under the neon protection, the sodium Metal 99.5, carbon tetrabromide and the ammonium chloride that take by weighing stoichiometric ratio are put into autoclave, add 8ml and seal through behind the pyrroles of drying treatment.Apply the pressure of 300MPa on autoclave, the temperature of controlling autoclave again is elevated to 500 ℃ with 1.5 ℃/minute speed, and the constant temperature and pressure reaction naturally cooled to room temperature after 30 hours.
After reaction finishes, at first pyrroles's suction filtration is fallen, remove organic by-products and other impurity in the product with acetone, ethanol, dilute hydrochloric acid successively then, use deionized water repetitive scrubbing product again, be neutrality up to filtrate.Heat product to 120 in a vacuum and ℃ carry out drying, just can obtain NANO CRYSTALLINE CARBON NITRIDES.
Embodiment 35: as described in embodiment 34, different is that the solvent pyrroles substitutes with ethylbenzene, and siccative paraffin sheet substitutes with sodium sheet and calcium oxide.
Embodiment 36: as described in embodiment 34, different is that the carbon source carbon tetrabromide substitutes with dithiocarbonic anhydride, and siccative paraffin sheet substitutes with soda-lime.
Embodiment 37: as described in embodiment 34, different is that the carbon source carbon tetrabromide substitutes with tetracol phenixin, and nitrogenous source ammonium chloride substitutes with lithium nitride and bicarbonate mixture (mol ratio 3: 1).
Embodiment 38: as described in embodiment 34, different is that sodium Metal 99.5 substitutes with potassium metal, and the carbon source carbon tetrabromide substitutes with tetracol phenixin, and nitrogenous source ammonium chloride substitutes with potassium azide.
Embodiment 39: as described in embodiment 34, different is that the carbon source carbon tetrabromide substitutes with methylene dichloride, and nitrogenous source ammonium chloride substitutes with ammonium nitrate and urea admixture (mol ratio 1: 3).
Embodiment 40: as described in embodiment 34, different is that solvent benzol substitutes with methyl hydrazine, and the carbon source carbon tetrabromide substitutes with trichloromethane.
Embodiment 41: at first add Vanadium Pentoxide in FLAKES in benzene, leave standstill distillation after 18 hours, remove wherein water and oxygen.Under the helium protection, boron trichloride is added to 10 milliliters through in the benzene of drying treatment, obtain the solution that concentration is 0.005 mol.Feed Trimethylamine 99 then, form white floss, this precipitation is put into autoclave, add 8ml and seal through behind the benzene of drying treatment.Apply the pressure of 400MPa on autoclave, the temperature of controlling autoclave again is elevated to 260 ℃ with 0.01 ℃/minute speed, and the constant voltage reaction naturally cooled to room temperature after 48 hours.
After reaction finishes, at first the benzene suction filtration is fallen, remove organic by-products and other impurity in the product with acetone, ethanol, dilute hydrochloric acid successively then, use deionized water repetitive scrubbing product again, be neutrality up to filtrate.Heat product to 140 in a vacuum and ℃ carry out drying, it is nanocrystalline just can to obtain cubic boron nitride.
Embodiment 42: as described in embodiment 41, the concentration of different is boron trichloride benzole soln increases to 0.05 mol, and temperature of reaction is brought up to 300 ℃.
Embodiment 43: as described in embodiment 41, the concentration of different is boron trichloride benzole soln increases to 0.5 mol, and pressure is brought up to 600MPa.
Embodiment 44: as described in embodiment 41, the concentration of different is boron trichloride benzole soln increases to 2 mol, and benzene substitutes with chlorobenzene, and the siccative Vanadium Pentoxide in FLAKES substitutes with the metal magnesium sheet, and pressure is brought up to 1000MPa.
Embodiment 45: as described in embodiment 41, the concentration of different is boron trichloride benzole soln increases to 4 mol, and benzene substitutes with triethylamine, and the siccative Vanadium Pentoxide in FLAKES substitutes with hydrolith.
Embodiment 46: as described in embodiment 41, that different is nitrogenous source Trimethylamine 99 sodiumazide (NaN
3) and the mixture (mol ratio 1: 1) of Trimethylamine 99 substitute.
Embodiment 47: as described in embodiment 41, that different is nitrogenous source Trimethylamine 99 azide magnesium (Mg (N
3)
2) and the mixture (mol ratio 1: 2) of Trimethylamine 99 substitute.
Embodiment 48: as described in embodiment 41, different is that benzene substitutes with Skellysolve A, and the siccative Vanadium Pentoxide in FLAKES substitutes with KOH, and temperature of reaction is brought up to 320 ℃, nitrogenous source Trimethylamine 99 lithium nitride (Li
3N) and the mixture of Trimethylamine 99 (mol ratio 2: 1) substitute.
Embodiment 49: as described in embodiment 41, different is that benzene substitutes with hexachloroethane, and the siccative Vanadium Pentoxide in FLAKES substitutes with sal epsom, and boron source boron trichloride substitutes with boron tribromide, and the nitrogenous source Trimethylamine 99 substitutes with the mixture (mol ratio 1: 2) of urea and ammonium chloride.
Embodiment 50: as described in embodiment 41, different is that the siccative Vanadium Pentoxide in FLAKES substitutes with lithium aluminum hydride, and boron source boron trichloride substitutes with boron trifluoride, and the nitrogenous source Trimethylamine 99 substitutes with hydrazine.
Embodiment 51: as described in embodiment 41, different is that benzene substitutes with dimethylbenzene.
Embodiment 52: as described in embodiment 41, different is that benzene substitutes with methane amide.
Embodiment 53: as described in embodiment 41, different is that benzene substitutes with ionic liquid.
Embodiment 54: at first add sodium hydroxide at tetrahydrofuran (THF), leave standstill distillation after 20 hours, remove wherein water and oxygen.Under argon shield, take by weighing the sodiumazide (NaN of stoichiometric ratio
3) and Sodium tetrafluoroborate put into autoclave, add 8ml again through sealing behind the tetrahydrofuran (THF) of drying treatment.Apply the pressure of 1500MPa on autoclave, the temperature of controlling autoclave again is elevated to 350 ℃ with 6 ℃/minute speed, and the constant temperature and pressure reaction naturally cooled to room temperature after 96 hours.
After reaction finishes, at first the tetrahydrofuran (THF) suction filtration is fallen, remove organic by-products and other impurity in the product with acetone, ethanol, dilute hydrochloric acid successively then, use deionized water repetitive scrubbing product again, be neutrality up to filtrate.The product that obtains is heated to 160 ℃ in a vacuum and carries out drying, and it is nanocrystalline just can to obtain cubic boron nitride.
Embodiment 55: as described in embodiment 54, different is that the shielding gas argon gas substitutes with nitrogen, and pressure is brought up to 600MPa, and temperature is brought up to 400 ℃, and the reaction times is increased to 144 hours, and heat-up rate is increased to 12 ℃/minute.
Embodiment 56: as described in embodiment 54, different is that boron source Sodium tetrafluoroborate substitutes with pentaborane and magnesium diboride mixture (mol ratio 2: 1).
Embodiment 57: as described in embodiment 54, different is that boron source Sodium tetrafluoroborate substitutes with boric acid, and the nitrogenous source sodiumazide substitutes with hydrazine.
Embodiment 58: as described in embodiment 54, different is that boron source Sodium tetrafluoroborate substitutes with ammonium borate and sodium borohydride mixture (mol ratio 4: 1).
Embodiment 59: as described in embodiment 54, different is that boron source Sodium tetrafluoroborate substitutes with trimethyl borate, and the nitrogenous source sodiumazide substitutes with nitrogen trichloride.
Embodiment 60: as described in embodiment 54, different is that solvents tetrahydrofurane substitutes with aminopyridine, and the nitrogenous source sodiumazide substitutes with Monomethylamine.
Embodiment 61: at first add hydrolith in benzene, add salt of wormwood and leave standstill distillation after 60 hours in tetracol phenixin, remove wherein water and oxygen.Under the helium protection, boron trichloride is added in the benzene of 10 milliliters of above-mentioned processing.Feed Trimethylamine 99 then, form white floss, this floss is put into autoclave, add sodiumazide (NaN according to excessive one times amount
3) and 8ml through sealing behind the tetracol phenixin of drying treatment.Apply the pressure of 1200MPa on autoclave, the temperature of controlling autoclave again is elevated to 380 ℃ with 24 ℃/minute speed, and the constant temperature and pressure reaction naturally cooled to room temperature after 240 hours.
After reaction finishes, at first the tetracol phenixin suction filtration is fallen, remove organic by-products and other impurity in the product with acetone, ethanol, dilute hydrochloric acid successively then, use deionized water repetitive scrubbing product again, be neutrality up to filtrate.The product that obtains is heated to 180 ℃ in a vacuum and carries out drying, and it is nanocrystalline just can to obtain cube boron carbon nitrogen.
Embodiment 62: as described in embodiment 61, that different is nitrogenous source Trimethylamine 99 and sodiumazide ammonium chloride (NH
4Cl) and Zn (N
2H
4)
2Cl
2Mixture (mol ratio 1: 3) substitutes.
Embodiment 63: as described in embodiment 61, different is that solvent benzol substitutes with the benzene nitrile, and nitrogenous source Trimethylamine 99 and sodiumazide substitute with sodium amide and liquefied ammonia mixture (mol ratio 1: 1).
Embodiment 64: as described in embodiment 61, different is that boron source boron trichloride substitutes with boron tribromide, and nitrogenous source Trimethylamine 99 and sodiumazide substitute with phenylhydrazine.
Embodiment 65: as described in embodiment 61, different is that solvent benzol substitutes with benzonitrile, and nitrogenous source Trimethylamine 99 and sodiumazide substitute with hydrazine hydrochloride.
Embodiment 66: as described in embodiment 61, different is that boron source boron trichloride substitutes with boron trifluoride, nitrogenous source Trimethylamine 99 and sodiumazide urea and lithium nitride (Li
3N) mixture (mol ratio 1: 4) substitutes.
Embodiment 67: at first add sodium oxide and potassium oxide in aniline, leave standstill distillation after 36 hours, remove wherein water and oxygen.Under the neon protection, boron trichloride is added to 10 milliliters through in the aniline of drying treatment, add the acetonitrile of stoichiometric ratio then, will seal after this mixing solutions immigration autoclave.Apply the pressure of 2000MPa on autoclave, the temperature of controlling autoclave again is elevated to 400 ℃ with 30 ℃/minute speed, and the constant temperature and pressure reaction naturally cooled to room temperature after 288 hours.
After reaction finishes, at first the aniline suction filtration is fallen, remove organic by-products and other impurity in the product with acetone, ethanol, dilute hydrochloric acid successively then, use deionized water repetitive scrubbing product again, be neutrality up to filtrate.Heat product to 200 in a vacuum and ℃ carry out drying, it is nanocrystalline just can to obtain pure cube of boron carbon nitrogen.
Embodiment 68: as described in embodiment 67, different is that solvent aniline substitutes with tetraline, and acetonitrile is with 1, and the 3-dicyanobenzenes substitutes, and siccative hydrolith and salt of wormwood substitute with Calcium Bromide.
Embodiment 69: as described in embodiment 67, different is that solvent aniline substitutes with naphthane, and acetonitrile substitutes with propionitrile, and siccative hydrolith and salt of wormwood substitute with zinc bromide.
Embodiment 70: at first add calcium oxide and leave standstill distillation after 48 hours in dithiocarbonic anhydride, remove wherein water and oxygen.Under argon shield, the boric acid and the hydrazine that take by weighing stoichiometric ratio are put into autoclave, add 8ml again and seal through behind the dithiocarbonic anhydride of drying treatment.Apply the pressure of 800MPa on autoclave, the temperature of controlling autoclave again is elevated to 400 ℃ with 18 ℃/minute speed, and the constant temperature and pressure reaction naturally cooled to room temperature after 192 hours.
After reaction finishes, at first the dithiocarbonic anhydride suction filtration is fallen, remove organic by-products and other impurity in the product with acetone, ethanol, dilute hydrochloric acid successively then, use deionized water repetitive scrubbing product again, be neutrality up to filtrate.Heat product to 70 in a vacuum and ℃ carry out drying, the boron carbon nitrogen that just can obtain the mixture phase is nanocrystalline.
Embodiment 71: as described in embodiment 70, different is that boric acid substitutes with the tetrachloro potassium borate.
Embodiment 72: as described in embodiment 70, different is that boric acid substitutes with ammonium tetrafluoroborate.
Embodiment 73: as described in embodiment 70, different is that boric acid substitutes with diborane.
Embodiment 74: as described in embodiment 70, different is that boric acid substitutes with the tetrachloro Sodium Tetraborate, and hydrazine substitutes with methyl hydrazine.
Embodiment 75: as described in embodiment 70, that different is hydrazine sodiumazide and lithium nitride (Li
3N) mixture (mol ratio 1: 2) substitutes.
Embodiment 76: as described in embodiment 70, different is that boric acid substitutes with tetraborane, and hydrazine substitutes with magnesium nitride and bicarbonate mixture (mol ratio 2: 1).
Embodiment 77: as described in embodiment 70, different is that hydrazine substitutes with diamino-pyridine and potassium azide mixture (mol ratio 1: 3), and the siccative hydrolith substitutes with soda-lime.
Embodiment 78: as described in embodiment 70, different is that hydrazine substitutes with CaCl2 and ethyl aminoacetate mixture (mol ratio 4: 1).
Embodiment 79: as described in embodiment 70, different is that hydrazine substitutes with azide magnesium.
Embodiment 80: as described in embodiment 70, different is that boric acid substitutes with trimethyl borate, and hydrazine substitutes with phenylhydrazine, the siccative hydrolith mixture replacing of calcium oxide and hydrolith.
Embodiment 81: at first add Vanadium Pentoxide in FLAKES in tetracol phenixin, leave standstill distillation after 50 hours, remove wherein water and oxygen.Under the helium protection, the sodium Metal 99.5 that takes by weighing stoichiometric ratio is put into autoclave, adds 8ml again and seals through behind the tetracol phenixin of drying treatment.Add the pressure of 1300MPa in autoclave, the temperature of controlling autoclave again is elevated to 900 ℃ with 36 ℃/minute speed, and the constant temperature and pressure reaction naturally cooled to room temperature after 336 hours.
After reaction finishes, at first the tetracol phenixin suction filtration is fallen, remove organic by-products and other impurity in the product with acetone, ethanol, dilute hydrochloric acid successively then, use deionized water repetitive scrubbing product again, be neutrality up to filtrate.Product is heated to 90 ℃ in a vacuum and carries out drying, just can obtain the diamond nano crystalline substance.
Embodiment 82: as described in embodiment 81, different is that sodium Metal 99.5 substitutes with potassium metal, and the siccative Vanadium Pentoxide in FLAKES substitutes with potassium hydride KH.
Embodiment 83: as described in embodiment 81, different is that sodium Metal 99.5 substitutes with metallic lithium, and the siccative Vanadium Pentoxide in FLAKES substitutes with lithium hydride.
Embodiment 84: as described in embodiment 81, different is that sodium Metal 99.5 substitutes with MAGNESIUM METAL, and the siccative Vanadium Pentoxide in FLAKES substitutes with magnesium chloride.
Embodiment 85: as described in embodiment 81, different is that sodium Metal 99.5 substitutes with calcium metal, and the siccative Vanadium Pentoxide in FLAKES substitutes with calcium chloride.
Embodiment 86: as described in embodiment 81, different is that the carbon source tetracol phenixin substitutes with carbon tetrabromide, and the reductive agent sodium Metal 99.5 substitutes with lithium aluminum hydride.
Embodiment 87: as described in embodiment 81, different is that the carbon source tetracol phenixin substitutes with dithiocarbonic anhydride.
Embodiment 88: as described in embodiment 81, different is that the carbon source tetracol phenixin substitutes with methylene dichloride, and sodium Metal 99.5 substitutes with potassium hydride KH.
Embodiment 89: as described in embodiment 81, different is that the carbon source tetracol phenixin substitutes with trichloromethane, and sodium Metal 99.5 substitutes with sodium hydride.
Embodiment 90: as described in embodiment 81, different is that the carbon source tetracol phenixin substitutes with a monobromethane.
Embodiment 91: as described in embodiment 81, different is that the carbon source tetracol phenixin substitutes with methylene bromide.
Embodiment 92: at first add the sodium Metal 99.5 sheet in benzene, leave standstill distillation after 60 hours, remove wherein water and oxygen.Under the neon protection, the sodium Metal 99.5 and the magnesiumcarbonate that take by weighing stoichiometric ratio are put into autoclave, add 8ml again and seal through behind the benzene of drying treatment.Apply the pressure of 1200MPa on autoclave, the temperature of controlling autoclave again is elevated to 1000 ℃ with 42 ℃/minute speed, and the constant temperature and pressure reaction naturally cooled to room temperature after 384 hours.
After reaction finishes, at first the benzene suction filtration is fallen, remove organic by-products and other impurity in the product with acetone, ethanol, dilute hydrochloric acid successively then, use deionized water repetitive scrubbing product again, be neutrality up to filtrate.The product that obtains is heated to 110 ℃ in a vacuum and carries out drying, just can obtain diamond crystallites.
Embodiment 93: as described in embodiment 92, different is that the reductive agent sodium Metal 99.5 substitutes with metallic lithium, and solvent benzol substitutes with dimethylbenzene, and the siccative sodium Metal 99.5 substitutes with metal magnesium sheet and sal epsom.
Embodiment 94: as described in embodiment 92, different is that the reductive agent sodium Metal 99.5 substitutes with metal hydride calcium, and solvent benzol substitutes with toluene, siccative sodium Metal 99.5 potassium oxide and calcium oxide mixture replacing.
Embodiment 95: at first add calcium tablet in bromobenzene, leave standstill distillation after 72 hours, remove wherein water and oxygen.Under argon shield, the sodium Metal 99.5 and the dry ice that take by weighing stoichiometric ratio are put into autoclave, add 8ml again and seal through behind the bromobenzene of drying treatment.Apply the pressure of 1800MPa on autoclave, the temperature of controlling autoclave again is elevated to 900 ℃ with 48 ℃/minute speed, and the constant temperature and pressure reaction naturally cooled to room temperature after 432 hours.
After reaction finishes, at first the bromobenzene suction filtration is fallen, remove organic by-products and other impurity in the product with acetone, ethanol, dilute hydrochloric acid successively then, use deionized water repetitive scrubbing product again, be neutrality up to filtrate.The product that obtains is heated to 130 ℃ in a vacuum and carries out drying, just can obtain diamond crystallites.
Embodiment 96: as described in embodiment 95, different is that the siccative calcium tablet substitutes with the 4A molecular sieve, and sodium Metal 99.5 substitutes with sodium amide.
Embodiment 97: as described in embodiment 95, different is that the siccative calcium tablet substitutes with silica gel, and sodium Metal 99.5 substitutes with sodium phosphide, and dry ice substitutes with yellow soda ash.
Embodiment 98: as described in embodiment 95, different is that the solvent bromobenzene substitutes with toluene, and the siccative calcium tablet substitutes with POTASSIUM BOROHYDRIDE.
Embodiment 99: as described in embodiment 95, different is that sodium Metal 99.5 substitutes with MAGNESIUM METAL, and the siccative calcium tablet substitutes with magnesium chloride.
Embodiment 100: as described in embodiment 95, different is that pressure is brought up to 2000MPa, and temperature is set at 600 ℃, and the reaction times is increased to 480 hours, and heat-up rate is increased to 60 ℃/minute.
Claims (9)
1. a solvent thermal constant-pressure synthesis method of regulating and control boron-carbon-nitrogen material thing phase may further comprise the steps, and wherein the preparation steps of boron source liquid, carbon source liquid and nitrogenous source liquid is in no particular order:
(1) preparation of boron source liquid or carbon source liquid
In shielding gas, boron source or carbon source to be dissolved in the organic solvent of removing water and oxygen, concentration is 0.005～18 mol, obtains the solution or the suspension liquid of boron source or carbon source after stirring fast;
(2) preparation of nitrogenous source liquid
In shielding gas, the nitrogenous source with stoichiometric ratio dissolves in the organic solvent while stirring, obtains the solution or the suspension liquid of nitrogenous source;
(3) dress still
1. during diamond synthesis, only above-mentioned carbon source solution or suspension liquid are joined in the autoclave, then add the reductive agent of stoichiometric ratio again; Use shielding gas packaged autoclave behind the bubbling in solution then;
When 2. synthesizing boron nitride, above-mentioned boron source liquid and nitrogenous source liquid are mixed by stoichiometric ratio, in the autoclave of packing into after stirring; With shielding gas in mixing solutions bubbling to get rid of air wherein, packaged autoclave then;
When 3. synthesizing carbonitride, above-mentioned carbon source liquid and nitrogenous source liquid are mixed by stoichiometric ratio, in the autoclave of packing into after stirring; With shielding gas in mixing solutions bubbling to get rid of air wherein, packaged autoclave then;
(4) reaction
To before the autoclave heating, at first apply the pressure of a 40～2000MPa to it, the temperature of then controlling autoclave is heated to 220～1000 ℃ with 0.01～60 ℃/minute speed, and constant temperature and pressure reaction 8～480 hours naturally cools to room temperature then;
(5) product aftertreatment
Reaction is at first fallen the solvent suction filtration after finishing, and successively with acetone, ethanol, dilute hydrochloric acid washing, uses deionized water repetitive scrubbing product more then, is neutral up to filtrate; Above-mentioned product is heated to 60～200 ℃ of dryings in a vacuum, obtains even-grained boron-carbon-nitrogen material.
2. the solvent thermal constant-pressure synthesis method of regulation and control boron-carbon-nitrogen material thing phase as claimed in claim 1, it is characterized in that, the pre-treatment of described organic solvent is: add siccative and leave standstill distillation after 10～72 hours in organic solvent according to the consumption of 0.01～1.0 grams per milliliter solvent, remove the water and the oxygen that contain in desolvating.
3. the solvent thermal constant-pressure synthesis method of regulation and control boron-carbon-nitrogen material thing phase as claimed in claim 1 or 2, it is characterized in that described organic solvent is selected from one or more in benzene, alkylbenzene, halogeno-benzene, alkane and haloalkane, nitrile, pyridine, pyrroles, liquefied ammonia, organic amine, amides, tetraline, naphthane, dimethyl sulfoxide (DMSO), dithiocarbonic anhydride, tetrahydrofuran (THF), hexahydropyridine, aminopyridine, hydrazine class, the ion liquid solvent.
4. the solvent thermal constant-pressure synthesis method of regulation and control boron-carbon-nitrogen material thing phase as claimed in claim 2, it is characterized in that described siccative is selected from one or more in basic metal, alkalimetal oxide, alkalimetal hydride, alkali metal hydroxide, alkali metal sulfates, alkaline-earth metal, alkaline earth metal hydride, alkaline earth metal halide, alkaline earth metal oxide, alkaline earth metal sulphate, molecular sieve, activated alumina, Vanadium Pentoxide in FLAKES, lithium aluminum hydride, paraffin sheet, soda-lime, metal bromide, salt of wormwood or the silica gel.
5. the solvent thermal constant-pressure synthesis method of regulation and control boron-carbon-nitrogen material thing phase as claimed in claim 1 is characterized in that described shielding gas is selected from nitrogen, helium, neon or argon gas.
6. the solvent thermal constant-pressure synthesis method of regulation and control boron-carbon-nitrogen material thing phase as claimed in claim 1, it is characterized in that one or more are chosen in the boron source of using in the described step (1) from halogenation boron, borine, alkali metal borohydride, metal boride, boric acid, borate, halogen borate, boric acid ester compound or ammonium borate; Carbon source is chosen one or more from sulfide, carbon oxides, carbonate, halo piperazine or the organic amine of the halogenide of carbon, haloalkane, carbon.
7. the solvent thermal constant-pressure synthesis method of regulation and control boron-carbon-nitrogen material thing phase as claimed in claim 1, it is characterized in that the nitrogenous source that uses in the described step (2) is chosen one or more from metal nitride, trinitride, ammonia and ammonium salt, three halogenated nitrogens, organic amine, sodium amide, amino ester, hydrazine class or hydrazine class title complex.
8. the solvent thermal constant-pressure synthesis method of regulation and control boron-carbon-nitrogen material thing phase as claimed in claim 1, it is characterized in that the 1. middle reductive agent that uses of described step (3) is chosen one or more from basic metal, alkaline-earth metal, basic metal phosphide, basic metal aminocompound, alkalimetal hydride, metal borohydride.
9. the solvent thermal constant-pressure synthesis method of regulation and control boron-carbon-nitrogen material thing phase as claimed in claim 1, it is characterized in that, in the described step (4), when the temperature of autoclave so that 20～60 ℃ of fast speeds/when min was elevated to preset value, the sample that obtains was the very little boron carbon nitrogen nanocrystal of granularity; When the temperature of autoclave being elevated to preset value, obtaining granularity and reach micron order or the above boron carbon nitrogen crystalline material of micron order with 0.01～10 ℃/min of slower speed.
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| CN103883257A (en) * | 2014-02-14 | 2014-06-25 | 常州大学 | Method for manufacturing boron nitride toughened polycrystalline diamond |
| CN105692572A (en) * | 2016-03-11 | 2016-06-22 | 大连理工大学 | Method for synthesizing g-C3N4 nanomaterials with various shapes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS60180908A (en) * | 1984-02-27 | 1985-09-14 | Shigeo Nishida | Manufacture of artificial diamond |
| SU1490869A1 (en) * | 1987-09-30 | 1991-04-23 | Институт элементоорганических соединений им.А.Н.Несмеянова | Method of producing diamond powders |
| CN1066417C (en) * | 1997-11-05 | 2001-05-30 | 中国科学技术大学 | Thermal reduction process of metal solvent to synthesize diamond and other material with similar structure |
| JP4288457B2 (en) * | 2002-07-25 | 2009-07-01 | 白石工業株式会社 | Microcrystalline diamond, polycrystalline diamond and method for producing them |
| AU2002368368A1 (en) * | 2002-11-15 | 2004-06-15 | University Of Science And Technology Of China | Process for producing diamond, graphite or mixture of diamond and graphite |
| 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 |
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