CN105780123A - Hafnium-carbide nanometer whiskers and preparing method thereof - Google Patents
Hafnium-carbide nanometer whiskers and preparing method thereof Download PDFInfo
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- CN105780123A CN105780123A CN201610079179.3A CN201610079179A CN105780123A CN 105780123 A CN105780123 A CN 105780123A CN 201610079179 A CN201610079179 A CN 201610079179A CN 105780123 A CN105780123 A CN 105780123A
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/005—Growth of whiskers or needles
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
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Abstract
The invention discloses hafnium-carbide nanometer whiskers and a preparing method thereof.The preparing method includes the steps that a carbon precursor is dissolved into an organic solvent, the mixture is distilled, and a carbon-precursor organic-solvent soluble component is obtained; 30-50wt% of organic hafnium and 50-70wt% of the carbon-precursor organic-solvent soluble component are mixed, the mixture is dissolved into an organic solvent in the solid-liquid mass ratio of 1:(1-3), the temperature is preserved for 2 h-6 h under the conditions of inert atmosphere, stirring and the temperature of 250 DEG C-459 DEG C, and a hafnium-doped carbon precursor is obtained; a graphite crucible containing the hafnium-doped carbon precursor is placed into a carbonizing furnace, the temperature of 700 DEG C-900 DEG C is preserved for 1 h-3 h, a hafnium-doped-carbon-precursor-based carbon material is obtained, ground and formed, the formed blank is placed into an ethanol solution containing 3-10wt% of catalysts for soaking, the mixture is subjected to air drying and placed into a graphite crucible to be placed into a carbonizing furnace, the temperature is preserved for 1 h-4 h under the conditions of inert atmosphere and the temperature of 1,600 DEG C-1,900 DEG C, and the hafnium-carbide nanometer whiskers are obtained.The carbon precursor is resin or asphalt.The preparing method is simple in technology, low in cost and environmentally friendly, and the prepared product is high in purity and large in draw ratio.
Description
Technical field
The invention belongs to hafnium carbide whisker technique field, particularly relate to a kind of hafnium carbide nano whisker and preparation method thereof.
Background technology
Hafnium carbide whisker has a series of excellent properties, such as high rigidity, high-modulus, high hot strength, fabulous heat stability and chemical stability, good decay resistance and anti-wear performance, good heat conduction and electric conductivity, these excellent performances make its can serve as the reinforcement of high-performance ceramic based composites or carbon/carbon composite (field pine. the CVD synthesis of one-dimensional HfC, Flied emission and modified C/C composite thereof. Ph.D. Dissertation, Northwestern Polytechnical University, 2014.11).The electric emissivity of carbide hafnium whisker is higher than traditional polycrystalline tungsten filament, its performance is even better than SiC whisker, someone predicts that it is of future generation for daily and lighting for medical use filament material (J.V.Milewski, P.D.Milewski.Singlecrystalwhiskerelectriclightfilament [P] .US:4864186,1989.).Additionally, hafnium carbide nano whisker has low work function so that it is easily discharge electronics；High mechanical stability and low surface mobility can reduce the impact of survival gas absorption and ion bom bardment, make emission current more stable, current hafnium carbide nano whisker has been applied to (A.Mackie in feds, R.L.Hartman, P.R.Davis.Highcurrentdensityfieldemissionfromtransitionm etalcarbides (J) .AppliedSurfaceScience, 1993,67 (1-4): 29-35.).
At present, the research about hafnium carbide whisker is reported less, and its preparation mainly adopts CVD.Last century the eighties, Futamoto et al. (M.Futamoto, I.Yuito, U.Kawabe.Hafniumcarbideandnitridewhiskergrowthbychemical vapordeposition (J) .JournalofCrystalGrowth, 1983,61 (1): 69-74.) CVD is utilized to be prepared for hafnium carbide whisker.Detailed process is: at ambient pressure, and low-temperature space is heated to 250 DEG C of HfCl making solid phase4Powder body is sublimed into gas and CH4And H2Pass into high-temperature region together and chemical reaction occurs, in the graphite base of high-temperature region, finally obtain HfC whisker.Wherein, HfCl4For hafnium source, CH4For carbon source, H2For reducing gas, it is put in nickel (Ni) sheet between adjoining graphite substrate as catalyst.The growth course of hafnium carbide whisker is subject to VLS mechanism control, and its diameter and the maximum difference of length can to 25 μm and 4.5mm.
(the S.Motojima such as Motojima, Y.Kawashima.ChemicalvapourgrowthofHfCwhiskersandtheirmor phology (J) .JournalofMaterialsScience, 1996,31 (14): 3697-3700.) the atmospheric pressure cvd preparation process condition of HfC whisker has been carried out research in greater detail.Depositing temperature is 1,050 1250 DEG C, HfCl4Gas source is the reaction of hafnium metal powder and chlorine under 700 DEG C of conditions, and is loaded into conversion zone and CH with argon4And H2Reaction, grows HfC whisker in the graphite base be loaded with metal catalyst particles.
Above-mentioned atmospheric pressure cvd preparation technology is higher to equipment requirements, HfCl4Gas flow is difficult to control to, and the hafnium carbide whisker purity of preparation is low, diameter is big, draw ratio is little, and preparation cost is higher.
In recent years, (the J.S.Yuan such as Yuan, H.Zhang, J.Tang, N.Shinya, K.Nakajima, L.C.Qin.Synthesisandcharacterizationofsinglecrystallineh afniumcarbidenanowires (J) .JournaloftheAmericanCeramicSociety, 2012,95 (7): 2352-2355.) CVD is utilized to prepare the HfC nanometer monocrystalline whisker that diameter is less.They are 10-1Under the negative pressure of Pa, at HfCl4-CH4-H2Response system in be successfully prepared HfC nanometer monocrystalline whisker.Synthesis temperature is 1280 DEG C, and growth substrate is graphite flake, and metallic catalyst is the Ni nano-particle of diameter tens nanometers.Prepared HfC nano whisker diameter is 20 ~ 80nm, and length is tens microns.Though hafnium carbide whisker purity prepared by the method is little with diameter compared with high, but reaction condition is harsher, HfCl4Gas flow is difficult to control to still higher with preparation cost.
Summary of the invention
It is contemplated that overcome prior art defect, it is therefore an objective to technique is simple, reaction condition is gentle, preparation cost is low and eco-friendly hafnium carbide nano whisker preparation method to provide one, the hafnium carbide nano whisker purity prepared by the method is high big with draw ratio.
For achieving the above object, the comprising the concrete steps that of the technical solution used in the present invention:
The preparation of step one, hafnium doping Colophonium or hafnium doping resin
Colophonium after pulverizing or resin are dissolved in organic solvent, the mass ratio of solute and solvent is 1 (2 ~ 5), stands 1 ~ 5h, filters, filtrate after filtering is distilled under 125 ~ 150 DEG C of conditions, obtains Colophonium organic solvent soluble constituent or resin organic solvent soluble constituent.
The Colophonium organic solvent soluble constituent of organic hafnium of 30 ~ 50wt% and 50 ~ 70wt% is mixed or organic hafnium of 30 ~ 50wt% and the resin organic solvent soluble constituent of 50 ~ 70wt% are mixed, obtain the mixture of organic hafnium mixture with Colophonium organic solvent soluble constituent or organic hafnium and resin organic solvent soluble constituent；It is 1 (1 ~ 3) by solid-liquid mass ratio again, by the mixture of organic hafnium and Colophonium organic solvent soluble constituent or the mixture of organic hafnium Yu resin organic solvent soluble constituent is dissolved in organic solvent, stirring 2 ~ 3h, obtains the mixed liquor of organic hafnium mixed liquor with Colophonium organic solvent soluble constituent or organic hafnium and resin organic solvent soluble constituent.
By described organic hafnium and Colophonium organic solvent soluble constituent mixed liquor or organic hafnium and resin organic solvent soluble constituent mixed liquor are moved in reactor, under inert atmosphere and stirring condition, it is warming up to 250 DEG C ~ 450 DEG C, is incubated 2 ~ 6h；Then turn off stirring, in an inert atmosphere natural cooling, obtain hafnium doping Colophonium or hafnium doping resin.
The preparation of step 2, hafnium doping asphalt base charcoal materials or hafnium doping resin base Carbon Materials
Will be equipped with the graphite crucible of hafnium doping Colophonium and be placed in retort or the graphite crucible of the resin that adulterated by hafnium is placed in retort, with the ramp of 2 ~ 10 DEG C/min to 700 ~ 900 DEG C, insulation 1 ~ 3h, natural cooling, obtain hafnium doping asphalt base charcoal materials or hafnium doping resin base Carbon Materials.
Step 3, hafnium carbide nano whisker preparation
Hafnium is adulterated asphalt base charcoal materials or the resin base Carbon Materials that adulterated by hafnium is ground to the powder that particle diameter is 30 ~ 100 μm, add in mould, mechanical pressing, the demoulding, obtain base substrate；Base substrate is put into immersion 5 ~ 40min, natural air drying in the alcoholic solution containing 3 ~ 10wt% catalyst；Again air-dry base substrate is loaded graphite crucible and be placed in retort, under inert atmosphere protection, with the ramp of 2 ~ 10 DEG C/min to 1600 DEG C ~ 1900 DEG C, heat treatment 1 ~ 4h, natural cooling, obtain hafnium carbide nano whisker.
Described Colophonium is asphalt or coal tar pitch.
Described organic hafnium is the one in acetylacetone,2,4-pentanedione hafnium, cyclopentadienyl group tri-chlorination hafnium, pentamethylcyclopentadiene base tri-chlorination hafnium.
Described catalyst is the one in ferric nitrate, nickel nitrate, cobalt nitrate.
Described organic solvent is the one in toluene, dimethylbenzene, dehydrated alcohol.
Described machine pressure refers to pressurize 2 ~ 5min when 90 ~ 190MPa.
The rotating speed of described stirring is 200 ~ 500r/min.
Described noble gas is argon or is nitrogen.
Owing to adopting technique scheme, the present invention compared with prior art has following good effect:
(1) present invention is with Colophonium or resin organic solvent soluble constituent for carbon source, with organic hafnium for hafnium source, under catalyst action, is reacted by the copyrolysis in carbon source and hafnium source and prepares hafnium carbide nano whisker at charcoal material surface.
(2) present invention can realize the control to hafnium carbide nano whisker diameter and length by regulating carbon source and the proportioning in hafnium source and the heat treatment temperature of base substrate and time.
(3) the hafnium carbide nano whisker purity that prepared by the present invention is high, and the diameter of hafnium carbide nano whisker is 10 ~ 200nm, and length is 10 ~ 300 μm.
(4) preparation technology of hafnium carbide nano whisker provided by the invention is simple, and preparation cost is low, environmental friendliness.
Therefore, the present invention has that technique is simple, reaction condition is gentle, preparation cost is low and eco-friendly feature, and the hafnium carbide nano whisker purity prepared by the method is high and draw ratio is big.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of hafnium carbide nano whisker prepared by the present invention；
Fig. 2 is a kind of hafnium carbide nano whisker SEM photograph prepared by the present invention.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the invention will be further described, not the restriction to its protection domain.
In this detailed description of the invention: described machine pressure refers to pressurize 2 ~ 5min when 90 ~ 190MPa；The rotating speed of described stirring is 200 ~ 500r/min.Embodiment repeats no more.
Embodiment 1
A kind of hafnium carbide nano whisker and preparation method thereof.Comprising the concrete steps that of described preparation method:
The preparation of step one, hafnium doping Colophonium
Being dissolved in organic solvent by the Colophonium after pulverizing, the mass ratio of solute and solvent is 1 (2 ~ 5), stands 1 ~ 5h, filters, and the filtrate after filtering is distilled under 125 ~ 150 DEG C of conditions, obtains Colophonium organic solvent soluble constituent.
The Colophonium organic solvent soluble constituent of organic hafnium of 40 ~ 50wt% and 50 ~ 60wt% is mixed, obtains the mixture of organic hafnium and Colophonium organic solvent soluble constituent；It is 1 (1 ~ 3) by solid-liquid mass ratio again, the mixture of organic hafnium Yu Colophonium organic solvent soluble constituent is dissolved in organic solvent, stir 2 ~ 3h, obtain the mixed liquor of organic hafnium and Colophonium organic solvent soluble constituent.
Described organic hafnium and Colophonium organic solvent soluble constituent mixed liquor are moved in reactor, under inert atmosphere and stirring condition, is warming up to 250 DEG C ~ 350 DEG C, be incubated 4 ~ 6h；Then turn off stirring, in an inert atmosphere natural cooling, obtain hafnium doping Colophonium.
The preparation of step 2, hafnium doping asphalt base charcoal materials
Will be equipped with the graphite crucible of hafnium doping Colophonium and be placed in retort, with the ramp of 2 ~ 6 DEG C/min to 700 ~ 800 DEG C, be incubated 2 ~ 3h, natural cooling, obtain hafnium doping asphalt base charcoal materials.
Step 3, hafnium carbide nano whisker preparation
The asphalt base charcoal materials that adulterated by hafnium is ground to the powder that particle diameter is 30 ~ 100 μm, adds in mould, mechanical pressing, and the demoulding obtains base substrate；Base substrate is put into immersion 5 ~ 40min, natural air drying in the alcoholic solution containing 3 ~ 6wt% catalyst；Again air-dry base substrate is loaded graphite crucible and be placed in retort, under inert atmosphere protection, with the ramp of 2 ~ 6 DEG C/min to 1600 DEG C ~ 1800 DEG C, heat treatment 2 ~ 4h, natural cooling, obtain hafnium carbide nano whisker.
Described Colophonium is asphalt.
Described organic hafnium is acetylacetone,2,4-pentanedione hafnium.
Described catalyst is ferric nitrate.
Described organic solvent is toluene.
Described noble gas is argon.
Embodiment 2
A kind of hafnium carbide nano whisker and preparation method thereof.Comprising the concrete steps that of described preparation method:
The preparation of step one, hafnium doping Colophonium
Being dissolved in organic solvent by the Colophonium after pulverizing, the mass ratio of solute and solvent is 1 (2 ~ 5), stands 1 ~ 5h, filters, and the filtrate after filtering is distilled under 125 ~ 150 DEG C of conditions, obtains Colophonium organic solvent soluble constituent.
The Colophonium organic solvent soluble constituent of organic hafnium of 30 ~ 40wt% and 60 ~ 70wt% is mixed, obtains the mixture of organic hafnium and Colophonium organic solvent soluble constituent；It is 1 (1 ~ 3) by solid-liquid mass ratio again, the mixture of organic hafnium Yu Colophonium organic solvent soluble constituent is dissolved in organic solvent, stir 2 ~ 3h, obtain the mixed liquor of organic hafnium and Colophonium organic solvent soluble constituent.
Described organic hafnium and Colophonium organic solvent soluble constituent mixed liquor are moved in reactor, under inert atmosphere and stirring condition, is warming up to 350 DEG C ~ 450 DEG C, be incubated 2 ~ 4h；Then turn off stirring, in an inert atmosphere natural cooling, obtain hafnium doping Colophonium.
The preparation of step 2, hafnium doping asphalt base charcoal materials
Will be equipped with the graphite crucible of hafnium doping Colophonium and be placed in retort, with the ramp of 6 ~ 10 DEG C/min to 800 ~ 900 DEG C, be incubated 1 ~ 2h, natural cooling, obtain hafnium doping asphalt base charcoal materials.
Step 3, hafnium carbide nano whisker preparation
The asphalt base charcoal materials that adulterated by hafnium is ground to the powder that particle diameter is 30 ~ 100 μm, adds in mould, mechanical pressing, and the demoulding obtains base substrate；Base substrate is put into immersion 5 ~ 40min, natural air drying in the alcoholic solution containing 6 ~ 10wt% catalyst；Again air-dry base substrate is loaded graphite crucible and be placed in retort, under inert atmosphere protection, with the ramp of 6 ~ 10 DEG C/min to 1700 DEG C ~ 1900 DEG C, heat treatment 1 ~ 3h, natural cooling, obtain hafnium carbide nano whisker.
Described Colophonium is asphalt.
Described organic hafnium is acetylacetone,2,4-pentanedione hafnium.
Described catalyst is ferric nitrate.
Described organic solvent is toluene.
Described noble gas is argon
Embodiment 3
A kind of hafnium carbide nano whisker and preparation method thereof.Except following technical parameter, all the other are with embodiment 1:
Described Colophonium is coal tar pitch.
Described organic hafnium is cyclopentadienyl group tri-chlorination hafnium.
Described catalyst is nickel nitrate.
Described organic solvent is dimethylbenzene.
Described noble gas is nitrogen.
Embodiment 4
A kind of hafnium carbide nano whisker and preparation method thereof.Except following technical parameter, all the other are with embodiment 2:
Described Colophonium is coal tar pitch.
Described organic hafnium is cyclopentadienyl group tri-chlorination hafnium.
Described catalyst is nickel nitrate.
Described organic solvent is dimethylbenzene.
Described noble gas is nitrogen.
Embodiment 5
A kind of hafnium carbide nano whisker and preparation method thereof.Comprising the concrete steps that of described preparation method:
The preparation of step one, hafnium doping resin
Being dissolved in organic solvent by the resin after pulverizing, the mass ratio of solute and solvent is 1 (2 ~ 5), stands 1 ~ 5h, filters, and the filtrate after filtering is distilled under 125 ~ 150 DEG C of conditions, obtains resin organic solvent soluble constituent.
The resin organic solvent soluble constituent of organic hafnium of 40 ~ 50wt% and 50 ~ 60wt% is mixed, obtains the mixture of organic hafnium and resin organic solvent soluble constituent；It is 1 (1 ~ 3) by solid-liquid mass ratio again, the mixture of organic hafnium Yu resin organic solvent soluble constituent is dissolved in organic solvent, stir 2 ~ 3h, obtain the mixed liquor of organic hafnium and resin organic solvent soluble constituent.
Organic hafnium and resin organic solvent soluble constituent mixed liquor are moved in reactor, under inert atmosphere and stirring condition, is warming up to 250 DEG C ~ 350 DEG C, be incubated 4 ~ 6h；Then turn off stirring, in an inert atmosphere natural cooling, obtain hafnium doping resin.
The preparation of step 2, hafnium doping resin base Carbon Materials
The graphite crucible of resin of being adulterated by hafnium is placed in retort, with the ramp of 2 ~ 6 DEG C/min to 700 ~ 800 DEG C, is incubated 2 ~ 3h, natural cooling, obtains hafnium doping resin base Carbon Materials.
Step 3, hafnium carbide nano whisker preparation
The resin base Carbon Materials that adulterated by hafnium is ground to the powder that particle diameter is 30 ~ 100 μm, adds in mould, mechanical pressing, and the demoulding obtains base substrate；Base substrate is put into immersion 5 ~ 40min, natural air drying in the alcoholic solution containing 3 ~ 6wt% catalyst；Again air-dry base substrate is loaded graphite crucible and be placed in retort, under inert atmosphere protection, with the ramp of 2 ~ 6 DEG C/min to 1600 DEG C ~ 1800 DEG C, heat treatment 2 ~ 4h, natural cooling, obtain hafnium carbide nano whisker.
Described organic hafnium is pentamethylcyclopentadiene base tri-chlorination hafnium.
Described catalyst is cobalt nitrate.
Described organic solvent is dehydrated alcohol.
Described noble gas is argon.
Embodiment 6
A kind of hafnium carbide nano whisker and preparation method thereof.Comprising the concrete steps that of described preparation method:
The preparation of step one, hafnium doping resin
Being dissolved in organic solvent by the resin after pulverizing, the mass ratio of solute and solvent is 1 (2 ~ 5), stands 1 ~ 5h, filters, and the filtrate after filtering is distilled under 125 ~ 150 DEG C of conditions, obtains resin organic solvent soluble constituent.
The resin organic solvent soluble constituent of organic hafnium of 30 ~ 40wt% and 60 ~ 70wt% is mixed, obtains the mixture of organic hafnium and resin organic solvent soluble constituent；It is 1 (1 ~ 3) by solid-liquid mass ratio again, the mixture of organic hafnium Yu resin organic solvent soluble constituent is dissolved in organic solvent, stir 2 ~ 3h, obtain the mixed liquor of organic hafnium and resin organic solvent soluble constituent.
Organic hafnium and resin organic solvent soluble constituent mixed liquor are moved in reactor, under inert atmosphere and stirring condition, is warming up to 350 DEG C ~ 450 DEG C, be incubated 2 ~ 4h；Then turn off stirring, in an inert atmosphere natural cooling, obtain hafnium doping resin.
The preparation of step 2, hafnium doping resin base Carbon Materials
The graphite crucible of resin of being adulterated by hafnium is placed in retort, with the ramp of 6 ~ 10 DEG C/min to 800 ~ 900 DEG C, is incubated 1 ~ 2h, natural cooling, obtains hafnium doping resin base Carbon Materials.
Step 3, hafnium carbide nano whisker preparation
The resin base Carbon Materials that adulterated by hafnium is ground to the powder that particle diameter is 30 ~ 100 μm, adds in mould, mechanical pressing, and the demoulding obtains base substrate；Base substrate is put into immersion 5 ~ 40min, natural air drying in the alcoholic solution containing 6 ~ 10wt% catalyst；Again air-dry base substrate is loaded graphite crucible and be placed in retort, under inert atmosphere protection, with the ramp of 6 ~ 10 DEG C/min to 1700 DEG C ~ 1900 DEG C, heat treatment 1 ~ 3h, natural cooling, obtain hafnium carbide nano whisker.
Described organic hafnium is pentamethylcyclopentadiene base tri-chlorination hafnium.
Described catalyst is cobalt nitrate.
Described organic solvent is dehydrated alcohol.
Described noble gas is argon.
This detailed description of the invention compared with prior art has following good effect:
(1) this detailed description of the invention is with Colophonium or resin organic solvent soluble constituent for carbon source, with organic hafnium for hafnium source, under catalyst action, is reacted by the copyrolysis in carbon source and hafnium source and prepares hafnium carbide nano whisker at charcoal material surface.
(2) this detailed description of the invention can realize the control to hafnium carbide nano whisker diameter and length by regulating carbon source and the proportioning in hafnium source and the heat treatment temperature of base substrate and time.
(3) Fig. 1 is the XRD spectra of a kind of hafnium carbide nano whisker prepared by this detailed description of the invention, diffraction maximum corresponding (111), (200), (220) of β-HfC, (311), (222), (400) crystal face respectively at the angle of diffraction 2 θ=33 °, 39 °, 56 °, 67 °, 70 °, 83 ° places in figure, it was shown that the hafnium carbide nano whisker of preparation is β-HfC phase；
(4) Fig. 2 is the SEM photograph of a kind of hafnium carbide nano whisker of embodiment 2 preparation.Nano whisker is line style growth as can be seen from Figure 2, and diameter of whiskers is 10 ~ 200nm, and length is 10 ~ 300 μm, and whisker end is it is observed that melt catalyst pellet also.
(5) preparation technology of the hafnium carbide nano whisker that this detailed description of the invention provides is simple, and preparation cost is low, environmental friendliness.
Therefore, this detailed description of the invention has that technique is simple, reaction condition is gentle, preparation cost is low and eco-friendly feature, and the hafnium carbide nano whisker purity prepared by the method is high and draw ratio is big.
Claims (9)
1. the preparation method of a hafnium carbide nano whisker, it is characterised in that comprising the concrete steps that of described preparation method:
The preparation of step one, hafnium doping Colophonium or hafnium doping resin
Colophonium after pulverizing or resin are dissolved in organic solvent, the mass ratio of solute and solvent is 1 (2～5), stands 1～5h, filters, filtrate after filtering is distilled under 125～150 DEG C of conditions, obtains Colophonium organic solvent soluble constituent or resin organic solvent soluble constituent；
The Colophonium organic solvent soluble constituent of organic hafnium of 30～50wt% and 50～70wt% is mixed or organic hafnium of 30～50wt% and the resin organic solvent soluble constituent of 50～70wt% are mixed, obtain the mixture of organic hafnium mixture with Colophonium organic solvent soluble constituent or organic hafnium and resin organic solvent soluble constituent；It is 1 (1～3) by solid-liquid mass ratio again, by the mixture of organic hafnium and Colophonium organic solvent soluble constituent or the mixture of organic hafnium Yu resin organic solvent soluble constituent is dissolved in organic solvent, stirring 2～3h, obtains the mixed liquor of organic hafnium mixed liquor with Colophonium organic solvent soluble constituent or organic hafnium and resin organic solvent soluble constituent；
By described organic hafnium and Colophonium organic solvent soluble constituent mixed liquor or organic hafnium and resin organic solvent soluble constituent mixed liquor are moved in reactor, under inert atmosphere and stirring condition, it is warming up to 250 DEG C～450 DEG C, is incubated 2～6h；Then turn off stirring, in an inert atmosphere natural cooling, obtain hafnium doping Colophonium or hafnium doping resin；
The preparation of step 2, hafnium doping asphalt base charcoal materials or hafnium doping resin base Carbon Materials
Will be equipped with the graphite crucible of hafnium doping Colophonium and be placed in retort or the graphite crucible of the resin that adulterated by hafnium is placed in retort, with the ramp of 2～10 DEG C/min to 700～900 DEG C, insulation 1～3h, natural cooling, obtain hafnium doping asphalt base charcoal materials or hafnium doping resin base Carbon Materials；
Step 3, hafnium carbide nano whisker preparation
Hafnium is adulterated asphalt base charcoal materials or the resin base Carbon Materials that adulterated by hafnium is ground to the powder that particle diameter is 30～100 μm, add in mould, mechanical pressing, the demoulding, obtain base substrate；Base substrate is put into immersion 5～40min, natural air drying in the alcoholic solution containing 3～10wt% catalyst；Again air-dry base substrate is loaded graphite crucible and be placed in retort, under inert atmosphere protection, with the ramp of 2～10 DEG C/min to 1600 DEG C～1900 DEG C, heat treatment 1～4h, natural cooling, obtain hafnium carbide nano whisker.
2. the preparation method of hafnium carbide nano whisker according to claim 1, it is characterised in that described Colophonium is asphalt or coal tar pitch.
3. the preparation method of hafnium carbide nano whisker according to claim 1, it is characterised in that described organic hafnium is the one in acetylacetone,2,4-pentanedione hafnium, cyclopentadienyl group tri-chlorination hafnium, pentamethylcyclopentadiene base tri-chlorination hafnium.
4. the preparation method of hafnium carbide nano whisker according to claim 1, it is characterised in that described catalyst is the one in ferric nitrate, nickel nitrate, cobalt nitrate.
5. the preparation method of hafnium carbide nano whisker according to claim 1, it is characterised in that described organic solvent is the one in toluene, dimethylbenzene, dehydrated alcohol.
6. the preparation method of hafnium carbide nano whisker according to claim 1, it is characterised in that described machine pressure refers to pressurize 2～5min when 90～190MPa.
7. the preparation method of hafnium carbide nano whisker according to claim 1, it is characterised in that the rotating speed of described stirring is 200～500r/min.
8. the preparation method of hafnium carbide nano whisker according to claim 1, it is characterised in that described noble gas is argon or for nitrogen.
9. a hafnium carbide nano whisker, it is characterised in that described hafnium carbide nano whisker is the hafnium carbide nano whisker prepared by the preparation method of hafnium carbide nano whisker according to any one of claim 1～8.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106282356A (en) * | 2016-08-30 | 2017-01-04 | 天津诺禾医学检验所有限公司 | A kind of method and device based on amplicon secondary order-checking point mutation detection |
| CN108083808A (en) * | 2016-11-21 | 2018-05-29 | 武汉科技大学 | A kind of nano silicon carbide hafnium ceramic organic precursor and preparation method thereof |
| CN112195503A (en) * | 2020-09-24 | 2021-01-08 | 西北工业大学 | Method for synthesizing hafnium carbide crystal whisker with large length-diameter ratio by carbothermic reduction method |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0477399A (en) * | 1990-07-17 | 1992-03-11 | Tokai Carbon Co Ltd | Production of sic whisker |
| CN102126859A (en) * | 2011-03-03 | 2011-07-20 | 西北工业大学 | Method for preparing bamboo-shaped SiC nanowire-toughened HfC ceramic |
| CN102225762A (en) * | 2011-05-25 | 2011-10-26 | 山东理工大学 | Preparation method of hafnium carbide powder |
| CN102730685A (en) * | 2012-07-03 | 2012-10-17 | 西北工业大学 | Method for preparing one-dimensional hafnium carbide nanometer material |
| CN102965638A (en) * | 2012-11-19 | 2013-03-13 | 西北工业大学 | Method for preparing C-coated HfC (hybrid fiber coaxial) whiskers |
| CN103194734A (en) * | 2013-04-15 | 2013-07-10 | 西北工业大学 | Preparation method of self-assembled three-dimensional hafnium carbide whisker network structure |
| CN103936464A (en) * | 2014-03-27 | 2014-07-23 | 西北工业大学 | Preparation method of HfC-SiC modified carbon/carbon composite material |
| CN103951470A (en) * | 2014-04-04 | 2014-07-30 | 西北工业大学 | Hafnium carbide nanowire-toughened ceramic coating layer of surface of carbon/carbon composites and preparation method thereof |
| CN103992115A (en) * | 2014-05-14 | 2014-08-20 | 西北工业大学 | Method for preparing C/SiC-HfC carbon fiber reinforced ultrahigh-temperature ceramic matrix composite |
| CN104150938A (en) * | 2014-08-06 | 2014-11-19 | 西北工业大学 | Preparation method for one-dimensional HfC (hafnium carbide) modified carbon/carbon composite material |
| CN104671245A (en) * | 2015-02-28 | 2015-06-03 | 武汉理工大学 | Preparation method of hafnium carbide nano-powder |
-
2016
- 2016-02-04 CN CN201610079179.3A patent/CN105780123B/en not_active Expired - Fee Related
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0477399A (en) * | 1990-07-17 | 1992-03-11 | Tokai Carbon Co Ltd | Production of sic whisker |
| CN102126859A (en) * | 2011-03-03 | 2011-07-20 | 西北工业大学 | Method for preparing bamboo-shaped SiC nanowire-toughened HfC ceramic |
| CN102225762A (en) * | 2011-05-25 | 2011-10-26 | 山东理工大学 | Preparation method of hafnium carbide powder |
| CN102730685A (en) * | 2012-07-03 | 2012-10-17 | 西北工业大学 | Method for preparing one-dimensional hafnium carbide nanometer material |
| CN102965638A (en) * | 2012-11-19 | 2013-03-13 | 西北工业大学 | Method for preparing C-coated HfC (hybrid fiber coaxial) whiskers |
| CN103194734A (en) * | 2013-04-15 | 2013-07-10 | 西北工业大学 | Preparation method of self-assembled three-dimensional hafnium carbide whisker network structure |
| CN103936464A (en) * | 2014-03-27 | 2014-07-23 | 西北工业大学 | Preparation method of HfC-SiC modified carbon/carbon composite material |
| CN103951470A (en) * | 2014-04-04 | 2014-07-30 | 西北工业大学 | Hafnium carbide nanowire-toughened ceramic coating layer of surface of carbon/carbon composites and preparation method thereof |
| CN103992115A (en) * | 2014-05-14 | 2014-08-20 | 西北工业大学 | Method for preparing C/SiC-HfC carbon fiber reinforced ultrahigh-temperature ceramic matrix composite |
| CN104150938A (en) * | 2014-08-06 | 2014-11-19 | 西北工业大学 | Preparation method for one-dimensional HfC (hafnium carbide) modified carbon/carbon composite material |
| CN104671245A (en) * | 2015-02-28 | 2015-06-03 | 武汉理工大学 | Preparation method of hafnium carbide nano-powder |
Non-Patent Citations (2)
| Title |
|---|
| J.S. YUAN，ET AL.: "Synthesis and characterization of single crystalline hafnium carbide nanowires", 《JOURNAL OF THE AMERICAN CERAMIC SOCIETY》 * |
| 田松: "一维HfC的CVD合成、场发射及其改性C/C复合材料", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106282356A (en) * | 2016-08-30 | 2017-01-04 | 天津诺禾医学检验所有限公司 | A kind of method and device based on amplicon secondary order-checking point mutation detection |
| CN106282356B (en) * | 2016-08-30 | 2019-11-26 | 天津诺禾医学检验所有限公司 | A kind of method and device based on amplification second filial sequencing point mutation detection |
| CN108083808A (en) * | 2016-11-21 | 2018-05-29 | 武汉科技大学 | A kind of nano silicon carbide hafnium ceramic organic precursor and preparation method thereof |
| CN108083808B (en) * | 2016-11-21 | 2021-02-12 | 武汉科技大学 | Nano hafnium carbide ceramic organic precursor and preparation method thereof |
| CN112195503A (en) * | 2020-09-24 | 2021-01-08 | 西北工业大学 | Method for synthesizing hafnium carbide crystal whisker with large length-diameter ratio by carbothermic reduction method |
| CN112195503B (en) * | 2020-09-24 | 2022-07-26 | 西北工业大学 | Method for synthesizing hafnium carbide crystal whisker with large length-diameter ratio by carbothermic reduction method |
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