CN109158612A - A kind of preparation method of tungsten alloy forerunner composite granule, tungsten alloy and preparation method thereof - Google Patents
A kind of preparation method of tungsten alloy forerunner composite granule, tungsten alloy and preparation method thereof Download PDFInfo
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- CN109158612A CN109158612A CN201811117809.7A CN201811117809A CN109158612A CN 109158612 A CN109158612 A CN 109158612A CN 201811117809 A CN201811117809 A CN 201811117809A CN 109158612 A CN109158612 A CN 109158612A
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- 229910001080 W alloy Inorganic materials 0.000 title claims abstract description 148
- 238000002360 preparation method Methods 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 239000008187 granular material Substances 0.000 title claims abstract description 64
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000007788 liquid Substances 0.000 claims abstract description 86
- 239000006185 dispersion Substances 0.000 claims abstract description 75
- 239000011812 mixed powder Substances 0.000 claims abstract description 50
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 36
- 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 abstract description 30
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 28
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002815 nickel Chemical class 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 33
- 229910052721 tungsten Inorganic materials 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 3
- 238000009702 powder compression Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 36
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000004411 aluminium Substances 0.000 abstract description 16
- 239000000919 ceramic Substances 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 9
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 abstract description 8
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 abstract description 8
- 238000005728 strengthening Methods 0.000 abstract description 8
- 238000000975 co-precipitation Methods 0.000 abstract description 5
- 230000002708 enhancing effect Effects 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 29
- 239000001257 hydrogen Substances 0.000 description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 230000009467 reduction Effects 0.000 description 23
- 229910045601 alloy Inorganic materials 0.000 description 16
- 239000000956 alloy Substances 0.000 description 16
- 239000010937 tungsten Substances 0.000 description 16
- 238000001354 calcination Methods 0.000 description 15
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 14
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 14
- 229910002651 NO3 Inorganic materials 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 239000008236 heating water Substances 0.000 description 9
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 8
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 230000006698 induction Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 5
- -1 iron ion Chemical class 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 229910017343 Fe2 (SO4)3 Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005484 gravity Effects 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- B22F1/0003—
-
- 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
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The present invention relates to a kind of preparation methods of tungsten alloy forerunner composite granule, tungsten alloy and preparation method thereof, belong to high-temperature structural material technology field.The preparation method of tungsten alloy forerunner's composite granule of the invention, comprising the following steps: ammonium paratungstate, soluble ferric iron salt, the mixed dispersion liquid of soluble nickel salt and aluminum soluble salt are provided；The pH of mixed dispersion liquid is adjusted to being not more than 1.5 using oxalic acid, fully reacting, then remove solvent obtain mixed powder to get.The preparation method of tungsten alloy forerunner's composite granule of the invention, it is adjusted using pH of the oxalic acid to mixed dispersion liquid, since newly-generated wolframic acid, ferric oxalate, nickel oxalate and oxalic acid aluminium are common reaction co-precipitations, improve the uniformity consistency of each component in mixed powder, resulting composite granule can be with refined crystalline strengthening and dispersion-strengtherning tungsten alloy, the toughness that tungsten alloy can also be improved while tungsten alloy intensity can be increased substantially can be used for preparing the high tough tungsten alloy of nano-ceramic particle disperse enhancing.
Description
Technical field
The present invention relates to a kind of preparation methods of tungsten alloy forerunner composite granule, tungsten alloy and preparation method thereof, belong to height
Warm technical field of structural materials.
Background technique
High-specific gravity tungsten alloy is a kind of high density, high intensity, high ductility material, is widely used in military affairs, aerospace, smelting
The fields such as gold, machinery, however due to coarse grains, black brittleness, radiation brittleness, ductile-brittle transition temperature be higher, recrystallization temperature
The disadvantages of low and high temperature intensity is insufficient limits it and widely applies.Oxide (such as La2O3、Y2O3Deng) and carbide (example
Such as TaC, ZrC) have the characteristics that fusing point is high, elevated temperature strength is high, good chemical stability, therefore it is often used as alloy (Cu
Alloy, Al alloy, Mg alloy, W alloy etc.) the second phase of dispersion-strengtherning.Gu traditional tungsten alloy preparation process is solid+(liquid) system
Powder, sintering, still uses generally existing second phase of tungsten alloy of technique production to be unevenly distributed, causes to be present in tungsten conjunction compacting
Coarse grains and there is crystal boundary segregation in the second phase agglomeration in Jin Jing's grain, and the tungsten alloy of sintered state
The defects such as that there are hardness numbers is not high, toughness is lower, intensity is low.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of tungsten alloy forerunner composite granule, can be improved tungsten obtained and close
The toughness of gold.
The present invention also provides a kind of high tenacity tungsten alloys and preparation method thereof.
In order to achieve the goal above, technical solution used by tungsten alloy forerunner's composite granule of the invention is:
A kind of preparation method of tungsten alloy forerunner composite granule, comprising the following steps:
Ammonium paratungstate, soluble ferric iron salt, the mixed dispersion liquid of soluble nickel salt and aluminum soluble salt are provided；Using oxalic acid tune
The pH of mixed dispersion liquid is saved to being not more than 1.5, then fully reacting removes solvent and obtains mixed powder.
The preparation method of tungsten alloy forerunner's composite granule of the invention, is adjusted using pH of the oxalic acid to mixed dispersion liquid
Whole, hydrogen ion and tungstate ion, which can react, in solution generates wolframic acid precipitating；Oxalate denominationby and iron ion, nickel ion, aluminium from
Son reaction generates ferric oxalate, nickel oxalate and oxalic acid aluminum precipitation, since newly-generated wolframic acid, ferric oxalate, nickel oxalate and oxalic acid aluminium are
The reason of common reaction co-precipitation, improve the uniformity consistency of each component in mixed powder, this liquid liquid mixing-co-precipitation
Method made from composite granule, can increase substantially tungsten alloy intensity with refined crystalline strengthening and dispersion-strengtherning tungsten alloy
The toughness that tungsten alloy can also be improved simultaneously can be used for preparing the high tough tungsten alloy of nano-ceramic particle disperse enhancing.
The preparation method of above-mentioned tungsten alloy forerunner's composite granule, further includes calcining resulting mixed powder, so
It is restored afterwards with reducibility gas.Composite granule can be converted to the oxide of the metals such as tungsten, nickel, iron, aluminium by calcining,
The metal object outside alumina is restored by restoring.In reduction process, the second phase alumina is attached to the metal of tungsten, nickel and iron
Oxide surface can prevent growing up for tungsten, nickel and iron crystal grain, so that it is more tiny, equally distributed compound to obtain particle size
Tungsten powder.
Preferably, during adjusting pH, mixed dispersion liquid is heated；The temperature of the heating is 60~100 DEG C.
Heating is carried out when adjusting pH can promote the quick forming core of precipitation reaction, and such wolframic acid, ferric oxalate, nickel oxalate and oxalic acid aluminium can phases
Forming core mutually is depended on, to achieve the purpose that mutually to inhibit growth, such each component can also refine while reaching molecular level mixing
Crystal grain, moreover it is possible to which the rate for promoting precipitating to generate shortens the reaction time, reduces cost, increase economic efficiency.When in order to make to adjust pH
The amount of the oxalic acid of addition is easier to control, and while heating, is stirred to mixed dispersion liquid.
Ammonium paratungstate in mixed dispersion liquid, soluble nickel salt, the amount of soluble ferric iron salt and aluminum soluble salt, can basis
Tungsten in the tungsten alloy of design, nickel, iron, aluminium element amount controlled.Preferably, in the mixed powder, tungsten atom, iron are former
The molar ratio of son, nickle atom and aluminium atom is 1:0.01~0.30:0.05~0.38:0~0.22.Control each original in mixed powder
In the range, the beneficial effect with refined crystalline strengthening and dispersion-strengtherning, if exceeding the range, second meets out the ratio of son
The phenomenon that now reunion is grown up.
Technical solution used by the preparation method of tungsten alloy of the invention are as follows:
A kind of preparation method of tungsten alloy, comprising the following steps:
1) ammonium paratungstate, soluble ferric iron salt, the mixed dispersion liquid of soluble nickel salt and aluminum soluble salt are provided；Using oxalic acid
The pH of mixed dispersion liquid is adjusted to being not more than 1.5, then fully reacting removes solvent and obtains mixed powder；
2) mixed powder obtained in step 1) is calcined, is then restored with reducibility gas, obtained compound
Tungsten powder；
3) by the resulting compound tungsten powder compression moulding of step 2), sintering to get.
The preparation method of tungsten alloy of the invention, it is coprecipitated by liquid liquid mixing-in the case where not introducing other impurities
Solution-the co-reducing process that forms sediment-be divided into enables each element with reaching molecule stage uniformly mixing in tungsten alloy, and in tungsten alloy matrix
The second phase of ceramic alumina is added, can not only inhibiting tungsten alloy, crystal grain is grown up during the sintering process, it is help to obtain fine grain alloy,
And introducing aluminium element can absorb O element, reduce impurity and the cyrystal boundary segregations such as O, P in alloy, improve tungsten alloy inner element
Distribution.Wherein ceramic alumina disperse phase is tiny and is uniformly distributed in tungsten basal body, solve tungsten alloy consistency it is not high, second
Mutually be unevenly distributed, elevated temperature strength is insufficient and the problems such as heat creep resistance energy difference, be application and hair of the tungsten alloy in frontier
Exhibition provides new direction, and provides to introduce the second phase of enhancing in other alloys (such as acid bronze alloy, nickel-base alloy etc.)
A kind of new idea and method.
It is described to be sintered to discharge plasma sintering.Sintering temperature can be reduced using discharge plasma sintering (SPS),
Relatively low sintering temperature obtains higher consistency, and since discharge plasma densified sintering product process is very fast,
Crystal grain is not grown up also while can guarantee consistency, so that the lesser alloy of crystallite dimension is obtained, while not reducing intensity
Good ductility can also be obtained.
In the mixed powder, tungsten atom, iron atom, nickle atom and aluminium atom molar ratio be 1:0.01~0.30:
0.05~0.38:0~0.22.The ratio for controlling each atom in mixed powder in the range, has refined crystalline strengthening and disperse strong
The beneficial effect of change, if exceeding the range, the second phase will appear the phenomenon that reunion is grown up.
Technical solution used by tungsten alloy of the invention are as follows:
Tungsten alloy made from a kind of preparation method using above-mentioned tungsten alloy.
It is a kind of nano-ceramic particle disperse increasing made from the preparation method of tungsten alloy of the invention using above-mentioned tungsten alloy
Strong high tough tungsten alloy, the second phase ceramics alumina particle is evenly distributed in tungsten alloy, have consistency is high, elevated temperature strength is high,
The advantages that heat creep resistance can be good.
Specific embodiment
The present invention provides a kind of preparation methods of tungsten alloy forerunner's composite granule that can be improved tungsten alloy toughness, including
Following steps:
Ammonium paratungstate, soluble ferric iron salt, the mixed dispersion liquid of soluble nickel salt and aluminum soluble salt are provided；Using oxalic acid tune
The pH of mixed dispersion liquid is saved to being not more than 1.5, then fully reacting removes solvent and obtains mixed powder.
The preparation method of tungsten alloy forerunner's composite granule of the invention, is adjusted using pH of the oxalic acid to mixed dispersion liquid
Whole, hydrogen ion and tungstate ion, which can react, in solution generates wolframic acid precipitating；Oxalate denominationby and iron ion, nickel ion, aluminium from
Son reaction generates ferric oxalate, nickel oxalate and oxalic acid aluminum precipitation, since newly-generated wolframic acid, ferric oxalate, nickel oxalate and oxalic acid aluminium are
The reason of common reaction co-precipitation, improve the uniformity consistency of each component in mixed powder, this liquid liquid mixing-co-precipitation
Method made from composite granule, can increase substantially tungsten alloy intensity with refined crystalline strengthening and dispersion-strengtherning tungsten alloy
The toughness that tungsten alloy can also be improved simultaneously can be used for preparing the high tough tungsten alloy of nano-ceramic particle disperse enhancing.
The soluble ferric iron salt can be ferric sulfate [Fe2(SO4)3], ferric nitrate [Fe (NO3)3], iron chloride (FeCl3) in
At least one.The soluble nickel salt can be nickel sulfate (NiSO4·6H2O), nickel nitrate [Ni (NO3)2], nickel chloride
(NiCl2At least one of).The aluminum soluble salt can be aluminum sulfate [Al2(SO4)3], aluminum nitrate [Al (NO3)3·
9H2At least one of O].
Preferably, during adjusting pH, mixed dispersion liquid is heated；The temperature of the heating is 60~100 DEG C.
Heating is carried out when adjusting pH can promote the quick forming core of precipitation reaction, and such wolframic acid, ferric oxalate, nickel oxalate and oxalic acid aluminium can phases
Forming core mutually is depended on, to achieve the purpose that mutually to inhibit growth, such each component can also refine while reaching molecular level mixing
Crystal grain, moreover it is possible to which the rate for promoting precipitating to generate shortens the reaction time, reduces cost, increase economic efficiency.When in order to make to adjust pH
The amount of the oxalic acid of addition is easier to control, and while heating, is stirred to mixed dispersion liquid.
Preferably, the pH for adjusting the mixed dispersion liquid after pH is 0~1.5.It can be anti-in solution that pH, which is adjusted, in the range
Enough hydrogen ions should be provided, the smaller hydrogen ion of pH value is more, and reaction is accelerated, and forming core rate improves, and the powder just obtained is thinner
It is small.
Preferably, the concentration of ammonium paratungstate is 1.8~2.8g/mL in the mixed dispersion liquid.Secondary tungsten in mixed dispersion liquid
It when the concentration of sour ammonium is larger, cannot be completely dissolved, but ammonium paratungstate can be completely dissolved after adjusting pH value.
Preferably, removal solvent is to be separated by solid-liquid separation the mixed dispersion liquid after fully reacting, then obtained solid is done
It is dry.
Preferably, the preparation method of above-mentioned tungsten alloy composite granule further includes the mixed dispersion liquid progress after adjusting pH
It is heated to fully reacting, then removes solvent again.By heating to mixed dispersion liquid and can shorten the same of reaction time
When, promote the complete progress reacted in mixed dispersion liquid to reach 100% recycling of metal ion.Preferably, the heating
Temperature is 60~100 DEG C.
Preferably, the preparation method of above-mentioned tungsten alloy forerunner's composite granule, further includes carrying out resulting mixed powder
Calcining, is then restored with reducibility gas.Composite granule can be converted to the metals such as tungsten, nickel, iron, aluminium by calcining
Oxide is restored the metal object outside alumina by restoring.In reduction process, the second phase alumina be attached to tungsten, nickel and
The metal oxide surface of iron can prevent growing up for tungsten, nickel and iron crystal grain, to obtain, particle size is more tiny, uniformly divides
The compound tungsten powder of cloth.
Ammonium paratungstate in mixed dispersion liquid, soluble nickel salt, the amount of soluble ferric iron salt and aluminum soluble salt, can basis
Tungsten in the tungsten alloy of design, nickel, iron, aluminium element amount controlled.Preferably, in the mixed powder, tungsten atom, iron are former
The molar ratio of son, nickle atom and aluminium atom is 1:0.01~0.30:0.05~0.38:0~0.22.Control each original in mixed powder
In the range, the beneficial effect with refined crystalline strengthening and dispersion-strengtherning, if exceeding the range, second meets out the ratio of son
The phenomenon that now reunion is grown up.In mixed powder, the content of aluminium is not 0.Preferably, in mixed powder, tungsten atom, iron atom, nickel
The molar ratio of atom and aluminium atom is 1:0.01~0.30:0.05~0.38:0.004~0.22.
The temperature of the calcining is 550~650 DEG C, and the time of calcining is 0.5~2h.In order to shorten calcination time, reduce
Energy consumption, and guarantee the effect of calcining, before calcining, mixed powder is sprawled into the bed of material as 5~8mm.
Described to be reduced to restore twice, the temperature of the first reduction is 580~630 DEG C, and the time is 4~7h；Second of reduction
Temperature be 880~920 DEG C, the time be 8~12h.In order to enable the metal oxide of tungsten, nickel and iron to be reduced into completely
The calcined bed of material before being restored with reducibility gas, is sprawled the bed of material as 3~6mm by tungsten, nickel and ferrous metal.
Preferably, the reducibility gas used in reduction process is hydrogen.
The present invention also provides a kind of preparation methods of the tungsten alloy of high tenacity, comprising the following steps:
1) ammonium paratungstate, soluble ferric iron salt, the mixed dispersion liquid of soluble nickel salt and aluminum soluble salt are provided；Using oxalic acid
The pH of mixed dispersion liquid is adjusted to being not more than 1.5, then fully reacting removes solvent and obtains mixed powder；
2) mixed powder obtained in step 1) is calcined, is then restored with reducibility gas, obtained compound
Tungsten powder；
3) by the resulting compound tungsten powder compression moulding of step 2), sintering to get.
The preparation method of tungsten alloy of the invention, it is coprecipitated by liquid liquid mixing-in the case where not introducing other impurities
Solution-the co-reducing process that forms sediment-be divided into enables each element with reaching molecule stage uniformly mixing in tungsten alloy, and in tungsten alloy matrix
The second phase of ceramic alumina is added, can not only inhibiting tungsten alloy, crystal grain is grown up during the sintering process, it is help to obtain fine grain alloy,
And introducing aluminium element can absorb O element, reduce impurity and the cyrystal boundary segregations such as O, P in alloy, improve tungsten alloy inner element
Distribution.Wherein ceramic alumina disperse phase is tiny and is uniformly distributed in tungsten basal body, solve tungsten alloy consistency it is not high, second
Mutually be unevenly distributed, elevated temperature strength is insufficient and the problems such as heat creep resistance energy difference, be application and hair of the tungsten alloy in frontier
Exhibition provides new direction, and provides to introduce the second phase of enhancing in other alloys (such as acid bronze alloy, nickel-base alloy etc.)
A kind of new idea and method.
Preferably, the soluble ferric iron salt is ferric sulfate [Fe2(SO4)3], ferric nitrate [Fe (NO3)3], iron chloride (FeCl3)
At least one of.The soluble nickel salt is nickel sulfate (NiSO4·6H2O), nickel nitrate [Ni (NO3)2], nickel chloride (NiCl2)
At least one of.The aluminum soluble salt is aluminum sulfate [Al2(SO4)3], aluminum nitrate [Al (NO3)3·9H2O] at least one
Kind.
Preferably, during adjusting pH, mixed dispersion liquid is stirred and is heated.Heating is carried out when adjusting pH to be promoted
Into the quick forming core of precipitation reaction, such wolframic acid, ferric oxalate, nickel oxalate and oxalic acid aluminium can mutually depend on forming core, to reach phase
Mutually inhibit the purpose of growth, such each component can also refine crystal grain while reaching molecular level mixing.The temperature of the heating
It is 60~100 DEG C.
Preferably, the pH for adjusting the mixed dispersion liquid after pH is 0~1.5.
Preferably, the concentration of ammonium paratungstate is 1.8~2.8g/mL in the mixed dispersion liquid.
The removal solvent is that the mixed dispersion liquid after adjusting pH is separated by solid-liquid separation, then obtained solid is dried.
The preparation method of above-mentioned tungsten alloy composite granule further includes heating the mixed dispersion liquid after adjustment pH, so
Remove solvent again afterwards.Preferably, the temperature of the heating is 60~100 DEG C.
The temperature of the calcining is 550~650 DEG C, and the time of calcining is 0.5~2h.Preferably, before calcining, by mixed powder
Body sprawls the bed of material as 5~8mm.
Described to be reduced to restore twice, the temperature of the first reduction is 580~630 DEG C, and the time is 4~7h；Second of reduction
Temperature be 880~920 DEG C, the time be 8~12h.Preferably, before reduction, the calcined bed of material is sprawled as 3~6mm's
The bed of material.
The reducibility gas used in reduction process is hydrogen.
It is described to be sintered to discharge plasma sintering.The temperature of the discharge plasma sintering is 1180~1250 DEG C,
Time is 3~5min.Sintering temperature can be reduced using discharge plasma sintering (SPS), is obtained in relatively low sintering temperature
Higher consistency is obtained, and since discharge plasma densified sintering product process is very fast, can guarantee brilliant while consistency
Grain is not grown up also, to obtain the lesser alloy of crystallite dimension, good ductility can also be obtained while not reducing intensity.
Preferably, described to be sintered to discharge plasma sintering；The pressure of the compression moulding is 30~60MPa.
It is described to be sintered to vacuum frequency induction sintering；The pressure of the compression moulding is 180~200MPa.Vacuum frequency induction is burnt
Before knot, the dwell time of compression moulding is 1~3min.The temperature of the vacuum frequency induction sintering is 1400~1500 DEG C, the time
For 4~8h.
In the mixed powder, tungsten atom, iron atom, nickle atom and aluminium atom molar ratio be 1:0.01~0.30:
0.05~0.38:0~0.22.The ratio for controlling each atom in mixed powder in the range, has refined crystalline strengthening and disperse strong
The beneficial effect of change, if exceeding the range, the second phase will appear the phenomenon that reunion is grown up.In mixed powder, the content of aluminium is not
It is 0.Preferably, in mixed powder, tungsten atom, iron atom, nickle atom and aluminium atom molar ratio be 1:0.01~0.30:0.05
~0.38:0.004~0.22.
The present invention also provides tungsten alloys made from a kind of preparation method using above-mentioned tungsten alloy.
It is a kind of nano-ceramic particle disperse increasing made from the preparation method of tungsten alloy of the invention using above-mentioned tungsten alloy
Strong high tough tungsten alloy, the second phase ceramics alumina particle is evenly distributed in tungsten alloy, have consistency is high, elevated temperature strength is high,
The advantages that heat creep resistance can be good.
Below in conjunction with specific embodiment, further description of the technical solution of the present invention.
The embodiment 1 of the preparation method of tungsten alloy forerunner's composite granule
The preparation method of tungsten alloy forerunner's composite granule of the present embodiment, includes the following steps:
1) by 131.28kg ammonium paratungstate (APT), 15.60kg nickel sulfate (NiSO4·6H2O), 5.36kg ferric sulfate [Fe2
(SO4)3] and 0.84kg aluminum sulfate [Al2(SO4)3] be added in 51L distilled water, it is to be dissolved to obtain mixed dispersion liquid later completely；
Oxalic acid is added in gained mixed dispersion liquid and adjusts pH=1.5, is then heated using 100 DEG C of water-bath, to
After the temperature of mixed dispersion liquid rises to 100 DEG C, continue the heating water bath using 100 DEG C, to mixed dispersion liquid one in heating process
Directly it is stirred；After complete reaction, it filters, is dry, obtaining mixed powder；
2) 1h is calcined at 550 DEG C after gained mixed powder being sprawled into the bed of material with a thickness of 5mm, then by calcined product
It is put into tubular reduction furnace, after sprawling into the bed of material with a thickness of 3mm, is passed through hydrogen and restores 7h at 590 DEG C, then cross 60 meshes
Net, extracting screen underflow are replaced in tubular reduction furnace, after sprawling into the bed of material with a thickness of 3mm, are passed through hydrogen and are restored at 880 DEG C
12h, then cross 60 mesh screens to get.
The embodiment 2 of the preparation method of tungsten alloy forerunner's composite granule
The preparation method of tungsten alloy forerunner's composite granule of the present embodiment, includes the following steps:
1) by 134.26kg ammonium paratungstate (APT), 9.36kg nickel sulfate (NiSO4·6H2O), 3.21kg ferric sulfate [Fe2
(SO4)3] and 0.34kg aluminum sulfate [Al2(SO4)3] be added in 49L distilled water, it is to be dissolved to obtain mixed dispersion liquid later completely；
Oxalic acid is added in gained mixed dispersion liquid and adjusts pH=1.5, is then heated using 90 DEG C of water-bath, to mixed
Close dispersion liquid temperature rise to 90 DEG C after, continue the heating water bath using 90 DEG C, it is straight to mixed dispersion liquid one in heating process
Row stirring；After complete reaction, it filters, is dry, obtaining mixed powder；
2) 1.5h is calcined at 550 DEG C after gained mixed powder being sprawled into the bed of material with a thickness of 6mm, then produces calcining
Object is put into tubular reduction furnace, after sprawling into the bed of material with a thickness of 4mm, is passed through at 600 DEG C of hydrogen and is restored 6h, and 80 meshes are then crossed
Net, extracting screen underflow are replaced in tubular reduction furnace, after sprawling into the bed of material with a thickness of 4mm, are passed through hydrogen and are restored at 890 DEG C
11h, then cross 80 mesh screens to get.
The embodiment 3 of the preparation method of tungsten alloy forerunner's composite granule
The preparation method of tungsten alloy forerunner's composite granule of the present embodiment, includes the following steps:
1) by 128.17kg ammonium paratungstate (APT), 15.20kg nickel nitrate [Ni (NO3)2], 9.08kg ferric nitrate [Fe
(NO3)3] and 3.68kg aluminum nitrate [Al (NO3)3·9H2O] it is added in 52L distilled water, it is to be dissolved to obtain mixing dispersion later completely
Liquid；
Oxalic acid is added in gained mixed dispersion liquid and adjusts pH=1.0, is then heated using 90 DEG C of water-bath, to mixed
Close dispersion liquid temperature rise to 90 DEG C after, continue the heating water bath using 90 DEG C, it is straight to mixed dispersion liquid one in heating process
Row stirring；After complete reaction, it filters, is dry, obtaining mixed powder；
2) 2h is calcined at 550 DEG C after gained mixed powder being sprawled into the bed of material with a thickness of 7mm, then by calcined product
It is put into tubular reduction furnace, after sprawling into the bed of material with a thickness of 5mm, is passed through at 610 DEG C of hydrogen and restores 5h, then sieve with 100 mesh sieve
Net, extracting screen underflow are replaced in tubular reduction furnace, after sprawling into the bed of material with a thickness of 5mm, are passed through hydrogen and are restored at 900 DEG C
10h, then sieve with 100 mesh sieve net to get.
The embodiment 4 of the preparation method of tungsten alloy forerunner's composite granule
The preparation method of tungsten alloy forerunner's composite granule of the present embodiment, includes the following steps:
1) by 121.93kg ammonium paratungstate (APT), 21.84kg nickel sulfate (NiSO4·6H2O), 7.50kg ferric sulfate [Fe2
(SO4)3] and 36.76kg aluminum nitrate [Al (NO3)3·9H2O] it is added in 63L distilled water, it is to be dissolved to obtain mixing point later completely
Dispersion liquid；
Oxalic acid is added in gained mixed dispersion liquid and adjusts pH=1.0, is then heated using 85 DEG C of water-bath, to mixed
Close dispersion liquid temperature rise to 85 DEG C after, continue the heating water bath using 85 DEG C, it is straight to mixed dispersion liquid one in heating process
Row stirring；After complete reaction, it filters, is dry, obtaining mixed powder；
2) 0.5h is calcined at 600 DEG C after gained mixed powder being sprawled into the bed of material with a thickness of 6mm, then produces calcining
Object is put into tubular reduction furnace, after sprawling into the bed of material with a thickness of 6mm, is passed through at 620 DEG C of hydrogen and is restored 5h, and 120 mesh are then crossed
Sieve, extracting screen underflow are replaced in tubular reduction furnace, after sprawling into the bed of material with a thickness of 6mm, are passed through hydrogen and are gone back at 900 DEG C
Former 9h, then cross 120 mesh screens to get.
The embodiment 5 of the preparation method of tungsten alloy forerunner's composite granule
The preparation method of tungsten alloy forerunner's composite granule of the present embodiment, includes the following steps:
1) by 119.16kg ammonium paratungstate (APT), 31.20kg nickel sulfate (NiSO4·6H2O), 12.96kg ferric nitrate [Fe
(NO3)3] and 29.41kg aluminum nitrate [Al (NO3)3·9H2O] it is added in 64.24L distilled water, it is to be dissolved to be mixed later completely
Dispersion liquid；
Oxalic acid is added in gained mixed dispersion liquid and adjusts pH=0.5, is then heated using 90 DEG C of water-bath, it is to be mixed
After the temperature of dispersion liquid rises to 90 DEG C, continues the heating water bath using 90 DEG C, mixed dispersion liquid is carried out always in heating process
Stirring；After complete reaction, it filters, is dry, obtaining mixed powder；
2) 1h is calcined at 650 DEG C after gained mixed powder being sprawled into the bed of material with a thickness of 8mm, then by calcined product
It is put into tubular reduction furnace, after sprawling into the bed of material with a thickness of 6mm, is passed through hydrogen and restores 4h at 620 DEG C, then cross 100 mesh
Sieve, extracting screen underflow are replaced in tubular reduction furnace, after sprawling into the bed of material with a thickness of 6mm, are passed through hydrogen and are gone back at 920 DEG C
Former 8h, then sieve with 100 mesh sieve net to get.
The embodiment 6 of the preparation method of tungsten alloy forerunner's composite granule
The preparation method of tungsten alloy forerunner's composite granule of the present embodiment, includes the following steps:
1) by 128.51kg ammonium paratungstate (APT), 15.20kg nickel nitrate [Ni (NO3)2], 9.08kg ferric nitrate [Fe
(NO3)3] and 1.84kg aluminum nitrate [Al (NO3)3·9H2O] it is added in 52L distilled water, it is to be dissolved to obtain mixing dispersion later completely
Liquid；
Oxalic acid is added in gained mixed dispersion liquid and adjusts pH=0.5, is then heated using 65 DEG C of water-bath, to mixed
Close dispersion liquid temperature rise to 65 DEG C after, continue the heating water bath using 65 DEG C, it is straight to mixed dispersion liquid one in heating process
Row stirring；After complete reaction, it filters, is dry, obtaining mixed powder；
2) 2h is calcined at 550 DEG C after gained mixed powder being sprawled into the bed of material with a thickness of 7mm, then by calcined product
It is put into tubular reduction furnace, after sprawling into the bed of material with a thickness of 5mm, is passed through hydrogen and restores 5h at 610 DEG C, then cross 100 mesh
Sieve, extracting screen underflow are replaced in tubular reduction furnace, after sprawling into the bed of material with a thickness of 5mm, are passed through hydrogen and are gone back at 900 DEG C
Former 10h, then sieve with 100 mesh sieve net to get.
The embodiment 7 of the preparation method of tungsten alloy forerunner's composite granule
The preparation method of tungsten alloy forerunner's composite granule of the present embodiment, includes the following steps:
1) 130.24kg ammonium paratungstate (APT), 9.36kg nickel sulfate (NiSO4·6H2O), 3.21kg ferric sulfate [Fe2
(SO4)3] and 10.06kg aluminum sulfate [Al2(SO4)3] be added in 51L distilled water, it is to be dissolved to obtain mixed dispersion liquid later completely；
Oxalic acid is added in gained mixed dispersion liquid and adjusts pH=1.0, is then heated using 75 DEG C of water-bath, to mixed
Close dispersion liquid temperature rise to 75 DEG C after, continue the heating water bath using 75 DEG C, it is straight to mixed dispersion liquid one in heating process
Row stirring；After complete reaction, it filters, is dry, obtaining mixed powder；
2) 1.5h is calcined at 550 DEG C after gained mixed powder being sprawled into the bed of material with a thickness of 6mm, then produces calcining
Object is put into tubular reduction furnace, after sprawling into the bed of material with a thickness of 4mm, is passed through hydrogen and is restored 6h at 600 DEG C, and 80 mesh are then crossed
Sieve, extracting screen underflow are replaced in tubular reduction furnace, after sprawling into the bed of material with a thickness of 4mm, are passed through hydrogen and are gone back at 890 DEG C
Former 11h, then cross 80 mesh screens to get.
The embodiment 8 of the preparation method of tungsten alloy forerunner's composite granule
The preparation method of tungsten alloy forerunner's composite granule of the present embodiment, includes the following steps:
1) by 126.78kg ammonium paratungstate (APT), 10.80kg nickel chloride (NiCl2), 6.08kg iron chloride (FeCl3) and
11.03kg aluminum nitrate [Al (NO3)3·9H2O] it is added in 54L distilled water, it is to be dissolved to obtain mixed dispersion liquid later completely；
Oxalic acid is added in gained mixed dispersion liquid and adjusts pH=0.7, is then heated using 90 DEG C of water-bath, to mixed
Close dispersion liquid temperature rise to 90 DEG C after, continue the heating water bath using 90 DEG C, it is straight to mixed dispersion liquid one in heating process
Row stirring；After complete reaction, it filters, is dry, obtaining mixed powder；
2) 2h is calcined at 550 DEG C after gained mixed powder being sprawled into the bed of material with a thickness of 7mm, then by calcined product
It is put into tubular reduction furnace, after sprawling into the bed of material with a thickness of 5mm, is passed through hydrogen and restores 5h at 610 DEG C, then cross 100 mesh
Sieve, extracting screen underflow are replaced in tubular reduction furnace, after sprawling into the bed of material with a thickness of 5mm, are passed through hydrogen and are gone back at 900 DEG C
Former 10h, then sieve with 100 mesh sieve net to get.
The embodiment 9 of the preparation method of tungsten alloy forerunner's composite granule
The preparation method of the tungsten alloy composite precursor of the present embodiment, comprising the following steps:
1) by 126.78kg ammonium paratungstate (APT), 21.41kg nickel chloride (NiCl2), 21.01kg iron chloride (FeCl3) and
16.75kg aluminum nitrate [Al (NO3)3·9H2O] it is added in 54L distilled water, it is to be dissolved to obtain mixed dispersion liquid later completely；Through counting
The molar ratio for calculating tungsten atom in mixed dispersion liquid, nickle atom, iron atom and aluminium atom is about 1:0.37:0.29:0.1；
Gained mixed dispersion liquid is heated to 90 DEG C by the water-bath for taking 90 DEG C in a water bath, is then added in mixed dispersion liquid
Enter oxalic acid and adjust pH=0.7, continues the heating water bath using 90 DEG C, mixed dispersion liquid is stirred always in heating process；
After complete reaction, it filters, is dry, obtaining mixed powder；
2) 2h is calcined at 550 DEG C after gained mixed powder being sprawled into the bed of material with a thickness of 7mm, then by calcined product
It is put into tubular reduction furnace, after sprawling into the bed of material with a thickness of 5mm, is passed through hydrogen and restores 5h at 610 DEG C, then cross 100 mesh
Sieve, extracting screen underflow are replaced in tubular reduction furnace, after sprawling into the bed of material with a thickness of 5mm, are passed through hydrogen and are gone back at 900 DEG C
Former 10h, then sieve with 100 mesh sieve net to get.
The embodiment 1 of the preparation method of tungsten alloy
The preparation method of the tungsten alloy of the present embodiment, comprising the following steps:
Tungsten alloy forerunner's composite granule made from the embodiment 1 of the preparation method of tungsten alloy forerunner's composite granule is put into soft
In gum cover, it is subsequently placed in progress isostatic cool pressing, pressure maintaining 3min in 180MPa super-pressure room, obtains cold pressing green compact, then green compact are put
Enter in Medium frequency induction sintering furnace, be passed through hydrogen, under the protection of hydrogen with 1420 DEG C of sintering 8h to get.
The embodiment 2 of the preparation method of tungsten alloy
The preparation method of the tungsten alloy of the present embodiment, comprising the following steps:
Tungsten alloy forerunner's composite granule made from the embodiment 2 of the preparation method of tungsten alloy forerunner's composite granule is put into soft
In gum cover, it is subsequently placed in progress isostatic cool pressing, pressure maintaining 2min in 190MPa super-pressure room, obtains cold pressing green compact, then green compact are put
Enter in Medium frequency induction sintering furnace, be passed through hydrogen, under the protection of hydrogen with 1440 DEG C of sintering 6h to get.
The embodiment 3 of the preparation method of tungsten alloy
The preparation method of the tungsten alloy of the present embodiment, comprising the following steps:
Tungsten alloy forerunner's composite granule made from the embodiment 3 of the preparation method of tungsten alloy forerunner's composite granule is put into soft
In gum cover, it is subsequently placed in progress isostatic cool pressing, pressure maintaining 1min in 200MPa super-pressure room, obtains cold pressing green compact, then green compact are put
Enter in Medium frequency induction sintering furnace, be passed through hydrogen, under the protection of hydrogen with 1460 DEG C of sintering 5h to get.
The embodiment 4 of the preparation method of tungsten alloy
The preparation method of the tungsten alloy of the present embodiment, comprising the following steps:
Tungsten alloy forerunner's composite granule made from the embodiment 4 of the preparation method of tungsten alloy forerunner's composite granule is put into soft
In gum cover, it is subsequently placed in progress isostatic cool pressing, pressure maintaining 3min in 200MPa super-pressure room, obtains cold pressing green compact, then green compact are put
Enter in Medium frequency induction sintering furnace, be passed through hydrogen, under the protection of hydrogen with 1500 DEG C of sintering 4h to get.
The embodiment 5 of the preparation method of tungsten alloy
The preparation method of the tungsten alloy of the present embodiment, comprising the following steps:
Tungsten alloy forerunner's composite granule made from the embodiment 5 of the preparation method of tungsten alloy forerunner's composite granule is put into stone
Mo Zhong, be subsequently placed in discharge plasma sintering furnace be sintered to get；The temperature of sintering is 1250 DEG C, and soaking time is
5min, the pressure 30MPa of sintering.
The embodiment 6 of the preparation method of tungsten alloy
The preparation method of the tungsten alloy of the present embodiment, comprising the following steps:
Tungsten alloy forerunner's composite granule made from the embodiment 6 of the preparation method of tungsten alloy forerunner's composite granule is put into stone
Mo Zhong, be subsequently placed in discharge plasma sintering furnace be sintered to get；The temperature of sintering is 1200 DEG C, and soaking time is
3min, the pressure 40MPa of sintering.
The embodiment 7 of the preparation method of tungsten alloy
The preparation method of the tungsten alloy of the present embodiment, comprising the following steps:
Tungsten alloy forerunner's composite granule made from the embodiment 7 of the preparation method of tungsten alloy forerunner's composite granule is put into stone
Mo Zhong, be subsequently placed in discharge plasma sintering furnace be sintered to get；The temperature of sintering is 1180 DEG C, and soaking time is
5min, the pressure 50MPa of sintering.
The embodiment 8 of the preparation method of tungsten alloy
The preparation method of the tungsten alloy of the present embodiment, comprising the following steps:
Tungsten alloy forerunner's composite granule made from the embodiment 8 of the preparation method of tungsten alloy forerunner's composite granule is put into stone
Mo Zhong, be subsequently placed in discharge plasma sintering furnace be sintered to get；The temperature of sintering is 1190 DEG C, and soaking time is
5min, the pressure 50MPa of sintering.
The embodiment 9 of the preparation method of tungsten alloy
The preparation method of the tungsten alloy of the present embodiment, comprising the following steps:
Tungsten alloy forerunner's composite granule made from the embodiment 9 of the preparation method of tungsten alloy forerunner's composite granule is put into stone
Mo Zhong, be subsequently placed in discharge plasma sintering furnace be sintered to get；The temperature of sintering is 1190 DEG C, and soaking time is
5min, the pressure 50MPa of sintering.
The embodiment of tungsten alloy
The tungsten alloy of the present embodiment is the preparation method system in the Examples 1 to 9 using the preparation method of tungsten alloy respectively
, details are not described herein again.
Comparative example
The preparation method of tungsten alloy forerunner's composite granule of this comparative example, tungsten alloy forerunner's composite granule with embodiment 1
The difference of preparation method be only adjusted using pH of the citric acid to mixed dispersion liquid.
Then by tungsten alloy forerunner's composite granule of comparative example using the middle tungsten in the embodiment 1 of the preparation method of tungsten alloy
Tungsten alloy is made in the preparation method of alloy.
Experimental example
Tungsten alloy obtained in the Examples 1 to 9 and comparative example of the preparation method of tungsten alloy is taken, is measured using division lines method
The grain size of alloy measures alloy density using Archimedes's drainage and calculates relative density (relative to each alloy
Theoretical density), using the microhardness of HVS-1000A microhardness testers measurement alloy, while using SHIMADZU AG-I
250KN precision universal testing machine measures the tensile strength of alloy, as a result see the table below 1.
The performance of tungsten alloy in the Examples 1 to 9 and comparative example of the preparation method of 1 tungsten alloy of table
By data in table 1 it is found that compared to comparative example, oxalic acid pair is used in the Examples 1 to 9 of the preparation method of tungsten alloy
The pH of mixed dispersion liquid is adjusted, and gained tungsten alloy has crystal grain tiny and the high characteristic of consistency, not only possesses high drawing
The advantage in terms of the comprehensive performances such as intensity and excellent toughness is stretched, reason is the prepared each component uniformity of powder
Good, powder granule is tiny, and sintering activity is good；And introduce the effect that nano-second-phase plays refined crystalline strengthening and dispersion-strengtherning.
Claims (8)
1. a kind of preparation method of tungsten alloy forerunner composite granule, it is characterised in that: the following steps are included:
Ammonium paratungstate, soluble ferric iron salt, the mixed dispersion liquid of soluble nickel salt and aluminum soluble salt are provided；It is adjusted using oxalic acid mixed
The pH of dispersion liquid is closed to being not more than 1.5, then fully reacting removes solvent and obtains mixed powder.
2. the preparation method of tungsten alloy forerunner composite granule according to claim 1, it is characterised in that: further include by gained
Mixed powder calcined, then restored with reducibility gas.
3. the preparation method of tungsten alloy forerunner composite granule according to claim 1, it is characterised in that: adjust the process of pH
In, mixed dispersion liquid is heated；The temperature of the heating is 60~100 DEG C.
4. the preparation method of tungsten alloy forerunner composite granule according to any one of claims 1 to 3, feature exist
In: in the mixed powder, tungsten atom, iron atom, nickle atom and aluminium atom molar ratio be 1:0.01~0.30:0.05~
0.38:0~0.22.
5. a kind of preparation method of tungsten alloy, it is characterised in that: the following steps are included:
1) ammonium paratungstate, soluble ferric iron salt, the mixed dispersion liquid of soluble nickel salt and aluminum soluble salt are provided；It is adjusted using oxalic acid
To being not more than 1.5, then fully reacting removes solvent and obtains mixed powder the pH of mixed dispersion liquid；
2) mixed powder obtained in step 1) is calcined, is then restored with reducibility gas, obtain compound tungsten powder；
3) by the resulting compound tungsten powder compression moulding of step 2), sintering to get.
6. the preparation method of tungsten alloy according to claim 5, it is characterised in that: described to be sintered to discharge plasma burning
Knot.
7. the preparation method of tungsten alloy according to claim 5, it is characterised in that: in the mixed powder, tungsten atom, iron
The molar ratio of atom, nickle atom and aluminium atom is 1:0.01~0.30:0.05~0.38:0~0.22.
8. tungsten alloy made from a kind of preparation method using tungsten alloy as claimed in claim 5.
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|---|---|---|---|---|
| CN110014163A (en) * | 2019-04-19 | 2019-07-16 | 广东省材料与加工研究所 | Tungsten alloy powder and its preparation method and application |
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