CN103194734A - Preparation method of self-assembled three-dimensional hafnium carbide whisker network structure - Google Patents
Preparation method of self-assembled three-dimensional hafnium carbide whisker network structure Download PDFInfo
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- CN103194734A CN103194734A CN2013101299800A CN201310129980A CN103194734A CN 103194734 A CN103194734 A CN 103194734A CN 2013101299800 A CN2013101299800 A CN 2013101299800A CN 201310129980 A CN201310129980 A CN 201310129980A CN 103194734 A CN103194734 A CN 103194734A
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Abstract
The invention relates to a preparation method of a self-assembled three-dimensional hafnium carbide whisker network structure. In the method, a template for the three-dimensional network structure is not used, the self-assembled three-dimensional HfC whisker network structure is prepared on the surface of a 2-dimensional needle punched carbon felt for the first time directly by a catalyst aided chemical vapor deposition method, and the prepared product is lower in impurity content in comparison with other elements introduced by a template method.
Description
Technical field
The present invention relates to a kind of preparation method of self assembled three-dimensional hafnium carbide whisker network structure, the preparation method of especially a kind of self assembled three-dimensional hafnium carbide (HfC) whisker network structure.
Background technology
HfC has the fusing point (3890 ° of C) of superelevation, is one of ultrahigh-temperature pottery of infusibility; Simultaneously, it also have high rigidity (Vickers' hardness: 26.1GPa), high elastic coefficient (350 – 510GPa) and good chemical stability.Because this a series of excellent properties, it has been used as wear-resistance thin film and the thermal protection coating in aerospace field; In addition, HfC whisker or nano wire also can be used as the enhancing body of ultrahigh-temperature matrix material, simultaneously because it stablizes the field emmision material that also can be used as the point-like electron source with special physicochemical character.Therefore, three-dimensional HfC whisker network structure has potential important application in the miniature function under hyperthermal environments.One-dimensional material is because its special applications in the micro-nano technical field has received a large amount of concerns, for example: micron-sized fiber or whisker, nano level nano wire or nanotube.A series of material such as carbon, carbide, oxide compound, semiconductor material, metal etc. have been developed and have been prepared into the one dimension line structure, and their special physical propertiess make it obtain important application at nanoelectronic and optoelectronic areas.And micro-nano rank functional apparatus preparation needs, and the multidimensional structure that is assembled into by one-dimensional material shows its potential technical significance just gradually.At present, existing investigator has prepared two-dimentional oxide nano thread or nano belt network structure by the autocatalysis chemical Vapor deposition process in smooth substrate, and it can use the miniature function as optoelectronic device; Simultaneously, along with the development of lithium cell, the cathode material that three-dimensional Graphene network structure can be used as ultracapacitor has received very big concern, and preparing the most frequently used a kind of method of this structure is to be the chemical gaseous phase depositing process of masterplate and catalyzer with the nickel foam.Yet, adopt catalytic chemical vapor deposition technique to prepare one-dimensional metal carbide material self assembled three-dimensional structure and yet there are no report at home and abroad.
Summary of the invention
The technical problem that solves
For fear of the deficiencies in the prior art part, the present invention proposes a kind of preparation method of self assembled three-dimensional hafnium carbide whisker network structure, has prepared new three-dimensional HfC whisker network structure.
Technical scheme
A kind of preparation method of self assembled three-dimensional hafnium carbide whisker network structure is characterized in that step is as follows:
Step 1: compound concentration is the Ni (NO of 0.05～2mol/L
3)
2Or NiCl
2Ethanolic soln;
Step 2: the 2D needled carbon felt that cleans up is placed in the solution of step 1 preparation and soaks 1～2h, take out oven dry in the loft drier that 2D needled carbon felt is placed on 40～55 ℃ then;
Step 3: the 2D needled carbon felt of step 2 oven dry is put in the deposition mould in the tube type resistance furnace, is evacuated to 2kPa, feed inert argon as shielding gas; Heat-up rate with 5～10 ℃/min rises to 1200～1400 ℃ with furnace temperature, feeds H then
2, HfCl
4And CH
4Gas, control H
2, HfCl
4And CH
4Dividing potential drop be respectively 0.80～0.98,0.10～0.01,0.10～0.01; Regulate vacuum pumping speed, the deposition pressure in the CVD stove is controlled at 2kPa～30kPa; Depositing time is 2～10h; Deposition stops to feed reactant gases after finishing, and closes heating power supply and lowers the temperature naturally, makes self assembled three-dimensional HfC whisker network structure at 2D needled carbon felt deposition surface.
The HfC l that feeds in the described step 3
4Gas flow is 80～150mg/min.
Described Ni (NO
3)
2Be analytical pure, quality percentage composition 〉=99.8%.
Described NiCl
2Be analytical pure, quality percentage composition 〉=99.8%.
Described ethanol is analytical pure, quality percentage composition 〉=99.8%.
Described HfCl
4Be analytical pure, quality percentage composition 〉=99.8%.
Described Ar is purity greater than 99.999% high-purity gas.
Described CH
4For purity greater than 99.999% high-purity gas.
Described H
2For purity greater than 99.999% high-purity gas.
Beneficial effect
The preparation method of a kind of self assembled three-dimensional hafnium carbide whisker network structure that the present invention proposes, do not use the masterplate of three-dimensional net structure, directly by the auxiliary chemical gaseous phase depositing process of catalyzer first in the surface preparation of 2D needled carbon felt the three-dimensional HfC whisker network structure of self-assembly, the foreign matter content that prepared product is compared other elements that the masterplate method introduces is few.
Description of drawings
Fig. 1: be method flow diagram of the present invention;
Fig. 2: be the prepared self assembled three-dimensional HfC of the present invention whisker network structure microscopic appearance
Fig. 3: be the prepared self assembled three-dimensional HfC of the present invention whisker network structure microscopic appearance
Fig. 4: choose diffraction pattern under the TEM, prove that the HfC whisker that makes up three-dimensional HfC whisker network structure is monocrystalline.
Embodiment
Now in conjunction with the embodiments, accompanying drawing is further described the present invention:
Embodiment 1:
1, configuration concentration is the Ni (NO of 1mol/L
3)
2Ethanolic soln.
2, will clean up the 2D carbon felt that is of a size of 60mm * 45mm * 10mm and be put in the described solution of step 1 and soak 2h, take out dry for standby in the loft drier that the carbon felt is placed on 50 ℃ then.
3, chemical vapor deposition (CVD) prepared self assembled three-dimensional HfC whisker network structure, method is as follows:
Ni (NO will be impregnated with in the step 2
3)
22D needled carbon felt be put in deposition in the vertical tube type resistance furnace with in the graphite jig, be evacuated to about 2kPa, feed inert argon as shielding gas, with the heat-up rate of 5 ℃/min furnace temperature is risen to 1250 ℃; When temperature reaches depositing temperature in the stove, feed H
2, HfCl
4And CH
4Gas, control H
2, HfCl
4And CH
4Dividing potential drop be respectively 0.90,0.05,0.05, HfCl
4Gas flow is 115mg/min; Regulate vacuum pumping speed, the deposition pressure in the CVD stove is controlled at 10kPa; Depositing time is 8h.Closing heating power supply after deposition finishes lowers the temperature naturally.Namely make self assembled three-dimensional HfC whisker network structure at 2D needled carbon felt deposition surface, the about 50 μ m of single HfC diameter of whiskers of assembling three-dimensional net structure; In addition, except growth three-dimensional net structure is arranged on carbon felt surface, also having diameter is the HfC whisker of several microns sizes.
Embodiment 2:
1, configuration concentration is the NiCl of 0.5mol/L
2Ethanolic soln.
2, will clean up the 2D carbon felt that is of a size of 60mm * 45mm * 10mm and be put in the described solution of step 1 and soak 2h, take out dry for standby in the loft drier that the carbon felt is placed on 50 ℃ then.
3, chemical vapor deposition (CVD) prepared self assembled three-dimensional HfC whisker network structure, method is as follows:
NiCl will be impregnated with in the step 2
22D needled carbon felt be put in deposition in the vertical tube type resistance furnace with in the graphite jig, be evacuated to about 2kPa, feed inert argon as shielding gas, with the heat-up rate of 5 ℃/min furnace temperature is risen to 1300 ℃; When temperature reaches depositing temperature in the stove, feed H
2, HfCl
4And CH
4Gas, control H
2, HfCl
4And CH
4Dividing potential drop be respectively 0.80,0.10,0.10, HfCl
4Gas flow is 150mg/min; Regulate vacuum pumping speed, the deposition pressure in the CVD stove is controlled at 5kPa; Depositing time is 6h.Closing heating power supply after deposition finishes lowers the temperature naturally.Namely make self assembled three-dimensional HfC whisker network structure at 2D needled carbon felt deposition surface; In addition, diameter being arranged is that the HfC whisker growth of several microns sizes is on carbon felt surface.
Claims (9)
1. the preparation method of a self assembled three-dimensional hafnium carbide whisker network structure is characterized in that step is as follows:
Step 1: compound concentration is the Ni (NO of 0.05～2mol/L
3)
2Or NiCl
2Ethanolic soln;
Step 2: the 2D needled carbon felt that cleans up is placed in the solution of step 1 preparation and soaks 1～2h, take out oven dry in the loft drier that 2D needled carbon felt is placed on 40～55 ℃ then;
Step 3: the 2D needled carbon felt of step 2 oven dry is put in the deposition mould in the tube type resistance furnace, is evacuated to 2kPa, feed inert argon as shielding gas; Heat-up rate with 5～10 ℃/min rises to 1200～1400 ℃ with furnace temperature, feeds H then
2, HfCl
4And CH
4Gas, control H
2, HfCl
4And CH
4Dividing potential drop be respectively 0.80～0.98,0.10～0.01,0.10～0.01; Regulate vacuum pumping speed, the deposition pressure in the CVD stove is controlled at 2kPa～30kPa; Depositing time is 2～10h; Deposition stops to feed reactant gases after finishing, and closes heating power supply and lowers the temperature naturally, makes self assembled three-dimensional HfC whisker network structure at 2D needled carbon felt deposition surface.
2. according to the preparation method of the described self assembled three-dimensional hafnium carbide of claim 1 whisker network structure, it is characterized in that: the HfCl that feeds in the described step 3
4Gas flow is 80～150mg/min.
3. according to the preparation method of the described self assembled three-dimensional hafnium carbide of claim 1 whisker network structure, it is characterized in that: described Ni (NO
3)
2Be analytical pure, quality percentage composition 〉=99.8%.
4. according to the preparation method of the described self assembled three-dimensional hafnium carbide of claim 1 whisker network structure, it is characterized in that: described NiCl
2Be analytical pure, quality percentage composition 〉=99.8%.
5. according to the preparation method of the described self assembled three-dimensional hafnium carbide of claim 1 whisker network structure, it is characterized in that: described ethanol is analytical pure, quality percentage composition 〉=99.8%.
6. according to the preparation method of the described self assembled three-dimensional hafnium carbide of claim 1 whisker network structure, it is characterized in that: described HfCl
4Be analytical pure, quality percentage composition 〉=99.8%.
7. according to the preparation method of the described self assembled three-dimensional hafnium carbide of claim 1 whisker network structure, it is characterized in that: described Ar is purity greater than 99.999% high-purity gas.
8. according to the preparation method of the described self assembled three-dimensional hafnium carbide of claim 1 whisker network structure, it is characterized in that: described CH
4For purity greater than 99.999% high-purity gas.
9. according to the preparation method of the described self assembled three-dimensional hafnium carbide of claim 1 whisker network structure, it is characterized in that: described H
2For purity greater than 99.999% high-purity gas.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693285A (en) * | 2016-01-20 | 2016-06-22 | 西北工业大学 | Method for preparing hafnium carbide (HfC) nano-wires on 2D needled carbon felt |
| CN105780123A (en) * | 2016-02-04 | 2016-07-20 | 武汉科技大学 | Hafnium-carbide nanometer whiskers and preparing method thereof |
| CN107004829A (en) * | 2014-10-31 | 2017-08-01 | Ppg工业俄亥俄公司 | Include the lithium ion battery electrode of graphene carbon particle |
| CN107572525A (en) * | 2017-10-23 | 2018-01-12 | 重庆交通大学 | The preparation method of two-dimentional hafnium carbide nanometer sheet |
| CN111943678A (en) * | 2020-08-14 | 2020-11-17 | 西北工业大学 | HfxZr1-xC ceramic solid solution nanowire and preparation method thereof |
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| US20100316873A1 (en) * | 2006-09-08 | 2010-12-16 | Gm Global Technology Operations, Inc | One-dimensional metal nanostructures |
| 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 |
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2013
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| US20100316873A1 (en) * | 2006-09-08 | 2010-12-16 | Gm Global Technology Operations, Inc | One-dimensional metal nanostructures |
| 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 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107004829A (en) * | 2014-10-31 | 2017-08-01 | Ppg工业俄亥俄公司 | Include the lithium ion battery electrode of graphene carbon particle |
| CN105693285A (en) * | 2016-01-20 | 2016-06-22 | 西北工业大学 | Method for preparing hafnium carbide (HfC) nano-wires on 2D needled carbon felt |
| CN105693285B (en) * | 2016-01-20 | 2018-04-06 | 西北工业大学 | A kind of method that hafnium carbide nano wire is prepared in 2D acupuncture carbon felts |
| CN105780123A (en) * | 2016-02-04 | 2016-07-20 | 武汉科技大学 | Hafnium-carbide nanometer whiskers and preparing method thereof |
| CN105780123B (en) * | 2016-02-04 | 2018-02-09 | 武汉科技大学 | A kind of hafnium carbide nano whisker and preparation method thereof |
| CN107572525A (en) * | 2017-10-23 | 2018-01-12 | 重庆交通大学 | The preparation method of two-dimentional hafnium carbide nanometer sheet |
| CN111943678A (en) * | 2020-08-14 | 2020-11-17 | 西北工业大学 | HfxZr1-xC ceramic solid solution nanowire and preparation method thereof |
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