CN107234241B - A kind of micrometer level porous tungsten and preparation method thereof - Google Patents
A kind of micrometer level porous tungsten and preparation method thereof Download PDFInfo
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- CN107234241B CN107234241B CN201710413422.5A CN201710413422A CN107234241B CN 107234241 B CN107234241 B CN 107234241B CN 201710413422 A CN201710413422 A CN 201710413422A CN 107234241 B CN107234241 B CN 107234241B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
- B22F3/1134—Inorganic fillers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
Abstract
The present invention is a kind of micrometer level porous tungsten and preparation method thereof, belong to porous metal material technical field, its preparation step is: using the micron order pore creating material NaCl obtained through ball mill crushing, tungsten powder and organic additive be added in organic solvent carry out ball milling obtain curtain coating slurry, slurry is cast to form strip after be cut into specific shape；It is put into mold after lamination, carries out Low Temperature Heat Treatment dumping in a vacuum, low temperature hot-press sintering in a vacuum after dumping obtains green compact；Green compact are placed in the deionized water of flowing and remove pore creating material, are dried in a vacuum drying oven, obtain POROUS TUNGSTEN green compact, POROUS TUNGSTEN green compact high temperature sintering under an ar atmosphere obtains the POROUS TUNGSTEN.POROUS TUNGSTEN consistency prepared by the present invention is 35%-90%, and macropore diameter is 3-6 μm, and small aperture is 0.1 μm -0.7 μm, has the advantages of pore size distribution is uniform, pore size is controllable, and porosity change range is big, sintering temperature is substantially reduced.
Description
Technical field
The present invention relates to porous metal material technical fields, and in particular to a kind of micrometer level porous tungsten and preparation method thereof.
Background technique
Tungsten is infusibility non-ferrous metal, and fusing point, boiling point and density are highest in all metals, chemical property also pole
It is stablized, and all soda acids are resistant under room temperature and are corroded, meanwhile, it is extremely heavy that the excellent thermal property of tungsten, mechanical property also enable it have
The purposes wanted.Thus, tungsten be widely used in contemporary mechanics of communication, electronic computer, aerospace exploitation, medical and health, photosensitive material,
Photoelectric material, energy and material and catalyst material etc., especially its porous body or porous matrix material are widely used as high current
The emitter of electronic emission material is poured in the porous cathode of density, ion engine, mercury vapour liquid in mercury ion rocket engine
Isolated vaporizer, high temperature fluid filter and electronic package material etc..
However, the features such as high fusing point of tungsten electrode and great density makes the preparation of POROUS TUNGSTEN, there are certain difficulties, such as
Very high heating temperature is needed, is difficult to select suitable pore creating material etc..Just conventional sintering method common at present and organic matrix leaching
For starching drying and sintering method, have the shortcomings that following obvious: the sintering temperature of conventional sintering method is high, and porosity is lower, hole point
Cloth is uneven；Organic matrix soaking paste drying and sintering method although even aperture distribution easy to operate, sintering temperature is still very high, production
Inefficiency.
It can find the shortcomings that for improvement conventional method, there are many scholars to use with document by consulting domestic and international patent
New method prepares POROUS TUNGSTEN.Patent CN103774184A discloses a kind of method of electrolytic preparation POROUS TUNGSTEN, and this method utilizes
The characteristics of tungsten is electrolysed in molten salt solution by electrochemical action, using AC power source and DC power supply in containing additive
NaOH solution in tungsten metal carry out electrolytic preparation POROUS TUNGSTEN, although POROUS TUNGSTEN even aperture distribution made from this method,
It is that pore size is uncontrollable, porosity is low.Document " Reactive sintering of porous tungsten:A cost
effective sustainable technique for the manufacturing of high current density
Cathodes to be used in flashlamps " disclose a kind of reaction work using aluminium as pore creating material and sintering aid
Change the method for sintering preparation POROUS TUNGSTEN, this method uses the tungsten powder mixing cold moudling of aluminium and pre-oxidation, then molding blank is existed
The technology path of pressureless sintering under reducing gas, since the self-propagating reaction of aluminium and tungsten oxide provides big energy, sintering
Temperature is substantially reduced, and hardness is evenly distributed, but the POROUS TUNGSTEN porosity of this method preparation is lower, and pore size and pattern can not
Control.To sum up, the preparation of POROUS TUNGSTEN is in during ceaselessly exploring and constantly improving.Current present Research also table
Bright, taking the relevant report of pore creating material method preparation POROUS TUNGSTEN all not can be implemented simultaneously both at home and abroad at present, pore creating material is low in cost, makes
Hole works well, pore size is controllable, hole morphological rules, porosity ranges change greatly.
Summary of the invention
The technical problems to be solved by the present invention are: being directed to the deficiency of existing preparation process, one kind is provided in curtain coating slurry
Middle addition pore creating material, the micrometer level porous tungsten and preparation method thereof obtained with tape casting combination hot pressing or pressureless sintering.This side
Method equipment is simple, can operate continuously, high production efficiency, automatization level are high, process stabilizing, and the tape casting diaphragm performance of acquisition is equal
One, diaphragm thickness is controllable, and POROUS TUNGSTEN hole obtained morphological rules, even aperture distribution, hole are adjustable, also, curtain coating slurry
Remaining micro C element can be such that sintering temperature is substantially reduced.
The present invention solves its technical problem, and the following technical solution is employed:
A kind of preparation method of micrometer level porous tungsten, comprising the following steps:
1) raw material NaCl, ethyl alcohol and ball-milling medium are subjected to ball milling, are then dried to obtain NaCl powder；
2) it stocks up: according to NaCl powder, the 32.6-38.4% of tungsten powder, 0%-8.5% that mass percent is 50-60%
Organic solvent and 5.3-7.4% organic additive stock, wherein organic additive includes the polyethylene of 2.5%-3.5%
Butyral, 0.8%-1.2% Hypermer KD-1 and 2.0%-2.7% glycerol；
3) preparation of curtain coating slurry: NaCl powder and tungsten powder and organic additive are added in organic solvent and carry out ball
Mill obtains curtain coating slurry；
4) be cast the processing of strip: the curtain coating slurry that step 3) is obtained is cast drying setting in casting machine, is flowed
Prolong strip, curtain coating strip is cut into specific shape, by the strip lamination of predetermined number of layers, the strip after lamination is under vacuum conditions
Dumping is kept the temperature, then the heat preservation sintering under identical vacuum degree, progress hot pressed sintering obtain green compact again；
5) sintering obtains POROUS TUNGSTEN: green compact are placed in flowing water and rinse, and are then dried to obtain POROUS TUNGSTEN green compact, POROUS TUNGSTEN
Green compact high temperature sintering under an inert atmosphere obtains the POROUS TUNGSTEN.
Specific charging sequence in above scheme, in the step 3) are as follows: first by tungsten powder and NaCl and Hypermer KD-1
It is added to ball milling in organic solvent, adds polyvinyl butyral and glycerol, ball milling obtains curtain coating slurry.
In above scheme, the partial size of the NaCl powder in the step 1) is 3-6 μm.
In above scheme, the organic solvent in the step 1) is the ethyl alcohol and butanone that mass ratio presses 1:1 mixing.
In above scheme, the purity of the tungsten powder in the step 2) is 99.9%, and partial size is 0.5-5 μm.
In above scheme, the sintering temperature of the high temperature sintering in the step 5) is 1300-1700 DEG C, soaking time 1-
3h, sintering pressure 0-10MPa.
In above scheme, the vacuum condition in the step 4) is better than 9.9 × 10-3The vacuum degree of Pa, holding temperature are
780 DEG C, soaking time 2h, sintering pressure 10-30MPa.
In above scheme, the drying in the step 5) is vacuum drying, and drying temperature is 80 degree, and drying time is 12 small
When.
In above scheme, the purity of the raw material NaCl in the step 1) is 99.9%, crosses 60 meshes.
The micrometer level porous tungsten that the preparation method of the micrometer level porous tungsten is prepared, the macropore hole of the POROUS TUNGSTEN
Diameter is 3-6 μm, and small aperture is 0.1 μm -0.7 μm, and consistency range is 35%-90%.
The POROUS TUNGSTEN that the present invention obtains has following clear advantage compared with prior art:
First, making film strips component uniform using casting technology, and then keep the porous material pore size distribution obtained uniform.Simultaneously
Casting technology also has that process equipment is simple, can operate continuously, the advantages of high production efficiency, automatization level are high, process stabilizing.
Second, pore creating material NaCl is low in cost, size and pattern can by simple technology controlling and process, meanwhile, curtain coating material
Slurry is stable complex phase slurry, and settlement stability caused by can solving pore creating material NaCl and W density variation greatly realizes porous W hole
Rate accurately controls on a large scale.
Third, the organic matter that casting technology is introduced into can remain minimal amount of unsetting C in dumping, be conducive to the diffusion of W
Mass transfer, hence it is evident that reduce the temperature of W sintering, traditional W pressureless sintering temperature more than 2000 DEG C is reduced to 1400- by the present invention
1700℃。
Detailed description of the invention
Fig. 1 is the preparation technology flow chart of POROUS TUNGSTEN.
Fig. 2 is the NaCl powder SEM spectrum that ball milling obtains for 24 hours in the embodiment of the present invention 5.
Fig. 3 is the green compact SEM spectrum in the embodiment of the present invention 5.
Fig. 4 is the POROUS TUNGSTEN green compact SEM spectrum in the embodiment of the present invention 5.
Fig. 5 is the POROUS TUNGSTEN SEM spectrum in the embodiment of the present invention 5.
Specific embodiment
SEM spectrum is obtained by (U.S., FEI Co.) field emission scanning electron microscope of Quanta FEG 250.
Density is measured by Archimedes's drainage, is first sealed sample with one layer of very thin vaseline before test, fine and close
Degree is actual density and theoretical density (19.30g/cm3The ratio between).
The technique for the tape casting combination high temperature sintering preparation POROUS TUNGSTEN that the present invention uses specifically:
A kind of preparation method of micrometer level porous tungsten, comprising the following steps:
1) raw material NaCl, ethyl alcohol and ball-milling medium are subjected to ball milling, are then dried in vacuo 12h at 60 DEG C and obtain NaCl
Powder；
2) it stocks up: according to NaCl powder, the 32.6-38.4% of tungsten powder, 0%-8.5% that mass percent is 50-60%
Organic solvent and 5.3-7.4% organic additive stock, wherein organic additive includes the polyethylene of 2.5%-3.5%
Butyral, 0.8%-1.2% Hypermer KD-1 and 2.0%-2.7% glycerol；
3) preparation of curtain coating slurry: NaCl powder and tungsten powder and organic additive are added in organic solvent and carry out ball
Mill obtains curtain coating slurry；
4) be cast the processing of strip: the curtain coating slurry that step 3) is obtained is cast drying setting in casting machine, is flowed
Prolong strip, curtain coating strip is cut into specific shape, by the strip lamination of predetermined number of layers.Strip after lamination better than 9.9 ×
10-3Under the vacuum degree of Pa, 780 DEG C of heat preservation 2h carry out dumping, organic cracking are discharged, then 780 DEG C of guarantors under identical vacuum degree
Warm 2h, sintering pressure 10-30MPa carry out hot pressed sintering, obtain green compact；
5) sintering obtains POROUS TUNGSTEN: green compact, which are placed in the deionized water of flowing, rinses 12h, then is placed in 80 DEG C of vacuum ovens
Middle 12h obtains POROUS TUNGSTEN green compact.POROUS TUNGSTEN green compact high temperature sintering under an ar atmosphere obtains the POROUS TUNGSTEN, high temperature sintering
Sintering temperature is 1300-1700 DEG C, soaking time 1-3h, sintering pressure 0-10MPa.
Embodiment 1:
The present embodiment provides a kind of preparation methods of micrometer level porous tungsten, comprising the following steps:
A. the preparation of curtain coating slurry: 100gNaCl, 50g ethyl alcohol are added in nylon tank, the ball milling in planetary ball mill
36h, wherein NaCl material purity is 99.9%, crosses 60 meshes, rotational speed of ball-mill 250rpm.The suspension of acquisition is poured into beaker
In, room temperature stands 1h in a vacuum drying oven, pours out supernatant liquid, and surplus materials is true at 60 DEG C in a vacuum drying oven in beaker
The dry 12h of sky, taking NaCl powder 2.4g and 56g partial size is 5 μm of W powder, and the Hypermer KD-1 (analysis is pure) of 0.9g is added
In the dehydrated alcohol (analysis is pure) of 18.3g and butanone (analysis is pure) solvent of 18.3g, ball milling 3h, ball milling in high energy batch mixer
Medium is stainless steel ball, steel ball quality 100g.Add the polyvinyl butyral (analysis is pure) of 2.6g, the glycerol of 2.1g
(analysis is pure), ball milling 3h obtain curtain coating slurry.
B. it is cast the processing of strip: curtain coating slurry obtained in step A being cast to drying setting in casting machine, is flowed
Prolong strip, strip will be cast and be cut into the disk that diameter is 20mm, by 100 layers of sequin lamination.Strip after lamination is in vacuum
Degree is better than 9.9 × 10-3In the environment of Pa, 780 DEG C of heat preservation 2h carry out heat treatment dumping；Then carry out once sintered given birth to
Base, sintering temperature be 780 DEG C, keep the temperature 2h, when temperature is under 750 DEG C apply 30MPa pressure, when temperature is on 750 DEG C without
Pressure.
C. sintering obtains POROUS TUNGSTEN: the green compact obtained in step B being placed in the deionized water of flowing after rinsing 12h, is taken
Green compact out are placed in a vacuum drying oven 80 DEG C of drying 12h, obtain POROUS TUNGSTEN green compact.POROUS TUNGSTEN green compact are sintered under an ar atmosphere, are burnt
Knot system is that 10 DEG C/min is warming up to 1100 DEG C, and 5 DEG C/min rises to 1400 DEG C, and soaking time 3h, 10 DEG C/min are down to 1100
DEG C, the near room temperature of 20 DEG C/min is sintered whole application 10MPa pressure, obtains the POROUS TUNGSTEN.
Archimedes's water discharge method is used to measure the consistency of the POROUS TUNGSTEN as 82.0%, pore size distribution is uniform, macropore diameter
It is 3-5 μm, small aperture is 0.2 μm -0.7 μm.
Embodiment 2:
The present embodiment provides a kind of preparation methods of micrometer level porous tungsten, comprising the following steps:
A. the preparation of curtain coating slurry: the Hypermer KD-1 (analysis is pure) for the W powder, 1.2g that 60g partial size is 0.5 μm is taken, is added
Enter in the dehydrated alcohol (analysis is pure) of 16.3g and butanone (analysis is pure) solvent of 16.3g, the ball milling 3h in high energy batch mixer, then
The polyvinyl butyral (analysis is pure) of 3.5g, the glycerol (analysis is pure) of 2.7g is added, ball milling 3h obtains curtain coating slurry.
B. it is cast the processing of strip: curtain coating slurry obtained in step A being cast to drying setting in casting machine, is flowed
Prolong strip, strip will be cast and be cut into the disk that diameter is 20mm, by 100 layers of sequin lamination.Strip after lamination is in vacuum
Degree is better than 9.9 × 10-3In the environment of Pa, 780 DEG C of heat preservation 2h carry out heat treatment dumping；Then carry out once sintered given birth to
Base, sintering temperature be 780 DEG C, keep the temperature 2h, when temperature is under 750 DEG C apply 30MPa pressure, when temperature is on 750 DEG C without
Pressure.
C. sintering obtains POROUS TUNGSTEN: the green compact obtained in step B being placed in the deionized water of flowing after rinsing 12h, is taken
Green compact out are placed in a vacuum drying oven 80 DEG C of drying 12h, obtain POROUS TUNGSTEN green compact.POROUS TUNGSTEN green compact are sintered under an ar atmosphere, are burnt
Knot system is that 10 DEG C/min is warming up to 1100 DEG C, and 5 DEG C/min rises to 1700 DEG C, and soaking time 1h, 10 DEG C/min are down to 1100
DEG C, the near room temperature of 20 DEG C/min is sintered whole application 10MPa pressure, obtains the POROUS TUNGSTEN.
Archimedes's water discharge method is used to measure the consistency of the POROUS TUNGSTEN as 90%, pore size distribution is uniform, and small aperture is
0.1μm-0.6μm。
Embodiment 3:
The present embodiment provides a kind of preparation methods of micrometer level porous tungsten, comprising the following steps:
A. the preparation of curtain coating slurry: 100gNaCl, 50g ethyl alcohol are added in nylon tank, the ball milling in planetary ball mill
For 24 hours, wherein NaCl material purity is 99.9%, crosses 60 meshes, rotational speed of ball-mill 250rpm.The suspension of acquisition is poured into beaker
In, room temperature stands 1h in a vacuum drying oven, pours out supernatant liquid, and surplus materials is true at 60 DEG C in a vacuum drying oven in beaker
The dry 12h of sky takes the Hypermer KD-1 (analysis is pure) for the W powder, 0.8g that NaCl powder 2.4g and 50g partial size is 1 μm, is added
In the dehydrated alcohol (analysis is pure) of 22.15g and butanone (analysis is pure) solvent of 22.15g, ball milling 3h, ball in high energy batch mixer
Grinding media is stainless steel ball, steel ball quality 100g.Add the polyvinyl butyral (analysis is pure) of 2.5g, the glycerol of 2.0g
(analysis is pure), ball milling 3h obtain curtain coating slurry.
B. it is cast the processing of strip: curtain coating slurry obtained in step A being cast to drying setting in casting machine, is flowed
Prolong strip, strip will be cast and be cut into the disk that diameter is 20mm, by 100 layers of sequin lamination.Strip after lamination is in vacuum
Degree is better than 9.9 × 10-3In the environment of Pa, 780 DEG C of heat preservation 2h carry out heat treatment dumping；Then carry out once sintered given birth to
Base, sintering temperature be 780 DEG C, keep the temperature 2h, when temperature is under 750 DEG C apply 30MPa pressure, when temperature is on 750 DEG C without
Pressure.
C. sintering obtains POROUS TUNGSTEN: the green compact obtained in step B being placed in the deionized water of flowing after rinsing 12h, is taken
Green compact out are placed in a vacuum drying oven 80 DEG C of drying 12h, obtain POROUS TUNGSTEN green compact.POROUS TUNGSTEN green compact are sintered under an ar atmosphere, are burnt
Knot system is that 10 DEG C/min is warming up to 1100 DEG C, and 5 DEG C/min rises to 1500 DEG C, and soaking time 3h, 10 DEG C/min are down to 1100
DEG C, the near room temperature of 20 DEG C/min, sintering whole process obtains the POROUS TUNGSTEN without pressure.
Archimedes's water discharge method is used to measure the consistency of the POROUS TUNGSTEN as 74.4%, pore size distribution is uniform, macropore diameter
It is 4-6 μm, small aperture is 0.1 μm -0.5 μm.
Embodiment 4:
The present embodiment provides a kind of preparation methods of micrometer level porous tungsten, comprising the following steps:
A. the preparation of curtain coating slurry: 100gNaCl, 50g ethyl alcohol are added in nylon tank, the ball milling in planetary ball mill
For 24 hours, wherein NaCl material purity is 99.9%, crosses 60 meshes, rotational speed of ball-mill 250rpm.The suspension of acquisition is poured into beaker
In, room temperature stands 1h in a vacuum drying oven, pours out supernatant liquid, and surplus materials is true at 60 DEG C in a vacuum drying oven in beaker
The dry 12h of sky takes the Hypermer KD-1 (analysis is pure) for the W powder, 1g that NaCl powder 8.2g and 50g partial size is 1 μm, is added
In the dehydrated alcohol (analysis is pure) of 16.2g and butanone (analysis is pure) solvent of 16.2g, ball milling 3h, ball milling in high energy batch mixer
Medium is stainless steel ball, steel ball quality 100g.The glycerol of the polyvinyl butyral (analysis is pure), 2.4g that add 3g (divides
Analyse pure), ball milling 3h obtains curtain coating slurry.
B. it is cast the processing of strip: curtain coating slurry obtained in step A being cast to drying setting in casting machine, is flowed
Prolong strip, strip will be cast and be cut into the disk that diameter is 20mm, by 100 layers of sequin lamination.Strip after lamination is in vacuum
Degree is better than 9.9 × 10-3In the environment of Pa, 780 DEG C of heat preservation 2h carry out heat treatment dumping；Then carry out once sintered given birth to
Base, sintering temperature be 780 DEG C, keep the temperature 2h, when temperature is under 750 DEG C apply 10MPa pressure, when temperature is on 750 DEG C without
Pressure.
C. sintering obtains POROUS TUNGSTEN: the green compact obtained in step B being placed in the deionized water of flowing after rinsing 12h, is taken
Green compact out are placed in a vacuum drying oven 80 DEG C of drying 12h, obtain POROUS TUNGSTEN green compact.POROUS TUNGSTEN green compact are sintered under an ar atmosphere, are burnt
Knot system is that 10 DEG C/min is warming up to 1100 DEG C, and 5 DEG C/min rises to 1300 DEG C, and soaking time 3h, 10 DEG C/min are down to 1100
DEG C, the near room temperature of 20 DEG C/min, sintering whole process obtains the POROUS TUNGSTEN without pressure.
Archimedes's water discharge method is used to measure the consistency of the POROUS TUNGSTEN as 35%, pore size distribution is uniform, and macropore diameter is
4-6 μm, small aperture is 0.2 μm -0.7 μm.
Embodiment 5:
The present embodiment provides a kind of preparation methods of micrometer level porous tungsten, comprising the following steps:
A. the preparation of curtain coating slurry: 100gNaCl, 50g ethyl alcohol are added in nylon tank, the ball milling in planetary ball mill
For 24 hours, wherein NaCl material purity is 99.9%, crosses 60 meshes, rotational speed of ball-mill 250rpm.The suspension of acquisition is poured into beaker
In, room temperature stands 1h in a vacuum drying oven, pours out supernatant liquid, and surplus materials is true at 60 DEG C in a vacuum drying oven in beaker
The dry 12h of sky takes the Hypermer KD-1 (analysis is pure) for the W powder, 1g that NaCl powder 5.6g and 50g partial size is 1 μm, is added
In the dehydrated alcohol (analysis is pure) of 19.2g and butanone (analysis is pure) solvent of 19.2g, ball milling 3h, ball milling in high energy batch mixer
Medium is stainless steel ball, steel ball quality 100g.Add the polyvinyl butyral (analysis is pure) of 2.7g, the glycerol of 2.3g
(analysis is pure), ball milling 3h obtain curtain coating slurry.
B. it is cast the processing of strip: curtain coating slurry obtained in step A being cast to drying setting in casting machine, is flowed
Prolong strip, strip will be cast and be cut into the disk that diameter is 20mm, by 100 layers of sequin lamination.Strip after lamination is in vacuum
Degree is better than 9.9 × 10-3In the environment of Pa, 780 DEG C of heat preservation 2h carry out heat treatment dumping；Then carry out once sintered given birth to
Base, sintering temperature be 780 DEG C, keep the temperature 2h, when temperature is under 750 DEG C apply 10MPa pressure, when temperature is on 750 DEG C without
Pressure.
C. sintering obtains POROUS TUNGSTEN: the green compact obtained in step B being placed in the deionized water of flowing after rinsing 12h, is taken
Green compact out are placed in a vacuum drying oven 80 DEG C of drying 12h, obtain POROUS TUNGSTEN green compact.POROUS TUNGSTEN green compact are sintered under an ar atmosphere, are burnt
Knot system is that 10 DEG C/min is warming up to 1100 DEG C, and 5 DEG C/min rises to 1400 DEG C, and soaking time 3h, 10 DEG C/min are down to 1100
DEG C, the near room temperature of 20 DEG C/min, sintering whole process obtains the POROUS TUNGSTEN without pressure.
Archimedes's water discharge method is used to measure the consistency of the POROUS TUNGSTEN as 44.1%, pore size distribution is uniform, macropore diameter
It is 4-6 μm, small aperture is 0.2 μm -0.7 μm.
The embodiments described above only express several embodiments of the present invention, describe it is more detailed, but can not be because
This and be interpreted as limitations on the scope of the patent of the present invention.It should be pointed out that for those of ordinary skill in the art,
Under the premise of not departing from present inventive concept, several modifications and improvements can also be made, these are all within the scope of protection of the present invention.
Therefore the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of micrometer level porous tungsten, which comprises the following steps:
1) raw material NaCl, ethyl alcohol and ball-milling medium are subjected to ball milling, are then dried to obtain NaCl powder；
2) it stocks up: being that the tungsten powder of 50-60%, the NaCl powder of 0%-8.5%, 32.6-38.4% have according to mass percent
The organic additive of solvent and 5.3-7.4% stock, wherein organic additive includes the polyvinyl alcohol contracting of 2.5%-3.5%
Butyraldehyde, 0.8%-1.2% Hypermer KD-1 and 2.0%-2.7% glycerol；
3) preparation of curtain coating slurry: NaCl powder and tungsten powder and organic additive are added to progress ball milling in organic solvent and obtained
To curtain coating slurry；
4) be cast the processing of strip: the curtain coating slurry that step 3) is obtained is cast drying setting in casting machine, obtains being cast thin
Curtain coating strip is cut into specific shape by band, and by the strip lamination of predetermined number of layers, the strip after lamination is kept the temperature under vacuum conditions
Dumping, then the heat preservation sintering under identical vacuum degree, progress hot pressed sintering obtain green compact again；
5) sintering obtains POROUS TUNGSTEN: green compact are placed in flowing water and rinse, and are then dried to obtain POROUS TUNGSTEN green compact, POROUS TUNGSTEN green compact
High temperature sintering under an inert atmosphere obtains the POROUS TUNGSTEN.
2. the preparation method of micrometer level porous tungsten as described in claim 1, which is characterized in that specific in the step 3) plus
Material sequence are as follows: tungsten powder and NaCl and Hypermer KD-1 are first added to ball milling in organic solvent, add polyvinyl alcohol contracting fourth
Aldehyde and glycerol, ball milling obtain curtain coating slurry.
3. the preparation method of micrometer level porous tungsten as described in claim 1, which is characterized in that the NaCl powder in the step 1)
The partial size at end is 3-6 μm.
4. the preparation method of micrometer level porous tungsten as described in claim 1, which is characterized in that organic molten in the step 1)
Agent is the ethyl alcohol and butanone that mass ratio presses 1:1 mixing.
5. the preparation method of micrometer level porous tungsten as described in claim 1, which is characterized in that tungsten powder in the step 2)
Purity is 99.9%, and partial size is 0.5-5 μm.
6. the preparation method of micrometer level porous tungsten as described in claim 1, which is characterized in that the high temperature in the step 5) is burnt
The sintering temperature of knot is 1300-1700 DEG C, soaking time 1-3h, sintering pressure 0-10MPa.
7. the preparation method of micrometer level porous tungsten as described in claim 1, which is characterized in that the vacuum item in the step 4)
Part is better than 9.9 × 10-3The vacuum degree of Pa, holding temperature are 780 DEG C, soaking time 2h, sintering pressure 10-30MPa.
8. the preparation method of micrometer level porous tungsten as described in claim 1, which is characterized in that the drying in the step 5) is
Vacuum drying, drying temperature are 80 degree, and drying time is 12 hours.
9. the preparation method of micrometer level porous tungsten as described in claim 1, which is characterized in that the raw material in the step 1)
The purity of NaCl is 99.9%, crosses 60 meshes.
10. the micrometer level porous tungsten that the preparation method of micrometer level porous tungsten as described in claim 1 is prepared, feature exist
In the macropore diameter of the POROUS TUNGSTEN is 3-6 μm, and small aperture is 0.1 μm -0.7 μm, and consistency range is 35%-90%.
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| CN112652734A (en) * | 2019-10-11 | 2021-04-13 | 广州汽车集团股份有限公司 | Thick negative pole piece and preparation method thereof, lithium ion battery cell, lithium ion battery pack and application thereof |
| CN111020329B (en) * | 2019-11-22 | 2021-02-19 | 武汉理工大学 | Method for preparing porous tungsten material based on W-Fe-C system corrosion method |
| CN112548099B (en) * | 2020-06-05 | 2022-03-29 | 华南理工大学 | Method for preparing near-spherical pore porous alloy by using ammonium bicarbonate as pore-forming agent |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5846664A (en) * | 1995-07-25 | 1998-12-08 | Westaim Technologies, Inc. | Porous metal structures and processes for their production |
| US5902429A (en) * | 1995-07-25 | 1999-05-11 | Westaim Technologies, Inc. | Method of manufacturing intermetallic/ceramic/metal composites |
| CN101250638A (en) * | 2007-02-21 | 2008-08-27 | 德普伊产品公司 | Porous metal foam structures and methods |
| CN101497132A (en) * | 2009-03-17 | 2009-08-05 | 武汉理工大学 | Metal powder non-water-based curtain coating slurry and preparation method thereof |
| CN101817083A (en) * | 2010-04-06 | 2010-09-01 | 武汉理工大学 | Casting method for preparing Mg-Cu system density gradient material |
| CN101983807A (en) * | 2010-11-19 | 2011-03-09 | 武汉理工大学 | Preparation method of stable W-Cu metal tape-casting slurry with high solid phase content |
| CN103317140A (en) * | 2013-06-25 | 2013-09-25 | 武汉理工大学 | Method for manufacturing gradient composite of W-Cu system by aid of tape casting process |
| CN103710555A (en) * | 2013-12-04 | 2014-04-09 | 西安理工大学 | Method for preparing tungsten copper sheets or plates by utilization of tape casting method |
-
2017
- 2017-06-05 CN CN201710413422.5A patent/CN107234241B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5846664A (en) * | 1995-07-25 | 1998-12-08 | Westaim Technologies, Inc. | Porous metal structures and processes for their production |
| US5902429A (en) * | 1995-07-25 | 1999-05-11 | Westaim Technologies, Inc. | Method of manufacturing intermetallic/ceramic/metal composites |
| CN101250638A (en) * | 2007-02-21 | 2008-08-27 | 德普伊产品公司 | Porous metal foam structures and methods |
| CN101497132A (en) * | 2009-03-17 | 2009-08-05 | 武汉理工大学 | Metal powder non-water-based curtain coating slurry and preparation method thereof |
| CN101817083A (en) * | 2010-04-06 | 2010-09-01 | 武汉理工大学 | Casting method for preparing Mg-Cu system density gradient material |
| CN101983807A (en) * | 2010-11-19 | 2011-03-09 | 武汉理工大学 | Preparation method of stable W-Cu metal tape-casting slurry with high solid phase content |
| CN103317140A (en) * | 2013-06-25 | 2013-09-25 | 武汉理工大学 | Method for manufacturing gradient composite of W-Cu system by aid of tape casting process |
| CN103710555A (en) * | 2013-12-04 | 2014-04-09 | 西安理工大学 | Method for preparing tungsten copper sheets or plates by utilization of tape casting method |
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