CN107234241A - 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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- CN107234241A CN107234241A CN201710413422.5A CN201710413422A CN107234241A CN 107234241 A CN107234241 A CN 107234241A CN 201710413422 A CN201710413422 A CN 201710413422A CN 107234241 A CN107234241 A CN 107234241A
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- porous tungsten
- tungsten
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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, belongs to porous metal material technical field, and its preparation process is：Using the micron order pore creating material NaCl obtained through ball mill crushing, tungsten powder and organic additive are added to progress ball milling in organic solvent and obtain curtain coating slurry, and slurry, which is cast to be formed, is cut into given shape after strip；It is put into after lamination in mould, Low Temperature Heat Treatment dumping is carried out in a vacuum, low temperature hot-press sintering in a vacuum after dumping obtains green compact；Pore creating material is removed in the deionized water that green compact are placed in flowing, is dried in vacuum drying chamber, obtains POROUS TUNGSTEN green compact, POROUS TUNGSTEN green compact high temperature sintering under an ar atmosphere obtains described POROUS TUNGSTEN.POROUS TUNGSTEN consistency prepared by the present invention is 35% 90%, and macropore diameter is 36 μm, and small aperture is 0.1 μm 0.7 μm, with pore size distribution is uniform, pore size is controllable, the advantage that porosity change scope is big, sintering temperature is substantially reduced.
Description
Technical field
The present invention relates to porous metal material technical field, and in particular to a kind of micrometer level porous tungsten and preparation method thereof.
Background technology
Tungsten is infusibility non-ferrous metal, and its fusing point, boiling point and density are highests in all metals, its chemical property also pole
It is stable, and all soda acids are resistant under normal temperature and are corroded, meanwhile, the excellent thermal property of tungsten, mechanical property also make it have and extremely weighed
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., particularly its porous body or porous matrix material are widely used as high current
Mercury vapour liquid in the emitter of electronic emission material, mercury ion rocket engine is poured in the porous cathode of density, ion engine
Vaporizer, high temperature fluid filter and electronic package material of separation etc..
However, causing the preparation of POROUS TUNGSTEN to there is certain difficulty the features such as the high fusing point of tungsten electrode and great density, such as
Very high heating-up temperature is needed, it is difficult to select suitable pore creating material etc..Just conventional sintering method common at present and organic matrix leaching
Starch for drying and sintering method, there is following obvious shortcoming：The sintering temperature of conventional sintering method is high, and porosity is relatively low, hole point
Cloth is uneven；Organic matrix soaking paste drying and sintering method although even aperture distribution simple to operate, sintering temperature is still very high, production
Inefficiency.
It can find, to improve the shortcoming of conventional method, there are many scholars to employ by consulting domestic and international patent and document
New method prepares POROUS TUNGSTEN.Patent CN103774184A discloses a kind of method of electrolytic preparation POROUS TUNGSTEN, and this method is utilized
The characteristics of tungsten is electrolysed in molten salt solution by electrochemical action, using AC power and dc source 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》A kind of reaction using aluminium as pore creating material and sintering aid is disclosed to live
Change the method that sintering prepares POROUS TUNGSTEN, this method is using aluminium and the tungsten powder batch mixing cold moudling of pre-oxidation, then molding blank is existed
The technology path of pressureless sintering under reducing gas, because the self-propagating reaction of aluminium and tungsten oxide provides big energy, it is sintered
Temperature is substantially reduced, and hardness is evenly distributed, but POROUS TUNGSTEN porosity prepared by this method is relatively low, and pore size and pattern can not
Control.Sum it up, the preparation of POROUS TUNGSTEN is in during ceaselessly exploring and constantly improving.Current present Research also table
It is bright, take the relevant report of pore creating material method preparation POROUS TUNGSTEN all can not be while realizing that pore creating material is with low cost, make both at home and abroad at present
Hole works well, pore size is controllable, hole pattern rule, porosity ranges change greatly.
The content of the invention
The technical problems to be solved by the invention are：For existing preparation technology deficiency there is provided one kind in curtain coating slurry
Middle addition pore creating material, the micrometer level porous tungsten obtained with flow casting molding combination hot pressing or pressureless sintering and preparation method thereof.This side
Method equipment is simple, can operate continuously, production efficiency is high, automatization level is high, process stabilizing, and the tape casting diaphragm performance of acquisition is equal
One, diaphragm thickness is controllable, and obtained POROUS TUNGSTEN hole pattern rule, even aperture distribution, hole size is adjustable, also, curtain coating slurry
The micro C element of residual can be such that sintering temperature substantially reduces.
The present invention solves its technical problem and uses following technical scheme：
A kind of preparation method of micrometer level porous tungsten, comprises the following steps：
1) raw material NaCl, ethanol and ball-milling medium are subjected to ball milling, are then dried to obtain NaCl powder；
2) get the raw materials ready：According to the tungsten powder, 0%-8.5% NaCl powder, 32.6-38.4% that mass percent is 50-60%
Organic solvent and 5.3-7.4% organic additive get the raw materials ready, wherein organic additive includes 2.5%-3.5% polyethylene
The glycerine of butyral, 0.8%-1.2% Hypermer KD-1 and 2.0%-2.7%；
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) it is cast the processing of strip：By step 3) obtained curtain coating slurry is cast drying setting in casting machine, flowed
Prolong strip, curtain coating strip is cut into given shape, by the strip lamination of predetermined number of layers, the strip after lamination is under vacuum
Dumping is incubated, then the heat preservation sintering under identical vacuum again, carries out hot pressed sintering, obtain green compact；
5) sintering obtains POROUS TUNGSTEN：Green compact are placed in the water of flowing and rinsed, and are then dried to obtain POROUS TUNGSTEN green compact, POROUS TUNGSTEN
Green compact high temperature sintering under an inert atmosphere, obtains described POROUS TUNGSTEN.
In such scheme, the step 3) in specific charging sequence be：First by tungsten powder and NaCl and Hypermer KD-1
Ball milling in organic solvent is added to, polyvinyl butyral resin and glycerine is added, ball milling obtains curtain coating slurry.
In such scheme, the step 1) in the particle diameter of NaCl powder be 3-6 μm.
In such scheme, the step 1) in organic solvent press 1 for mass ratio:The ethanol and butanone of 1 mixing.
In such scheme, the step 2) in the purity of tungsten powder be 99.9%, particle diameter is 0.5-5 μm.
In such scheme, the step 5) in the sintering temperature of high temperature sintering be 1300-1700 DEG C, soaking time is 1-
3h, sintering pressure is 0-10MPa.
In such scheme, the step 4) in vacuum condition be better than 9.9 × 10-3Pa vacuum, holding temperature is
780 DEG C, soaking time is 2h, and sintering pressure is 10-30MPa.
In such scheme, the step 5) in drying be vacuum drying, drying temperature is 80 degree, and drying time is small for 12
When.
In such scheme, the step 1) in raw material NaCl purity be 99.9%, cross 60 mesh sieves.
The micrometer level porous tungsten that the preparation method of described micrometer level porous tungsten is prepared, the macropore hole of the POROUS TUNGSTEN
Footpath is 3-6 μm, and small aperture is 0.1 μm -0.7 μm, and consistency scope is 35%-90%.
The POROUS TUNGSTEN that the present invention is obtained has following clear advantage compared with prior art：
First, causing film strips component uniform using casting technology, and then make the porous material pore size distribution of acquisition uniform.Simultaneously
Casting technology also has the advantages that process equipment is simple, can operated continuously, production efficiency is high, automatization level is high, process stabilizing.
Second, pore creating material NaCl is with low cost, size and pattern can by simple technology controlling and process, meanwhile, curtain coating material
Slurry is stable complex phase slurry, it is possible to resolve pore creating material NaCl and the big caused settlement stability of W density variations, realizes porous W holes
Rate is accurately controlled 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 W diffusion
Mass transfer, hence it is evident that reduce the temperature of W sintering, traditional W pressureless sinterings temperature more than 2000 DEG C is reduced to 1400- by the present invention
1700℃。
Brief description of the drawings
Fig. 1 is the preparation technology flow chart of POROUS TUNGSTEN.
The NaCl powder SEM spectrums that Fig. 2 obtains for ball milling 24h 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.
Embodiment
SEM spectrum is obtained by Quanta FEG 250 (U.S., FEI Co.) field emission scanning electron microscope.
Density is measured by Archimedes's drainage, is first sealed sample with one layer of very thin vaseline before test, densification
Spend for actual density and solid density (19.30g/cm3The ratio between).
The technique that flow casting molding combination high temperature sintering that the present invention is used prepares POROUS TUNGSTEN is specially：
A kind of preparation method of micrometer level porous tungsten, comprises the following steps：
1) raw material NaCl, ethanol and ball-milling medium are subjected to ball milling, 12h is then dried in vacuo at 60 DEG C obtains NaCl
Powder；
2) get the raw materials ready：According to the tungsten powder, 0%-8.5% NaCl powder, 32.6-38.4% that mass percent is 50-60%
Organic solvent and 5.3-7.4% organic additive get the raw materials ready, wherein organic additive includes 2.5%-3.5% polyethylene
The glycerine of butyral, 0.8%-1.2% Hypermer KD-1 and 2.0%-2.7%；
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) it is cast the processing of strip：By step 3) obtained curtain coating slurry is cast drying setting in casting machine, flowed
Prolong strip, curtain coating strip is cut into given shape, by the strip lamination of predetermined number of layers.Strip after lamination better than 9.9 ×
10-3Under Pa vacuum, 780 DEG C of insulation 2h carry out dumping, organic cracking are discharged, then 780 DEG C of guarantors under identical vacuum
Warm 2h, sintering pressure is 10-30MPa, carries out hot pressed sintering, obtains 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 drying chambers
Middle 12h, obtains POROUS TUNGSTEN green compact.POROUS TUNGSTEN green compact high temperature sintering under an ar atmosphere, obtains described POROUS TUNGSTEN, high temperature sintering
Sintering temperature is 1300-1700 DEG C, and soaking time is 1-3h, and sintering pressure is 0-10MPa.
Embodiment 1：
The present embodiment provides a kind of preparation method of micrometer level porous tungsten, comprises the following steps：
A. the preparation of curtain coating slurry：100gNaCl, 50g ethanol are added in nylon tank, the ball milling in planetary ball mill
36h, wherein NaCl material purities are 99.9%, cross 60 mesh sieves, rotational speed of ball-mill is 250rpm.The suspension of acquisition is poured into beaker
In, normal temperature stands 1h in vacuum drying chamber, pours out surplus materials in supernatant liquid, beaker true at 60 DEG C in vacuum drying chamber
Sky dries 12h, takes the W powder that NaCl powder 2.4g and 56g particle diameter are 5 μm, and 0.9g Hypermer KD-1 (analysis is pure) are added
In 18.3g absolute ethyl alcohol (analysis is pure) and 18.3g butanone (analysis is pure) solvent, ball milling 3h, ball milling in high energy batch mixer
Medium is stainless steel ball, and steel ball quality is 100g.Add 2.6g polyvinyl butyral resin (analysis is pure), 2.1g glycerine
(analysis is pure), ball milling 3h obtains curtain coating slurry.
B. it is cast the processing of strip：The curtain coating slurry obtained in step A is cast drying setting in casting machine, flowed
Prolong strip, curtain coating strip is cut into a diameter of 20mm disk, by 100 layers of sequin lamination.Strip after lamination is in vacuum
Spend for better than 9.9 × 10-3In Pa environment, 780 DEG C of insulation 2h carry out heat treatment dumping；Then carry out once sintered given birth to
Base, sintering temperature be 780 DEG C, be incubated 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 are placed in the deionized water of flowing and rinsed after 12h, are taken
Go out green compact, be placed in 80 DEG C of drying 12h in vacuum drying chamber, 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 is 3h, and 10 DEG C/min is down to 1100
DEG C, the near room temperatures of 20 DEG C/min, sintering is whole to apply 10MPa pressure, obtains described POROUS TUNGSTEN.
Archimedes's water discharge method is used to measure the consistency of the POROUS TUNGSTEN for 82.0%, pore size distribution is uniform, macropore diameter
For 3-5 μm, small aperture is 0.2 μm -0.7 μm.
Embodiment 2：
The present embodiment provides a kind of preparation method of micrometer level porous tungsten, comprises the following steps：
A. the preparation of curtain coating slurry：The Hypermer KD-1 (analysis is pure) of W powder, 1.2g that 60g particle diameters are 0.5 μm are taken, plus
Enter in 16.3g absolute ethyl alcohol (analysis is pure) and 16.3g butanone (analysis is pure) solvent, the ball milling 3h in high energy batch mixer, then
3.5g polyvinyl butyral resin (analysis is pure), 2.7g glycerine (analysis is pure) is added, ball milling 3h obtains curtain coating slurry.
B. it is cast the processing of strip：The curtain coating slurry obtained in step A is cast drying setting in casting machine, flowed
Prolong strip, curtain coating strip is cut into a diameter of 20mm disk, by 100 layers of sequin lamination.Strip after lamination is in vacuum
Spend for better than 9.9 × 10-3In Pa environment, 780 DEG C of insulation 2h carry out heat treatment dumping；Then carry out once sintered given birth to
Base, sintering temperature be 780 DEG C, be incubated 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 are placed in the deionized water of flowing and rinsed after 12h, are taken
Go out green compact, be placed in 80 DEG C of drying 12h in vacuum drying chamber, 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 is 1h, and 10 DEG C/min is down to 1100
DEG C, the near room temperatures of 20 DEG C/min, sintering is whole to apply 10MPa pressure, obtains described POROUS TUNGSTEN.
Archimedes's water discharge method is used to measure the consistency of the POROUS TUNGSTEN for 90%, pore size distribution is uniform, and small aperture is
0.1μm-0.6μm。
Embodiment 3：
The present embodiment provides a kind of preparation method of micrometer level porous tungsten, comprises the following steps：
A. the preparation of curtain coating slurry：100gNaCl, 50g ethanol are added in nylon tank, the ball milling in planetary ball mill
24h, wherein NaCl material purities are 99.9%, cross 60 mesh sieves, rotational speed of ball-mill is 250rpm.The suspension of acquisition is poured into beaker
In, normal temperature stands 1h in vacuum drying chamber, pours out surplus materials in supernatant liquid, beaker true at 60 DEG C in vacuum drying chamber
Sky dries 12h, takes the Hypermer KD-1 (analysis is pure) of W powder, 0.8g that NaCl powder 2.4g and 50g particle diameter are 1 μm, adds
In 22.15g absolute ethyl alcohol (analysis is pure) and 22.15g butanone (analysis is pure) solvent, ball milling 3h, ball in high energy batch mixer
Grinding media is stainless steel ball, and steel ball quality is 100g.Add 2.5g polyvinyl butyral resin (analysis is pure), 2.0g glycerine
(analysis is pure), ball milling 3h obtains curtain coating slurry.
B. it is cast the processing of strip：The curtain coating slurry obtained in step A is cast drying setting in casting machine, flowed
Prolong strip, curtain coating strip is cut into a diameter of 20mm disk, by 100 layers of sequin lamination.Strip after lamination is in vacuum
Spend for better than 9.9 × 10-3In Pa environment, 780 DEG C of insulation 2h carry out heat treatment dumping；Then carry out once sintered given birth to
Base, sintering temperature be 780 DEG C, be incubated 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 are placed in the deionized water of flowing and rinsed after 12h, are taken
Go out green compact, be placed in 80 DEG C of drying 12h in vacuum drying chamber, 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 is 3h, and 10 DEG C/min is down to 1100
DEG C, the near room temperatures of 20 DEG C/min, sintering is whole without pressure, obtains described POROUS TUNGSTEN.
Archimedes's water discharge method is used to measure the consistency of the POROUS TUNGSTEN for 74.4%, pore size distribution is uniform, macropore diameter
For 4-6 μm, small aperture is 0.1 μm -0.5 μm.
Embodiment 4：
The present embodiment provides a kind of preparation method of micrometer level porous tungsten, comprises the following steps：
A. the preparation of curtain coating slurry：100gNaCl, 50g ethanol are added in nylon tank, the ball milling in planetary ball mill
24h, wherein NaCl material purities are 99.9%, cross 60 mesh sieves, rotational speed of ball-mill is 250rpm.The suspension of acquisition is poured into beaker
In, normal temperature stands 1h in vacuum drying chamber, pours out surplus materials in supernatant liquid, beaker true at 60 DEG C in vacuum drying chamber
Sky dries 12h, takes the Hypermer KD-1 (analysis is pure) of W powder, 1g that NaCl powder 8.2g and 50g particle diameter are 1 μm, adds
In 16.2g absolute ethyl alcohol (analysis is pure) and 16.2g butanone (analysis is pure) solvent, ball milling 3h, ball milling in high energy batch mixer
Medium is stainless steel ball, and steel ball quality is 100g.Polyvinyl butyral resin (analysis is pure), the 2.4g glycerine for adding 3g (divide
Analysis is pure), ball milling 3h obtains curtain coating slurry.
B. it is cast the processing of strip：The curtain coating slurry obtained in step A is cast drying setting in casting machine, flowed
Prolong strip, curtain coating strip is cut into a diameter of 20mm disk, by 100 layers of sequin lamination.Strip after lamination is in vacuum
Spend for better than 9.9 × 10-3In Pa environment, 780 DEG C of insulation 2h carry out heat treatment dumping；Then carry out once sintered given birth to
Base, sintering temperature be 780 DEG C, be incubated 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 are placed in the deionized water of flowing and rinsed after 12h, are taken
Go out green compact, be placed in 80 DEG C of drying 12h in vacuum drying chamber, 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 is 3h, and 10 DEG C/min is down to 1100
DEG C, the near room temperatures of 20 DEG C/min, sintering is whole without pressure, obtains described POROUS TUNGSTEN.
Archimedes's water discharge method is used to measure the consistency of the POROUS TUNGSTEN for 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 method of micrometer level porous tungsten, comprises the following steps：
A. the preparation of curtain coating slurry：100gNaCl, 50g ethanol are added in nylon tank, the ball milling in planetary ball mill
24h, wherein NaCl material purities are 99.9%, cross 60 mesh sieves, rotational speed of ball-mill is 250rpm.The suspension of acquisition is poured into beaker
In, normal temperature stands 1h in vacuum drying chamber, pours out surplus materials in supernatant liquid, beaker true at 60 DEG C in vacuum drying chamber
Sky dries 12h, takes the Hypermer KD-1 (analysis is pure) of W powder, 1g that NaCl powder 5.6g and 50g particle diameter are 1 μm, adds
In 19.2g absolute ethyl alcohol (analysis is pure) and 19.2g butanone (analysis is pure) solvent, ball milling 3h, ball milling in high energy batch mixer
Medium is stainless steel ball, and steel ball quality is 100g.Add 2.7g polyvinyl butyral resin (analysis is pure), 2.3g glycerine
(analysis is pure), ball milling 3h obtains curtain coating slurry.
B. it is cast the processing of strip：The curtain coating slurry obtained in step A is cast drying setting in casting machine, flowed
Prolong strip, curtain coating strip is cut into a diameter of 20mm disk, by 100 layers of sequin lamination.Strip after lamination is in vacuum
Spend for better than 9.9 × 10-3In Pa environment, 780 DEG C of insulation 2h carry out heat treatment dumping；Then carry out once sintered given birth to
Base, sintering temperature be 780 DEG C, be incubated 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 are placed in the deionized water of flowing and rinsed after 12h, are taken
Go out green compact, be placed in 80 DEG C of drying 12h in vacuum drying chamber, 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 is 3h, and 10 DEG C/min is down to 1100
DEG C, the near room temperatures of 20 DEG C/min, sintering is whole without pressure, obtains described POROUS TUNGSTEN.
Archimedes's water discharge method is used to measure the consistency of the POROUS TUNGSTEN for 44.1%, pore size distribution is uniform, macropore diameter
For 4-6 μm, small aperture is 0.2 μm -0.7 μm.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more detailed, but can not be because
This and be interpreted as the limitation to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art,
On the premise of not departing from present inventive concept, several modifications and improvements can also be made, these belong to protection scope of the present invention.
Therefore the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of preparation method of micrometer level porous tungsten, it is characterised in that comprise the following steps：
1) raw material NaCl, ethanol and ball-milling medium are subjected to ball milling, are then dried to obtain NaCl powder；
2) get the raw materials ready：According to mass percent having for 50-60% tungsten powder, 0%-8.5% NaCl powder, 32.6-38.4%
Machine solvent and 5.3-7.4% organic additive are got the raw materials ready, and wherein organic additive includes 2.5%-3.5% polyvinyl alcohol contracting
The glycerine of butyraldehyde, 0.8%-1.2% Hypermer KD-1 and 2.0%-2.7%；
3) preparation of curtain coating slurry：NaCl powder and tungsten powder and organic additive are added into progress ball milling in organic solvent to obtain
To curtain coating slurry；
4) it is cast the processing of strip：By step 3) obtained curtain coating slurry is cast drying setting in casting machine, obtains curtain coating thin
Band, is cut into given shape, by the strip lamination of predetermined number of layers, the strip after lamination is incubated under vacuum by curtain coating strip
Dumping, then the heat preservation sintering under identical vacuum again, carries out hot pressed sintering, obtains green compact；
5) sintering obtains POROUS TUNGSTEN：Green compact are placed in the water of flowing and rinsed, and are then dried to obtain POROUS TUNGSTEN green compact, POROUS TUNGSTEN green compact
High temperature sintering, obtains described POROUS TUNGSTEN under an inert atmosphere.
2. the preparation method of micrometer level porous tungsten as claimed in claim 1, it is characterised in that the step 3) in it is specific plus
Material order be：Tungsten powder and NaCl and Hypermer KD-1 are first added to ball milling in organic solvent, polyvinyl alcohol contracting fourth is added
Aldehyde and glycerine, ball milling obtain curtain coating slurry.
3. the preparation method of micrometer level porous tungsten as claimed in claim 1, it is characterised in that the step 1) in NaCl powder
The particle diameter at end is 3-6 μm.
4. the preparation method of micrometer level porous tungsten as claimed in claim 1, it is characterised in that the step 1) in it is organic molten
Agent is that mass ratio presses 1:The ethanol and butanone of 1 mixing.
5. the preparation method of micrometer level porous tungsten as claimed in claim 1, it is characterised in that the step 2) in tungsten powder
Purity is 99.9%, and particle diameter is 0.5-5 μm.
6. the preparation method of micrometer level porous tungsten as claimed in claim 1, it is characterised in that the step 5) in high temperature burn
The sintering temperature of knot is 1300-1700 DEG C, and soaking time is 1-3h, and sintering pressure is 0-10MPa.
7. the preparation method of micrometer level porous tungsten as claimed in claim 1, it is characterised in that the step 4) in vacuum bar
Part is better than 9.9 × 10-3Pa vacuum, holding temperature is 780 DEG C, and soaking time is 2h, and sintering pressure is 10-30MPa.
8. the preparation method of micrometer level porous tungsten as claimed in claim 1, it is characterised in that the step 5) in drying be
Vacuum drying, drying temperature is 80 degree, and drying time is 12 hours.
9. the preparation method of micrometer level porous tungsten as claimed in claim 1, it is characterised in that the step 1) in raw material
NaCl purity is 99.9%, crosses 60 mesh sieves.
10. the micrometer level porous tungsten that the preparation method of micrometer level porous tungsten as claimed in claim 1 is prepared, its feature exists
In the macropore diameter of the POROUS TUNGSTEN is 3-6 μm, and small aperture is 0.1 μm -0.7 μm, and consistency scope is 35%-90%.
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