CN105780123B - A kind of hafnium carbide nano whisker and preparation method thereof - Google Patents
A kind of hafnium carbide nano whisker and preparation method thereof Download PDFInfo
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- CN105780123B CN105780123B CN201610079179.3A CN201610079179A CN105780123B CN 105780123 B CN105780123 B CN 105780123B CN 201610079179 A CN201610079179 A CN 201610079179A CN 105780123 B CN105780123 B CN 105780123B
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- 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
- C30B29/10—Inorganic compounds or compositions
- C30B29/36—Carbides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- 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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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- 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
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
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Abstract
The present invention discloses a kind of hafnium carbide nano whisker and preparation method thereof.Carbonaceous presoma is dissolved in organic solvent, distills, obtains carbonaceous presoma organic solvent soluble constituent；The organic hafniums of 30 ~ 50wt% are mixed with 50 ~ 70wt% carbonaceous presoma organic solvent soluble constituents, it is that 1 ︰ (1 ~ 3) is dissolved in organic solvent by solid-liquid mass ratio, 2 ~ 6h is incubated under the conditions of inert atmosphere, stirring and 250 DEG C ~ 450 DEG C, obtains hafnium doping carbonaceous presoma.Graphite crucible equipped with hafnium doping carbonaceous presoma is inserted into retort, 700 ~ 900 DEG C of 1 ~ 3h of insulation, obtain hafnium doping carbonaceous presoma base Carbon Materials, grinding, shaping, base substrate is put into the ethanol solution of the catalyst containing 3 ~ 10wt% and soaked after shaping, air-dry, it is placed in after being fitted into graphite crucible in retort, 1 ~ 4h is incubated under the conditions of inert atmosphere and 1600 DEG C ~ 1900 DEG C, produces hafnium carbide nano whisker.The carbonaceous presoma is resin or pitch.Present invention process is simple, cost is low and environment-friendly, and made product purity is high and draw ratio is big.
Description
Technical field
The invention belongs to hafnium carbide whisker technique field, more particularly 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 tensile strength, fabulous heat
Stability and chemical stability, good decay resistance and anti-wear performance, good heat conduction and electric conductivity, these are excellent
Performance makes it may be used as reinforcement (the field one-dimensional HfC of the pine CVD of high-performance ceramic based composites or carbon/carbon composite
Synthesis, Flied emission and its modified C/C composite Ph.D. Dissertations, Northwestern Polytechnical University, 2014.11).Carbide hafnium
The electric emissivity of whisker is higher than traditional polycrystalline tungsten filament, and its performance is even more preferable than SiC whisker, and someone predicts that it is next
It is alternative in the daily and filament material of lighting for medical use (J. V. Milewski, P. D. Milewski. Single crystal
whisker electric light filament [P]. US:4864186, 1989. ).In addition, hafnium carbide nano whisker
With low work function, it is set easily to discharge electronics；High mechanical stability and low surface mobility can reduce survival
The influence of gas absorption and Ions Bombardment, make emission current more stable, hafnium carbide nano whisker has been applied to Flied emission at present
(A.Mackie, R.L.Hartman, P.R.Davis.High current density field emission in device
from transition metal carbides(J). Applied Surface Science,1993,67(1-4):29-
35.)。
At present, the research report about hafnium carbide whisker is less, and its preparation mainly uses CVD.Last century the eighties,
Futamoto et al. (M. Futamoto, I. Yuito, U. Kawabe. Hafnium carbide and nitride
whisker growth by chemical vapor deposition(J). Journal of Crystal Growth,
1983,61(1):69-74.) hafnium carbide whisker is prepared for using CVD.Detailed process is：At ambient pressure, low-temperature space is heated
The HfCl for making solid phase to 250 DEG C4Powder is sublimed into gas and and CH4And H2High-temperature region is passed through together to chemically react, and is finally existed
HfC whiskers are obtained in the graphite base of high-temperature region.Wherein, HfCl4For hafnium source, CH4For carbon source, H2For reducing gas, it is put in adjacent
Nickel (Ni) piece between graphite base is as catalyst.The growth course of hafnium carbide whisker is by VLS mechanism controls, its diameter and length
Degree is maximum respectively can be to 25 μm and 4.5 mm.
(S. Motojima, the Y. Kawashima. Chemical vapour growth of HfC such as Motojima
whiskers and their morphology (J). Journal of Materials Science, 1996, 31
(14):More detailed research 3697-3700.) has been carried out to the atmospheric pressure cvd preparation process condition of HfC whiskers.Depositing temperature is
1050-1250 DEG C, HfCl4The reaction of gas source hafnium metal powder and chlorine under the conditions of 700 DEG C, and it is loaded into reaction zone with argon gas
Domain and CH4And H2Reaction, HfC whiskers are grown in the graphite base for be loaded with metal catalyst particles.
Above-mentioned atmospheric pressure cvd preparation technology is higher to equipment requirement, HfCl4Gas flow is difficult to control, the hafnium carbide of preparation
Whisker purity is low, diameter is big, draw ratio is small, and it is higher to prepare cost.
In recent years, Yuan etc. (J.S. Yuan, H. Zhang, J. Tang, N. Shinya, K. Nakajima,
L.C. Qin. Synthesis and characterization of single crystalline hafnium
carbide nanowires (J). Journal of the American Ceramic Society, 2012,95(7):
2352-2355.) the smaller HfC nanometer monocrystalline whiskers of diameter have been prepared using CVD.They are 10-1Under Pa negative pressure,
HfCl4-CH4-H2Reaction system in be successfully prepared HfC nanometer monocrystalline whiskers.Synthesis temperature is 1280 DEG C, and growth substrate is
Graphite flake, metallic catalyst are the Ni nano particles of tens nanometers of diameter.The prepared a diameter of 20 ~ 80nm of HfC nano whiskers,
Length is tens microns.Though hafnium carbide whisker purity prepared by this method is small compared with high and diameter, reaction condition is harsher,
HfCl4Gas flow is unmanageable and preparation cost is still higher.
The content of the invention
It is contemplated that overcome prior art defect, it is therefore an objective to provide that a kind of technique is simple, reaction condition is gentle, is prepared into
This low and environment-friendly hafnium carbide nano whisker preparation method, the hafnium carbide nano whisker purity prepared with this method are high and long
Footpath is than big.
To achieve the above object, the technical solution adopted by the present invention comprises the concrete steps that：
Step 1: the preparation of hafnium doping pitch or hafnium doping resin
Pitch after crushing or resin are dissolved in organic solvent, the mass ratio of solute and solvent is 1 ︰（2~5）, standing 1 ~
5h, filtering, the filtrate after filtering is distilled under the conditions of 125 ~ 150 DEG C, producing pitch organic solvent soluble constituent or resin has
Solvent soluble constituent.
30 ~ 50wt% organic hafnium is mixed or by 30 ~ 50wt%'s with 50 ~ 70wt% pitch organic solvent soluble constituent
Organic hafnium mixes with 50 ~ 70wt% resin organic solvent soluble constituent, obtains organic hafnium and pitch organic solvent soluble constituent
The mixture of mixture or organic hafnium and resin organic solvent soluble constituent；It is again 1 ︰ (1 ~ 3) by solid-liquid mass ratio, by organic hafnium
Have with the mixture of pitch organic solvent soluble constituent or be dissolved in the mixture of organic hafnium and resin organic solvent soluble constituent
In solvent, stir 2 ~ 3h, obtain organic hafnium and pitch organic solvent soluble constituent mixed liquor or organic hafnium and resin it is organic
The mixed liquor of solvent-soluble ingredients.
Organic hafnium is with pitch organic solvent soluble constituent mixed liquor or solvable by organic hafnium and resin organic solvent
Component mixed liquor is moved in reactor, under inert atmosphere and stirring condition, is warming up to 250 DEG C ~ 450 DEG C, is incubated 2 ~ 6h；Then
Stop stirring, in an inert atmosphere natural cooling, obtain hafnium doping pitch or hafnium doping resin.
Step 2: the preparation of hafnium doping asphalt base charcoal materials or hafnium doping resin base Carbon Materials
The graphite crucible for graphite crucible equipped with hafnium doping pitch being placed in retort or adulterated hafnium resin is placed in charcoal
Change in stove, 700 ~ 900 DEG C are warming up to 2 ~ 10 DEG C/min speed, be incubated 1 ~ 3h, natural cooling, produce hafnium doping Pitch-based Carbon
Material or hafnium doping resin base Carbon Materials.
Step 3: the preparation of hafnium carbide nano whisker
Hafnium is adulterated into asphalt base charcoal materials or hafnium doping resin base Carbon Materials are ground to the powder that particle diameter is 30 ~ 100 μm,
Add in mould, mechanical pressing, the demoulding, produce base substrate；Base substrate is put into the ethanol solution of the catalyst containing 3 ~ 10wt% immersion 5 ~
40min, natural air drying；It is placed in after air-dried base substrate is fitted into graphite crucible again in retort, under inert atmosphere protection, with 2 ~ 10
DEG C/min speed is warming up to 1600 DEG C ~ 1900 DEG C, 1 ~ 4h is heat-treated, natural cooling, produces hafnium carbide nano whisker.
The pitch is asphalt or coal tar pitch.
Organic hafnium is in acetylacetone,2,4-pentanedione hafnium, cyclopentadienyl group tri-chlorination hafnium, pentamethylcyclopentadiene base tri-chlorination hafnium
One kind.
The catalyst is one kind in ferric nitrate, nickel nitrate, cobalt nitrate.
The organic solvent is one kind in toluene, dimethylbenzene, absolute ethyl alcohol.
The machine pressure refers to 2 ~ 5min of pressurize under the conditions of 90 ~ 190MPa.
The rotating speed of the stirring is 200 ~ 500r/min.
The inert gas is argon gas or is nitrogen.
Due to there is following good effect compared with prior art using above-mentioned technical proposal, the present invention：
(1) present invention is using pitch or resin organic solvent soluble constituent as carbon source, using organic hafnium as hafnium source, makees in catalyst
Under, reacted by the copyrolysis in carbon source and hafnium source and hafnium carbide nano whisker is made in charcoal material surface.
(2) present invention can be realized to carbon by adjusting the proportioning of carbon source and hafnium source and the heat treatment temperature of base substrate and time
Change the control of hafnium nano whisker diameter and length.
(3) hafnium carbide nano whisker purity prepared by the present invention is high, a diameter of 10 ~ 200nm of hafnium carbide nano whisker, long
Spend for 10 ~ 300 μm.
(4) preparation technology of hafnium carbide nano whisker provided by the invention is simple, and preparation cost is low, environment-friendly.
Therefore, the present invention has the characteristics of technique is simple, reaction condition is gentle, preparation cost is low and environment-friendly, with this
Hafnium carbide nano whisker purity prepared by method is high and draw ratio is big.
Brief description of the drawings
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.
Embodiment
The invention will be further described with reference to the accompanying drawings and detailed description, not to the limit of its protection domain
System.
In present embodiment：The machine pressure refers to 2 ~ 5min of pressurize under the conditions of 90 ~ 190MPa；The stirring turns
Speed is 200 ~ 500r/min.Repeated no more in embodiment.
Embodiment 1
A kind of hafnium carbide nano whisker and preparation method thereof.The preparation method comprises the concrete steps that：
Step 1: the preparation of hafnium doping pitch
Pitch after crushing is dissolved in organic solvent, the mass ratio of solute and solvent is 1 ︰（2~5）, stand 1 ~ 5h, mistake
Filter, the filtrate after filtering is distilled under the conditions of 125 ~ 150 DEG C, produces pitch organic solvent soluble constituent.
40 ~ 50wt% organic hafnium is mixed with 50 ~ 60wt% pitch organic solvent soluble constituent, obtains organic hafnium and drip
The mixture of blue or green organic solvent soluble constituent；It is again 1 ︰ (1 ~ 3) by solid-liquid mass ratio, organic hafnium and pitch organic solvent is solvable
The mixture of component is dissolved in organic solvent, is stirred 2 ~ 3h, is obtained the mixed liquor of organic hafnium and pitch organic solvent soluble constituent.
Organic hafnium and pitch organic solvent soluble constituent mixed liquor are moved in reactor, in inert atmosphere and stirring
Under the conditions of, 250 DEG C ~ 350 DEG C are warming up to, is incubated 4 ~ 6h；Then stirring is stopped, natural cooling, obtains hafnium and mix in an inert atmosphere
Miscellaneous pitch.
Step 2: the preparation of hafnium doping asphalt base charcoal materials
Graphite crucible equipped with hafnium doping pitch is placed in retort, 700 ~ 800 are warming up to 2 ~ 6 DEG C/min speed
DEG C, 2 ~ 3h is incubated, natural cooling, produces hafnium doping asphalt base charcoal materials.
Step 3: the preparation of hafnium carbide nano whisker
Hafnium doping asphalt base charcoal materials are ground to the powder that particle diameter is 30 ~ 100 μm, adds in mould, mechanical pressing, takes off
Mould, produce base substrate；Base substrate is put into 5 ~ 40min of immersion, natural air drying in the ethanol solution of the catalyst containing 3 ~ 6wt%；It will air-dry again
Base substrate is placed in retort after being fitted into graphite crucible, and under inert atmosphere protection, 1600 DEG C are warming up to 2 ~ 6 DEG C/min speed
~ 1800 DEG C, 2 ~ 4h is heat-treated, natural cooling, produces hafnium carbide nano whisker.
The pitch is asphalt.
Organic hafnium is acetylacetone,2,4-pentanedione hafnium.
The catalyst is ferric nitrate.
The organic solvent is toluene.
The inert gas is argon gas.
Embodiment 2
A kind of hafnium carbide nano whisker and preparation method thereof.The preparation method comprises the concrete steps that：
Step 1: the preparation of hafnium doping pitch
Pitch after crushing is dissolved in organic solvent, the mass ratio of solute and solvent is 1 ︰（2~5）, stand 1 ~ 5h, mistake
Filter, the filtrate after filtering is distilled under the conditions of 125 ~ 150 DEG C, produces pitch organic solvent soluble constituent.
30 ~ 40wt% organic hafnium is mixed with 60 ~ 70wt% pitch organic solvent soluble constituent, obtains organic hafnium and drip
The mixture of blue or green organic solvent soluble constituent；It is again 1 ︰ (1 ~ 3) by solid-liquid mass ratio, organic hafnium and pitch organic solvent is solvable
The mixture of component is dissolved in organic solvent, is stirred 2 ~ 3h, is obtained the mixed liquor of organic hafnium and pitch organic solvent soluble constituent.
Organic hafnium and pitch organic solvent soluble constituent mixed liquor are moved in reactor, in inert atmosphere and stirring
Under the conditions of, 350 DEG C ~ 450 DEG C are warming up to, is incubated 2 ~ 4h；Then stirring is stopped, natural cooling, obtains hafnium and mix in an inert atmosphere
Miscellaneous pitch.
Step 2: the preparation of hafnium doping asphalt base charcoal materials
Graphite crucible equipped with hafnium doping pitch is placed in retort, 800 are warming up to 6 ~ 10 DEG C/min speed ~
900 DEG C, 1 ~ 2h is incubated, natural cooling, produces hafnium doping asphalt base charcoal materials.
Step 3: the preparation of hafnium carbide nano whisker
Hafnium doping asphalt base charcoal materials are ground to the powder that particle diameter is 30 ~ 100 μm, adds in mould, mechanical pressing, takes off
Mould, produce base substrate；Base substrate is put into 5 ~ 40min of immersion, natural air drying in the ethanol solution of the catalyst containing 6 ~ 10wt%；Again by wind
Dry body body is placed in retort after being fitted into graphite crucible, under inert atmosphere protection, is warming up to 6 ~ 10 DEG C/min speed
1700 DEG C ~ 1900 DEG C, 1 ~ 3h is heat-treated, natural cooling, produces hafnium carbide nano whisker.
The pitch is asphalt.
Organic hafnium is acetylacetone,2,4-pentanedione hafnium.
The catalyst is ferric nitrate.
The organic solvent is toluene.
The inert gas is argon gas
Embodiment 3
A kind of hafnium carbide nano whisker and preparation method thereof.In addition to following technical parameters, remaining is the same as embodiment 1：
The pitch is coal tar pitch.
Organic hafnium is cyclopentadienyl group tri-chlorination hafnium.
The catalyst is nickel nitrate.
The organic solvent is dimethylbenzene.
The inert gas is nitrogen.
Embodiment 4
A kind of hafnium carbide nano whisker and preparation method thereof.In addition to following technical parameters, remaining is the same as embodiment 2：
The pitch is coal tar pitch.
Organic hafnium is cyclopentadienyl group tri-chlorination hafnium.
The catalyst is nickel nitrate.
The organic solvent is dimethylbenzene.
The inert gas is nitrogen.
Embodiment 5
A kind of hafnium carbide nano whisker and preparation method thereof.The preparation method comprises the concrete steps that：
Step 1: the preparation of hafnium doping resin
Resin after crushing is dissolved in organic solvent, the mass ratio of solute and solvent is 1 ︰（2~5）, stand 1 ~ 5h, mistake
Filter, the filtrate after filtering is distilled under the conditions of 125 ~ 150 DEG C, produces resin organic solvent soluble constituent.
40 ~ 50wt% organic hafnium is mixed with 50 ~ 60wt% resin organic solvent soluble constituent, obtains organic hafnium and tree
The mixture of fat organic solvent soluble constituent；It is again 1 ︰ (1 ~ 3) by solid-liquid mass ratio, organic hafnium and resin organic solvent is solvable
The mixture of component is dissolved in organic solvent, is stirred 2 ~ 3h, is obtained 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, in inert atmosphere and stirring condition
Under, 250 DEG C ~ 350 DEG C are warming up to, is incubated 4 ~ 6h；Then stop stirring, in an inert atmosphere natural cooling, obtain hafnium doping tree
Fat.
Step 2: the preparation of hafnium doping resin base Carbon Materials
The graphite crucible of hafnium doping resin is placed in retort, 700 ~ 800 DEG C are warming up to 2 ~ 6 DEG C/min speed,
2 ~ 3h is incubated, natural cooling, produces hafnium doping resin base Carbon Materials.
Step 3: the preparation of hafnium carbide nano whisker
Hafnium doping resin base Carbon Materials are ground to the powder that particle diameter is 30 ~ 100 μm, adds in mould, mechanical pressing, takes off
Mould, produce base substrate；Base substrate is put into 5 ~ 40min of immersion, natural air drying in the ethanol solution of the catalyst containing 3 ~ 6wt%；It will air-dry again
Base substrate is placed in retort after being fitted into graphite crucible, and under inert atmosphere protection, 1600 DEG C are warming up to 2 ~ 6 DEG C/min speed
~ 1800 DEG C, 2 ~ 4h is heat-treated, natural cooling, produces hafnium carbide nano whisker.
Organic hafnium is pentamethylcyclopentadiene base tri-chlorination hafnium.
The catalyst is cobalt nitrate.
The organic solvent is absolute ethyl alcohol.
The inert gas is argon gas.
Embodiment 6
A kind of hafnium carbide nano whisker and preparation method thereof.The preparation method comprises the concrete steps that：
Step 1: the preparation of hafnium doping resin
Resin after crushing is dissolved in organic solvent, the mass ratio of solute and solvent is 1 ︰（2~5）, stand 1 ~ 5h, mistake
Filter, the filtrate after filtering is distilled under the conditions of 125 ~ 150 DEG C, produces resin organic solvent soluble constituent.
30 ~ 40wt% organic hafnium is mixed with 60 ~ 70wt% resin organic solvent soluble constituent, obtains organic hafnium and tree
The mixture of fat organic solvent soluble constituent；It is again 1 ︰ (1 ~ 3) by solid-liquid mass ratio, organic hafnium and resin organic solvent is solvable
The mixture of component is dissolved in organic solvent, is stirred 2 ~ 3h, is obtained 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, in inert atmosphere and stirring condition
Under, 350 DEG C ~ 450 DEG C are warming up to, is incubated 2 ~ 4h；Then stop stirring, in an inert atmosphere natural cooling, obtain hafnium doping tree
Fat.
Step 2: the preparation of hafnium doping resin base Carbon Materials
The graphite crucible of hafnium doping resin is placed in retort, 800 ~ 900 DEG C are warming up to 6 ~ 10 DEG C/min speed,
1 ~ 2h is incubated, natural cooling, produces hafnium doping resin base Carbon Materials.
Step 3: the preparation of hafnium carbide nano whisker
Hafnium doping resin base Carbon Materials are ground to the powder that particle diameter is 30 ~ 100 μm, adds in mould, mechanical pressing, takes off
Mould, produce base substrate；Base substrate is put into 5 ~ 40min of immersion, natural air drying in the ethanol solution of the catalyst containing 6 ~ 10wt%；Again by wind
Dry body body is placed in retort after being fitted into graphite crucible, under inert atmosphere protection, is warming up to 6 ~ 10 DEG C/min speed
1700 DEG C ~ 1900 DEG C, 1 ~ 3h is heat-treated, natural cooling, produces hafnium carbide nano whisker.
Organic hafnium is pentamethylcyclopentadiene base tri-chlorination hafnium.
The catalyst is cobalt nitrate.
The organic solvent is absolute ethyl alcohol.
The inert gas is argon gas.
Present embodiment has following good effect compared with prior art：
(1) present embodiment is using pitch or resin organic solvent soluble constituent as carbon source, using organic hafnium as hafnium source,
Under catalyst action, reacted by the copyrolysis in carbon source and hafnium source and hafnium carbide nano whisker is made in charcoal material surface.
(2) present embodiment is by adjusting the proportioning of carbon source and hafnium source and the heat treatment temperature of base substrate and time energy
Realize the control to hafnium carbide nano whisker diameter and length.
(3) Fig. 1 is a kind of XRD spectra of hafnium carbide nano whisker prepared by present embodiment, the θ of the angle of diffraction 2 in figure
Diffraction maximum at=33 °, 39 °, 56 °, 67 °, 70 °, 83 ° corresponds to β-HfC's respectively（111）、（200）、（220）、（311）、
（222）、（400）Crystal face, the hafnium carbide nano whisker for showing to prepare is β-HfC phases；
(4) Fig. 2 is a kind of SEM photograph of hafnium carbide nano whisker prepared by embodiment 2.It is nanocrystalline as can be seen from Figure 2
Palpus grows in line style, and diameter of whiskers is 10 ~ 200nm, and length is 10 ~ 300 μm, and whisker end is observed that molten catalyst simultaneously
Bead.
(5) preparation technology for the hafnium carbide nano whisker that present embodiment provides is simple, and preparation cost is low, environment friend
It is good.
Therefore, present embodiment has the spy that technique is simple, reaction condition is gentle, preparation cost is low and environment-friendly
Point, the hafnium carbide nano whisker purity prepared with this method is high and draw ratio is big.
Claims (8)
1. a kind of preparation method of hafnium carbide nano whisker, it is characterised in that the preparation method comprises the concrete steps that：
Step 1: the preparation of hafnium doping pitch or hafnium doping resin
Pitch after crushing or resin are dissolved in organic solvent, the mass ratio of solute and solvent is 1 ︰ (2~5), standing 1~
5h, filtering, the filtrate after filtering is distilled under the conditions of 125~150 DEG C, producing pitch organic solvent soluble constituent or resin has
Solvent soluble constituent；
30~50wt% organic hafnium is mixed with 50~70wt% pitch organic solvent soluble constituent or by 30~50wt%
Organic hafnium mixed with 50~70wt% resin organic solvent soluble constituent, obtain organic hafnium and solvable group of pitch organic solvent
The mixture of the mixture or organic hafnium and resin organic solvent soluble constituent that divide；It is again 1 ︰ (1~3) by solid-liquid mass ratio, will
Mixture of organic hafnium with pitch organic solvent soluble constituent or the mixture by organic hafnium and resin organic solvent soluble constituent
It is dissolved in organic solvent, stirs 2~3h, obtains mixed liquor or organic hafnium and the tree of organic hafnium and pitch organic solvent soluble constituent
The mixed liquor of fat organic solvent soluble constituent；
By organic hafnium and pitch organic solvent soluble constituent mixed liquor or by organic hafnium and resin organic solvent soluble constituent
Mixed liquor is moved in reactor, under inert atmosphere and stirring condition, is warming up to 250 DEG C~450 DEG C, is incubated 2~6h；Then stop
Only stir, in an inert atmosphere natural cooling, obtain hafnium doping pitch or hafnium doping resin；
Step 2: the preparation of hafnium doping asphalt base charcoal materials or hafnium doping resin base Carbon Materials
The graphite crucible for graphite crucible equipped with hafnium doping pitch being placed in retort or adulterated hafnium resin is placed in retort
In, 700~900 DEG C are warming up to 2~10 DEG C/min speed, 1~3h is incubated, natural cooling, produces hafnium doping Pitch-based Carbon
Material or hafnium doping resin base Carbon Materials；
Step 3: the preparation of hafnium carbide nano whisker
Hafnium is adulterated into asphalt base charcoal materials or hafnium doping resin base Carbon Materials are ground to the powder that particle diameter is 30~100 μm, is added
Enter in mould, mechanical pressing, be stripped, produce base substrate；Base substrate is put into the ethanol solution of the catalyst containing 3~10wt% and soaks 5
~40min, natural air drying；It is placed in after air-dried base substrate is fitted into graphite crucible again in retort, under inert atmosphere protection, with 2
~10 DEG C/min speed is warming up to 1600 DEG C~1900 DEG C, is heat-treated 1~4h, natural cooling, produces hafnium carbide nano whisker.
2. the preparation method of hafnium carbide nano whisker according to claim 1, it is characterised in that the pitch is asphalt
Or coal tar pitch.
3. the preparation method of hafnium carbide nano whisker according to claim 1, it is characterised in that organic hafnium is levulinic
One kind in ketone 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 the catalyst be ferric nitrate,
One kind in nickel nitrate, cobalt nitrate.
5. the preparation method of hafnium carbide nano whisker according to claim 1, it is characterised in that the organic solvent be toluene,
One kind in dimethylbenzene, absolute ethyl alcohol.
6. the preparation method of hafnium carbide nano whisker according to claim 1, it is characterised in that the machine pressure refers to 90~
2~5min of pressurize under the conditions of 190MPa.
7. the preparation method of hafnium carbide nano whisker according to claim 1, it is characterised in that the rotating speed of the stirring is 200
~500r/min.
8. the preparation method of hafnium carbide nano whisker according to claim 1, it is characterised in that the inert gas is argon gas
Or it is nitrogen.
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| CN201610079179.3A CN105780123B (en) | 2016-02-04 | 2016-02-04 | A kind of hafnium carbide nano whisker and preparation method thereof |
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| CN108083808B (en) * | 2016-11-21 | 2021-02-12 | 武汉科技大学 | Nano hafnium carbide ceramic organic precursor and preparation method thereof |
| 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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