CN109457159A - A kind of preparation method of high-compactness fine grain tungsten sill - Google Patents
A kind of preparation method of high-compactness fine grain tungsten sill Download PDFInfo
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- CN109457159A CN109457159A CN201811584881.0A CN201811584881A CN109457159A CN 109457159 A CN109457159 A CN 109457159A CN 201811584881 A CN201811584881 A CN 201811584881A CN 109457159 A CN109457159 A CN 109457159A
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 51
- 239000010937 tungsten Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 65
- 239000000843 powder Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 50
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims description 27
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 22
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 22
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000003825 pressing Methods 0.000 claims description 21
- 230000009467 reduction Effects 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 239000013049 sediment Substances 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 238000009826 distribution Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 230000004907 flux Effects 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000002525 ultrasonication Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000010907 mechanical stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 5
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 230000002706 hydrostatic effect Effects 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 28
- 238000000280 densification Methods 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 238000005056 compaction Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000001272 pressureless sintering Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 11
- WUVRZBFIXJWTGS-UHFFFAOYSA-N yttrium(3+);trinitrate;hydrate Chemical compound O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WUVRZBFIXJWTGS-UHFFFAOYSA-N 0.000 description 8
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 229910052727 yttrium Inorganic materials 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000009768 microwave sintering Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000009707 resistance sintering Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0031—Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention belongs to powder metallurgical technologies, it is related to a kind of preparation method of high-compactness fine grain tungsten sill, method are as follows: the salt of rare earths and polymer are prepared powder precursor with liquid chemical method by S1.: S2. carries out de-agglomerated using high energy dispersion and handles to obtain finely dispersed doped tungsten powder, cold isostatic compaction is carried out again, obtains forming base；S3. high high-compactness fine grain tungsten sill is prepared using twice sintering process.Based on pressureless sintering, reinforced metal tungsten sintering process and control tungsten grain are grown up.The crystal grain in sintering later period is inhibited to grow up from two aspects: first is that using the dispersion-strengthened effect of the second phase, second is that low temperature two-step sintering method is grown up using grain boundary decision and the dynamic (dynamical) difference of crystal boundary migration to control crystal grain.The sintering densification temperature of tungsten can not only be reduced, moreover it is possible to effectively prevent the non-homogeneous of tungsten grain to grow up, obtain the metal tungsten material with high density, the nanocrystalline homogeneous texture that crystal grain is small, thermodynamic property is high.
Description
Technical field
The invention belongs to powder metallurgical technologies, specifically provide a kind of preparation of high-compactness fine grain tungsten sill
Method.
Tungsten has the excellent properties such as high-melting-point, low-vapor pressure, low sputtering yield, the delay of low tritium, as a kind of special
High-temperature structural material, the fields such as facing plasma material, weapons and aerospace in nuclear fusion experimental device have
Critically important application.However, tungsten shapes performance there are low temperature brittleness, recrystallization embrittlement and the problems such as radiation embrittlement
It is all extremely restricted with service life.Crystal grain refinement is considered as the raising tungsten plasticity and toughness and Flouride-resistani acid phesphatase of most prospect
The effective ways of energy.Preparing fine grain tungsten at present and generalling use nano-tungsten powder is raw material, due to the crystal boundary energy of nano-powder
Big with interfacial energy, the driving force of sintering is very big, so that the size of crystal grain is difficult to control.In order to inhibit the crystal grain of tungsten long
Greatly, frequently with two methods.One is special sintering technique is used, suppression is realized by the process means such as external force and auxiliary outfield
Tungsten particle processed is grown up.Resistance sintering under such as hot isostatic pressing, plasma activated sintering, microwave sintering, hyperpressure.These
Method is difficult to prepare complex-shaped tungsten product.In addition, the significant agglomeration of nano particle will lead to the non-homogeneous length of crystal grain
Greatly, the thermodynamic property of tungsten is caused to be greatly lowered.As it can be seen that densification problem and the crystal grain problem of growing up are current nano powders
It is sintered two greatest problems faced.Another kind is addition nano-second-phase oxide (La2O3, Y2O3, ZrO2) or carbide
(TiC, ZrC, HfC), nano particle evenly spreads in W matrix the migration that can limit W crystal boundary and dislocation, to inhibit crystal grain
It grows up, plays the effect of refinement crystal grain, the room temperature and elevated temperature strength, high-temperature stability and again of tungsten can also be significantly improved
Crystallization temperature.However, on the one hand, the uneven distribution of nano particle disperse and nano particle grain boundaries segregation for oxidation
The always very big challenge of object dispersion-strengtherning tungsten material；On the other hand, the addition of the second phase can reduce the densification of metal tungsten product
Rate, and the phase eliminates the higher driving force of residual holes needs and crystal grain is caused to be grown up after sintering.It can although adding oxide
With the significant crystallite dimension for reducing tungsten, but there is still a need for new processes to reach higher performance to meet application requirement.
The invention proposes one kind to be based on pressureless sintering, the new side that reinforced metal tungsten sintering process and control tungsten grain are grown up
Method.The crystal grain in sintering later period is inhibited to grow up from two aspects: first is that using the dispersion-strengthened effect of the second phase, second is that low temperature
Two-step sintering method is grown up using grain boundary decision and the dynamic (dynamical) difference of crystal boundary migration with controlling crystal grain.This method can not only reduce
The sintering densification temperature of tungsten, moreover it is possible to effectively prevent the non-homogeneous of tungsten grain to grow up, to obtain with nanocrystalline uniform
The metal tungsten material of structure.Concrete thought is that tungsten powder oxide-doped first is prepared by liquid phase chemical method, then uses high energy
Decentralized processing doped tungsten powder then carries out cold isostatic compaction, and high-compactness fine grain is then prepared using twice sintering process
Grain second-phase strength tungsten.Two-step sintering is green compact to be rapidly heated to a higher temperature T1, dropped immediately after short time heat preservation
Temperature is to lower temperature T2, then in low temperature T2The lower heat preservation long period.First step sintering temperature T1The key of selection is by metal base
The consistency of body is controlled in 75-85%, and has tiny, uniform pore structure.Hole will be formed in first step sintering process
Gap pore structure of uniform size, hole are grown up to subsequent crystal grain with inhibition, meanwhile, in first step sintering process
The characteristic that nano-second-phase is preferentially precipitated in powder particle neck and surface, using nanometer precipitated phase as quick diffusion admittance, drop
Low first step sintering temperature.Second step sintering temperature is lower, is eliminated in green body using grain boundary decision and long period heat preservation
Hole, the double inhibition of crystal boundary migration by hole and the second phase during this, but keep the activity of grain boundary decision.Therefore,
Crystal grain will not occur significantly to grow up, although this stage densification kinetics is slower, be enough that green body is made to obtain high densification
Degree.It can prepare close to fully dense second-phase strength tungsten product, consistency is greater than 98%, and can be realized metal product
Near-net forming.Fine grain effectively increases the mechanical property of tungsten, expands its use scope.It is high-densit to be prepared by a kind of low cost
Spend the method for fine grain tungsten sill.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of preparation methods of high-compactness fine grain tungsten sill,
The technical issues of solution is that existing tungsten metal sintering product densification is difficult, crystallite dimension is difficult to control and structural homogenity is poor
And the problem for causing its mechanical property not high.
The present invention is to solve above-mentioned technical problem by following technical proposals: firstly, being prepared using liquid chemical method
Then oxide-doped tungsten powder out carries out de-agglomerated processing to mixed nanometer tungsten powder with high-speed screw blade mixer.Then, it adopts
With cold isostatic compaction, realizes higher green density and improve the uniformity of green compact.Finally, passing through twice sintering process
Inhibit the acceleration crystal grain in tungsten sintering later period to grow up, realizes the complete densification of tungsten green body in cryogenic conditions, simultaneously effective control
Crystal grain is grown up, and the oxide-doped tungsten product finally prepared has the characteristics that high density, crystal grain are small, thermodynamic property is high.
To achieve the purpose of the present invention, using following technology of preparing scheme: a kind of high-compactness fine grain tungsten sill
Preparation method, method includes the following steps:
S1. the salt of rare earths and polymer are prepared into powder precursor with liquid chemical method:
S2. de-agglomerated is carried out using high energy dispersion to handle to obtain finely dispersed oxide-doped tungsten powder, then carry out cold
Hydrostatic pressing obtains forming base；
S3. high-compactness fine grain tungsten sill is prepared using twice sintering process.
Further, the specific steps of the S1 are as follows:
S1.1 is according to mass ratio under conditions of mechanical stirring and ultrasonication, by the salt of rare earths and polymer
(0.8~0.9): solution A is made in 1 dissolution in deionized water,
Ammonium paratungstate is (0.03~0.05) according to the mass ratio of solid phase and liquid phase by S1.2: 1 addition S1.1 obtains solution A
In, 5~after ten minutes, acid flux material and the reaction was continued 20-50 minutes generation suspension B is added,
Dehydrated alcohol is added into the suspension B by S1.3, after reaction 2-4 hours, suspension B is filtered, after washing repeatedly
Sediment C is obtained, then sediment C is placed in in 60 DEG C~80 DEG C of vacuum oven dry 10~for 24 hours, obtain powder forerunner
Body.
Further, the specific steps of the S2 are as follows:
Powder precursor is calcined 0.5-2h by S2.1 in air, and calcination temperature is 500 DEG C~600 DEG C, is subsequently placed into pipe
It is passed through high-purity hydrogen in formula furnace and carries out reduction treatment, reduction temperature is 600 DEG C~800 DEG C, heating rate is 5~10 DEG C/min,
Soaking time is 60~120min, obtains oxide-doped tungsten powder；
S2.2 carries out de-agglomerated processing to Oxidation Doping tungsten powder using high-speed screw blade mixer, and the revolving speed of blade is
2000-3000 revs/min, being crushed the time is 0.5-1 hours, obtains the narrower de-agglomerated powder of particle diameter distribution；
De-agglomerated powder is fitted into thin wall wrap model and carries out Vacuum Package by S2.3, then carries out isostatic cool pressing, isostatic cool pressing
Compacting pressure is 200~280MPa, and the dwell time is 5~10min, obtains forming base.
Further, the specific steps of the S3 are as follows:
S3.1 carries out two-step sintering for base is shaped in high-purity hydrogen protective atmosphere: first first step sintering is forming base with one
Fixed heating rate is heated to temperature T1, first time heat preservation is carried out, once sintered green body is obtained,
S3.2 then carries out second step sintering: by once sintered green body in T1On the basis of temperature is cooled to certain rate
T2, carry out second and keep the temperature, that is, finally obtain high-compactness fine grain tungsten sill.
Further, the salt of rare earths includes yttrium nitrate hydrate in described 1.1；
The polymer includes polyvinylpyrrolidone；
The acid flux material includes hydrochloric acid and nitric acid；The concentration of the acid flux material is 65%~68%；The acidity is molten
The volume ratio of agent and the solution A is 1:(4~6).
Further, the partial size of the de-agglomerated powder in the S2.2 is less than 0.2 μm.
Further, the relative density that base is shaped in the S2.3 is greater than 50%.
Further, first step sintering temperature T in the S3.11It is 1300~1600 DEG C, heating rate is 3-10 DEG C/min,
Soaking time is 1-2h.
Further, rate of temperature fall is 15-25 DEG C/min in the S3.2, and temperature is down to T2, T2Compare T1Low 50-250 DEG C,
T2Lower soaking time is 10-60h.
Further, the consistency of the obtained high-compactness fine grain tungsten sill is greater than 98%, average grain size
Less than 1 μm.
Compared with prior art, the invention has the following advantages that
One, oxide-doped tungsten powder is prepared using improved liquid phase chemical method, wherein joined Polymer surfactants
Agent PVP, and introduce ultrasonication.Presoma is by calcining and obtained nanometer powder after reduction treatment, particle diameter distribution
It is very narrow.
Two, the characteristic of initial powder also can generate significant impact to two-step sintering process, since powder used is to receive
The powder, granule of meter level is smaller to be more easy to appear reunion and forms hole inside aggregate, and high-speed rotating blade band is utilized
Dynamic powder particle high speed rotation, makes the group in nanometer powder using the high velocity impact between the shearing force and powder particle of blade
Aggressiveness is opened, and the size distribution of gained powder particle is narrower, and dispersibility is more preferable.To realize good filling uniformity, eliminate
The macrovoid that the aggregate of nanometer powder is formed during the sintering process, this hole passing through subsequent high temperature sintering very
Hardly possible is eliminated.Meanwhile the abnormal growth of crystal grain is significantly reduced, improve the uniformity of crystal grain distribution in sintered blank.
Three, twice sintering process can effectively inhibit the crystal grain acceleration for being sintered the later period in conventional sintering technique to grow up, and promote
It densifies and reduces crystal grain and grow up, the oxide-doped tungsten material of preparation is also able to maintain crystal grain while obtaining high consistency
It is tiny, and have high microstructure uniformity, significantly improve its mechanical property.
Four, sintering temperature is reduced 300-400 DEG C by twice sintering process, reduces energy consumption and cost.This method is applicable in
In the sintering densification of other second-phase strength metal materials.
Detailed description of the invention
Fig. 1 is a kind of flow chart of the preparation method of high-compactness fine grain tungsten sill of the present invention.
Fig. 2 is once sintered and twice sintering process correlation curve schematic diagram.
Fig. 3 is second-phase strength tungsten sin-tering mechanism schematic diagram.
Specific embodiment
Technical scheme is described further in the following with reference to the drawings and specific embodiments.
A kind of preparation method of high-compactness fine grain tungsten sill of the present invention, method includes the following steps:
S1. the salt of rare earths and polymer are prepared into powder precursor with liquid chemical method:
S2. de-agglomerated is carried out using high energy dispersion to handle to obtain finely dispersed oxide-doped tungsten powder, then carry out cold
Hydrostatic pressing obtains forming base；
S3. high-compactness fine grain tungsten sill is prepared using twice sintering process.
Further, the specific steps of the S1 are as follows:
S1.1 is according to mass ratio under conditions of mechanical stirring and ultrasonication, by the salt of rare earths and polymer
(0.8~0.9): solution A is made in 1 dissolution in deionized water,
Ammonium paratungstate is (0.03~0.05) according to the mass ratio of solid phase and liquid phase by S1.2: 1 addition S1.1 obtains solution A
In, 5~after ten minutes, acid flux material and the reaction was continued 20-50 minutes generation suspension B is added,
Dehydrated alcohol is added into the suspension B by S1.3, after reaction 2-4 hours, suspension B is filtered, after washing repeatedly
Sediment C is obtained, then sediment C is placed in in 60 DEG C~80 DEG C of vacuum oven dry 10~for 24 hours, obtain powder forerunner
Body.
The specific steps of the S2 are as follows:
Powder precursor is calcined 0.5-2h by S2.1 in air, and calcination temperature is 500 DEG C~600 DEG C, is subsequently placed into pipe
It is passed through high-purity hydrogen in formula furnace and carries out reduction treatment, reduction temperature is 600 DEG C~800 DEG C, heating rate is 5~10 DEG C/min,
Soaking time is 60~120min, obtains oxide-doped tungsten powder；
S2.2 carries out de-agglomerated processing to Oxidation Doping tungsten powder using high-speed screw blade mixer, and the revolving speed of blade is
2000-3000 revs/min, being crushed the time is 0.5-1 hours, obtains the narrower de-agglomerated powder of particle diameter distribution；
De-agglomerated powder is fitted into thin wall wrap model and carries out Vacuum Package by S2.3, then carries out isostatic cool pressing, isostatic cool pressing
Compacting pressure is 200~280MPa, and the dwell time is 5~10min, obtains forming base.
The specific steps of the S3 are as follows:
S3.1 carries out two-step sintering for base is shaped in high-purity hydrogen protective atmosphere: first first step sintering is forming base with one
Fixed heating rate is heated to temperature T1, first time heat preservation is carried out, once sintered green body is obtained,
S3.2 then carries out second step sintering: by once sintered green body in T1On the basis of temperature is cooled to certain rate
T2, second heat preservation is carried out to get to finally obtaining high-compactness fine grain tungsten sill.(as shown in Figure 3).
The salt of rare earths includes yttrium nitrate hydrate in described 1.1；The polymer includes polyvinylpyrrolidone；
The acid flux material includes hydrochloric acid and nitric acid；The concentration of the acid flux material is 65%~68%；The acidity is molten
The volume ratio of agent and the solution A is 1:(4~6).
The partial size of de-agglomerated powder in the S2.2 is less than 0.2 μm.
The relative density that base is shaped in the S2.3 is greater than 50%.
First step sintering temperature T in the S3.11It is 1300~1600 DEG C, heating rate is 3-10 DEG C/min, when heat preservation
Between be 1-2h.
Rate of temperature fall is 15-25 DEG C/min in the S3.2, and temperature is down to T2, T2Compare T1Low 50-250 DEG C, in T2Lower heat preservation
Time is 10-60h.
The consistency of the obtained high-compactness fine grain tungsten sill is greater than 98%, and average grain size is less than 1 μm.
Following embodiment is implemented down based on the technical solution of the present invention, gives detailed embodiment and specific
Operating process, but protection scope of the present invention is not limited to following embodiments.Method therefor is as without especially in following embodiments
Explanation is conventional method.
Embodiment 1: Ultra-fine Grained W-0.5wt.%Y is prepared2O3
Firstly, under conditions of mechanical stirring and ultrasonication, by 2g yttrium nitrate hydrate (Y (NO3)3·6H2O) and
2.5g polyvinylpyrrolidone (PVP), which is dissolved in 150ml deionized water, is made solution A.Then it is secondary that 120g is added into solution A
Ammonium tungstate (APT).After five minutes, 25ml nitric acid and the reaction was continued 30 minutes generation suspension B is added.Backward suspension B in plus
Enter 150ml dehydrated alcohol to filter suspension B after reaction 3 hours, repeatedly washed with dehydrated alcohol to remove PVP as much as possible
To obtain sediment C, then sediment C is placed in in 60 DEG C of vacuum oven dry 10h, obtain powder precursor.It will
Powder precursor calcines 1h in air, and calcination temperature is 500 DEG C.Then it puts it into tube furnace and is passed through high-purity hydrogen progress
Reduction treatment, reduction temperature is 600 DEG C, heating rate is 5~10 DEG C/min, soaking time 60min, is obtained oxide-doped
Tungsten powder.De-agglomerated processing is carried out to Oxidation Doping tungsten powder using high-speed screw blade mixer, the revolving speed of blade is 2000 revs/min
Clock, being crushed the time is 0.5 hour, obtains the narrower de-agglomerated powder of particle diameter distribution.De-agglomerated powder is fitted into thin wall wrap model
Vacuum Package is carried out, isostatic cool pressing is then carried out, it is 200MPa that isostatic cool pressing, which suppresses pressure, and dwell time 5min is obtained into
Shape green compact.Forming green body carries out first step sintering in hydrogen atmosphere, 1450 DEG C of first step sintering temperature, heating rate for 5 DEG C/
And then min, soaking time 1h are cooled to 1300 DEG C of heat preservation 20h of second step sintering temperature with 10 DEG C/min, obtain final surpass
Fine grain W-0.5wt.%Y2O3, consistency 98%, crystallite dimension is 0.5 μm.(as shown in Figure 1)
Embodiment 2: Ultra-fine Grained W-1wt.%Y is prepared2O3
Firstly, under conditions of mechanical stirring and ultrasonication, by 2g yttrium nitrate hydrate (Y (NO3)3·6H2O) and
2.5g polyvinylpyrrolidone (PVP), which is dissolved in 150ml deionized water, is made solution A.Then it is secondary that 60g is added into solution A
Ammonium tungstate (APT).After five minutes, 25ml nitric acid and the reaction was continued 30 minutes generation suspension B is added.Backward suspension B in plus
Enter 150ml dehydrated alcohol to filter suspension B after reaction 3 hours, repeatedly washed with dehydrated alcohol to remove PVP as much as possible
To obtain sediment C, then sediment C is placed in in 80 DEG C of vacuum oven dry 10h, obtain powder precursor.It will
Powder precursor calcines 1h in air, and calcination temperature is 600 DEG C.Then it puts it into tube furnace and is passed through high-purity hydrogen progress
Reduction treatment, reduction temperature is 700 DEG C, heating rate is 5~10 DEG C/min, soaking time 60min, is obtained oxide-doped
Tungsten powder.De-agglomerated processing is carried out to Oxidation Doping tungsten powder using high-speed screw blade mixer, the revolving speed of blade is 2000 revs/min
Clock, being crushed the time is 0.5 hour, obtains the narrower de-agglomerated powder of particle diameter distribution.De-agglomerated powder is fitted into thin wall wrap model
Vacuum Package is carried out, isostatic cool pressing is then carried out, it is 220MPa that isostatic cool pressing, which suppresses pressure, and dwell time 5min is obtained into
Shape green compact.Forming green body carries out first step sintering in hydrogen atmosphere, 1450 DEG C of first step sintering temperature, heating rate for 5 DEG C/
Min, soaking time are less than 1h, are and then cooled to 1350 DEG C of heat preservation 20h of second step sintering temperature with 10 DEG C/min, obtain final
Ultra-fine Grained W-1wt.%Y2O3, consistency 98%, crystallite dimension is 0.4 μm.
Embodiment 3: Ultra-fine Grained W-2wt.%Y is prepared2O3
Firstly, under conditions of mechanical stirring and ultrasonication, by 2g yttrium nitrate hydrate (Y (NO3)3·6H2O) and
2.5g polyvinylpyrrolidone (PVP), which is dissolved in 150ml deionized water, is made solution A.Then it is secondary that 30g is added into solution A
Ammonium tungstate (APT).After five minutes, 25ml nitric acid and the reaction was continued 30 minutes generation suspension B is added.Backward suspension B in plus
Enter 150ml dehydrated alcohol to filter suspension B after reaction 3 hours, repeatedly washed with dehydrated alcohol to remove PVP as much as possible
To obtain sediment C, then sediment C is placed in in 80 DEG C of vacuum oven dry 10h, obtain powder precursor.It will
Powder precursor calcines 1h in air, and calcination temperature is 600 DEG C.Then it puts it into tube furnace and is passed through high-purity hydrogen progress
Reduction treatment, reduction temperature is 750 DEG C, heating rate is 5~10 DEG C/min, soaking time 60min, is obtained oxide-doped
Tungsten powder.De-agglomerated processing is carried out to Oxidation Doping tungsten powder using high-speed screw blade mixer, the revolving speed of blade is 2000 revs/min
Clock, being crushed the time is 0.5 hour, obtains the narrower de-agglomerated powder of particle diameter distribution.De-agglomerated powder is fitted into thin wall wrap model
Vacuum Package is carried out, isostatic cool pressing is then carried out, it is 220MPa that isostatic cool pressing, which suppresses pressure, and dwell time 5min is obtained into
Shape green compact.Forming green body carries out first step sintering in hydrogen atmosphere, 1500 DEG C of first step sintering temperature, heating rate for 5 DEG C/
Min, soaking time are less than 1h, are and then cooled to second step sintering temperature 1350 with 10 DEG C/min and keep the temperature 10h, obtain final
Ultra-fine Grained W-2wt.%Y2O3, consistency 97%, crystallite dimension is 0.4 μm.
Embodiment 4: Ultra-fine Grained W-5wt.%Y is prepared2O3
Firstly, under conditions of mechanical stirring and ultrasonication, by 2g yttrium nitrate hydrate (Y (NO3)3·6H2O) and
2.5g polyvinylpyrrolidone (PVP), which is dissolved in 150ml deionized water, is made solution A.Then it is secondary that 15g is added into solution A
Ammonium tungstate (APT).After five minutes, 25ml nitric acid and the reaction was continued 30 minutes generation suspension B is added.Backward suspension B in plus
Enter 150ml dehydrated alcohol to filter suspension B after reaction 3 hours, repeatedly washed with dehydrated alcohol to remove PVP as much as possible
To obtain sediment C, then sediment C is placed in in 80 DEG C of vacuum oven dry 10h, obtain powder precursor.It will
Powder precursor calcines 1h in air, and calcination temperature is 600 DEG C.Then it puts it into tube furnace and is passed through high-purity hydrogen progress
Reduction treatment, reduction temperature is 800 DEG C, heating rate is 5~10 DEG C/min, soaking time 60min, is obtained oxide-doped
Tungsten powder.De-agglomerated processing is carried out to Oxidation Doping tungsten powder using high-speed screw blade mixer, the revolving speed of blade is 2000 revs/min
Clock, being crushed the time is 0.5 hour, obtains the narrower de-agglomerated powder of particle diameter distribution.De-agglomerated powder is fitted into thin wall wrap model
Vacuum Package is carried out, isostatic cool pressing is then carried out, it is 250MPa that isostatic cool pressing, which suppresses pressure, and dwell time 10min is obtained into
Shape green compact.Forming green body carries out first step sintering in hydrogen atmosphere, 1550 DEG C of first step sintering temperature, heating rate for 5 DEG C/
Min, soaking time are less than 1h, are and then cooled to 1350 DEG C of heat preservation 10h of second step sintering temperature with 10 DEG C/min, obtain final
Ultra-fine Grained W-5wt.%Y2O3, consistency 96%, crystallite dimension is 0.4 μm.
Embodiment 5: Ultra-fine Grained W-5wt.%Y is prepared2O3
Firstly, under conditions of mechanical stirring and ultrasonication, by 2g yttrium nitrate hydrate (Y (NO3)3·6H2O) and
2.5g polyvinylpyrrolidone (PVP), which is dissolved in 150ml deionized water, is made solution A.Then it is secondary that 15g is added into solution A
Ammonium tungstate (APT).After five minutes, 25ml nitric acid and the reaction was continued 30 minutes generation suspension B is added.Backward suspension B in plus
Enter 150ml dehydrated alcohol to filter suspension B after reaction 3 hours, repeatedly washed with dehydrated alcohol to remove PVP as much as possible
To obtain sediment C, then sediment C is placed in in 80 DEG C of vacuum oven dry 10h, obtain powder precursor.It will
Powder precursor calcines 1h in air, and calcination temperature is 600 DEG C.Then it puts it into tube furnace and is passed through high-purity hydrogen progress
Reduction treatment, reduction temperature is 800 DEG C, heating rate is 5~10 DEG C/min, soaking time 60min, is obtained oxide-doped
Tungsten powder.De-agglomerated processing is carried out to Oxidation Doping tungsten powder using high-speed screw blade mixer, the revolving speed of blade is 2000 revs/min
Clock, being crushed the time is 0.5 hour, obtains the narrower de-agglomerated powder of particle diameter distribution.De-agglomerated powder is fitted into thin wall wrap model
Vacuum Package is carried out, isostatic cool pressing is then carried out, it is 250MPa that isostatic cool pressing, which suppresses pressure, and dwell time 10min is obtained into
Shape green compact.Forming green body carries out first step sintering in hydrogen atmosphere, 1550 DEG C of first step sintering temperature, heating rate for 5 DEG C/
Min, soaking time are less than 1h, are and then cooled to 1350 DEG C of heat preservation 40h of second step sintering temperature with 15 DEG C/min, obtain final
Ultra-fine Grained W-5wt.%Y2O3, consistency 97%, crystallite dimension is 0.6 μm.
Embodiment 6: Ultra-fine Grained W-5wt.%Y is prepared2O3
Firstly, under conditions of mechanical stirring and ultrasonication, by 2g yttrium nitrate hydrate (Y (NO3)3·6H2O) and
2.5g polyvinylpyrrolidone (PVP), which is dissolved in 150ml deionized water, is made solution A.Then it is secondary that 15g is added into solution A
Ammonium tungstate (APT).After five minutes, 25ml hydrochloric acid and the reaction was continued 30 minutes generation suspension B is added.Backward suspension B in plus
Enter 150ml dehydrated alcohol to filter suspension B after reaction 3 hours, repeatedly washed with dehydrated alcohol to remove PVP as much as possible
To obtain sediment C, then sediment C is placed in in 80 DEG C of vacuum oven dry 10h, obtain powder precursor.It will
Powder precursor calcines 1h in air, and calcination temperature is 600 DEG C.Then it puts it into tube furnace and is passed through high-purity hydrogen progress
Reduction treatment, reduction temperature is 800 DEG C, heating rate is 5~10 DEG C/min, soaking time 60min, is obtained oxide-doped
Tungsten powder.De-agglomerated processing is carried out to Oxidation Doping tungsten powder using high-speed screw blade mixer, the revolving speed of blade is 2000 revs/min
Clock, being crushed the time is 0.5 hour, obtains the narrower de-agglomerated powder of particle diameter distribution.De-agglomerated powder is fitted into thin wall wrap model
Vacuum Package is carried out, isostatic cool pressing is then carried out, it is 250MPa that isostatic cool pressing, which suppresses pressure, and dwell time 25min is obtained into
Shape green compact.Forming green body carries out first step sintering in hydrogen atmosphere, 1550 DEG C of first step sintering temperature, heating rate for 5 DEG C/
Min, soaking time are less than 1h, are and then cooled to 1300 DEG C of heat preservation 60h of second step sintering temperature with 10 DEG C/min, obtain final
Ultra-fine Grained W-5wt.%Y2O3, consistency 98%, crystallite dimension is 0.8 μm.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of preparation method of high-compactness fine grain tungsten sill, it is characterised in that: method includes the following steps:
S1. powder precursor is prepared using liquid chemical method in the salt of rare earths and polymer:
S2. using high energy dispersion carry out de-agglomerated handle to obtain it is finely dispersed obtain oxide-doped tungsten powder, then carry out cold
Hydrostatic pressing obtains forming base；
S3. high-compactness fine grain tungsten sill is prepared using twice sintering process.
2. according to the method described in claim 1, it is characterized by: the specific steps of the S1 are as follows:
S1.1 be according to mass ratio under conditions of mechanical stirring and ultrasonication, by the salt of rare earths and polymer (0.8~
0.9): solution A is made in 1 dissolution in deionized water,
Ammonium paratungstate is (0.03~0.05) according to the mass ratio of solid phase and liquid phase by S1.2: 1 addition S1.1 is obtained in solution A, and 5
~after ten minutes, acid flux material and the reaction was continued 20-50 minutes generation suspension B is added,
Dehydrated alcohol is added into the suspension B by S1.3, after reaction 2-4 hours, filters suspension B, obtains after washing repeatedly
Sediment C, then sediment C is placed in in 60 DEG C~80 DEG C of vacuum oven dry 10~for 24 hours, obtain powder precursor.
3. according to the method described in claim 1, it is characterized by: the specific steps of the S2 are as follows:
Powder precursor is calcined 0.5-2h by S2.1 in air, and calcination temperature is 500 DEG C~600 DEG C, is subsequently placed into tube furnace
In be passed through high-purity hydrogen carry out reduction treatment, reduction temperature is 600 DEG C~800 DEG C, heating rate is 5~10 DEG C/min, heat preservation
Time is 60~120min, obtains oxide-doped tungsten powder；
S2.2 carries out de-agglomerated processing to Oxidation Doping tungsten powder using high-speed screw blade mixer, and the revolving speed of blade is 2000-
3000 revs/min, being crushed the time is 0.5-1h, obtains the narrower de-agglomerated powder of particle diameter distribution；
De-agglomerated powder is fitted into thin wall wrap model and carries out Vacuum Package by S2.3, then carries out isostatic cool pressing, isostatic cool pressing compacting
Pressure is 200~280MPa, and the dwell time is 5~10min, obtains forming base.
4. according to the method described in claim 1, it is characterized by: the specific steps of the S3 are as follows:
S3.1 carries out two-step sintering for base is shaped in high-purity hydrogen protective atmosphere: first first step sintering is forming base with certain
Heating rate is heated to temperature T1, first time heat preservation is carried out, once sintered green body is obtained,
S3.2 then carries out second step sintering: by once sintered green body in T1On the basis of temperature T is cooled to certain rate2, into
Second heat preservation of row is to get to finally obtaining high-compactness fine grain tungsten sill.
5. according to the method described in claim 2, it is characterized by: the salt of rare earths includes yttrium nitrate hydration in the S1.1
Object；
The polymer includes polyvinylpyrrolidone；
The acid flux material includes hydrochloric acid and nitric acid；The concentration of the acid flux material is 65%~68%；The acid flux material with
The volume ratio of the solution A is 1:(4~6).
6. according to the method described in claim 3, it is characterized by: the partial size of the de-agglomerated powder in the S2.2 is less than 0.2 μ
m。
7. method according to claim 3, it is characterised in that: the relative density for shaping base in the S2.3 is greater than 50%.
8. according to the method described in claim 4, it is characterized by: first step sintering temperature T in the S3.11For 1300~
1600 DEG C, heating rate is 3-10 DEG C/min, soaking time 1-2h.
9. according to the method described in claim 4, it is characterized by: rate of temperature fall is 15-25 DEG C/min, temperature in the S3.2
It is down to T2, T2Compare T1Low 50-250 DEG C, in T2Lower soaking time is 10-60h.
10. according to the method described in claim 1, it is characterized by: the obtained high-compactness fine grain tungsten sill
Consistency is greater than 98%, and average grain size is less than 1 μm.
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