CN1257785C - Method for preparing nano-grade tungsten-based composite powder by sol-spray drying-thermal reduction - Google Patents
Method for preparing nano-grade tungsten-based composite powder by sol-spray drying-thermal reduction Download PDFInfo
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- CN1257785C CN1257785C CN 03143136 CN03143136A CN1257785C CN 1257785 C CN1257785 C CN 1257785C CN 03143136 CN03143136 CN 03143136 CN 03143136 A CN03143136 A CN 03143136A CN 1257785 C CN1257785 C CN 1257785C
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- 239000000843 powder Substances 0.000 title claims abstract description 116
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 27
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000010937 tungsten Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000007921 spray Substances 0.000 title 1
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 238000001694 spray drying Methods 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 239000002585 base Substances 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 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 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000009938 salting Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 229910003271 Ni-Fe Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910018054 Ni-Cu Inorganic materials 0.000 claims description 3
- 229910018481 Ni—Cu Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- -1 this moment Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 102000002322 Egg Proteins Human genes 0.000 claims description 2
- 108010000912 Egg Proteins Proteins 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910017709 Ni Co Inorganic materials 0.000 claims description 2
- 229910003267 Ni-Co Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910003262 Ni‐Co Inorganic materials 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910008947 W—Co Inorganic materials 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- 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 2
- 210000003278 egg shell Anatomy 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- OIGNJSKKLXVSLS-VWUMJDOOSA-N prednisolone Chemical compound O=C1C=C[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OIGNJSKKLXVSLS-VWUMJDOOSA-N 0.000 claims 2
- 238000004458 analytical method Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract 1
- 239000010419 fine particle Substances 0.000 abstract 1
- 238000004663 powder metallurgy Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005551 mechanical alloying Methods 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 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 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to a preparation method of powder metallurgy technology, in particular to the field of preparing nano-scale composite powder, which is characterized in that: weighing each metal salt in proportion to prepare a salt solution and a mixed salt solution; adding a small amount of acid or alkali to control the pH value to be less than 4 or more than 10, adding 0.1-5% of surfactant, spray-drying at the temperature of 300-350 ℃ to prepare the nano-oxide composite powder or the composite salt composite powder precursor, carrying out primary reduction at the temperature of 400-600 ℃, and carrying out secondary reduction at the temperature of 650-1000 ℃ to obtain the nano-tungsten-based composite powder. The nano tungsten-based composite powder prepared by the method has the characteristics of fine particle size, uniform component distribution and high purity, the Fisher particle size of the powder is smaller than 1.0 mu m, the specific surface particle size after dispersion and the shape analysis particle size of the powder are smaller than 100nm, the tungsten grain size of the powder is 20-50nm, the powder is spherical, the oxygen content is lower than 0.2%, and the powder has good sintering activity.
Description
Technical field
The present invention relates to the preparation method of powdered metallurgical material, particularly preparation has the method for the nanoscale tungsten base composite powder of high performance " super even, ultrapure, ultra-fine ", as W-Ni-fe, W-Cu, W-Ni-Cu etc.
Background technology
Tungsten-bast alloy has high density and excellent mechanical property, electrical property and hot property, and environmentally safe is used for preparing armor-piercing bullet, broken first cavity liner material, electric contact material, electrode material, microelectronics Packaging is heat sink.Adopt traditional micron order W, the prepared tungsten-bast alloys of element powders such as Ni, fe, it is thick that tungsten grain is organized, and density is lower, and mechanical property is lower, can not satisfy the new material performance requirement.Though grain refinement can improve alloy property, can also improve Adiabatic Shear.As by alloying, add Mo, Re, refinement tungsten grains such as cold working, but some method often makes grain refining effect not obvious, can be cost with the ductility of sacrificial alloy also.
Because the alloy organizing size has very big relation with the original particle size of powder, is refinement tungsten alloy microscopic structure valid approach so adopt nanometer powder.The preparation of tungsten-bast alloy composite powders such as relevant nanometer W-Ni-Fe, mainly containing freezing---seasoning (U.S. George D White and William E Gunrell), adopting this method can prepare tungstenic is three kinds of W-Ni-fe tungsten-bast alloy composite powders of 70%, 90% and 97%.The characteristics of this method are with ammonium metatungstate and nickel nitrate, ferric nitrate (or nickelous sulfate, ferric sulfate) be raw material, it is mixed according to certain ratio, prepare corresponding mixing salt solution, salting liquid is freezing, near the dry preparation complex salt presoma sublimation point of water with complex salt calcining, reduction, prepares W (Ni, Fe) composite powder then again.Adopt the prepared powder of this method to be coralliform, powder size is about 100nm, still, this method is freezing---and evaporation moisture content is chronic in the drying process link, be unfavorable for producing of powder batch, the formability of powder is bad simultaneously, easily introduces being mingled with of S, O when producing powder.
Human sol-gel methods such as Srikanth Raghunathan have prepared W-Cu, W-Mo, WC-Co composite powder, and it is to prepare gluey presoma earlier, carries out hydrogen reduction again and obtains nanometer powder.Its technical process is too complicated, is not suitable for producing in batches powder.
Composite powders such as the nanocrystalline W-Ni-Fe of domestic and international more employing prepared by mechanical alloy recent years, but the powder of its preparation exist be mingled with, many defectives are lumpd in oxidation and reunion.
Summary of the invention:
The objective of the invention is to overcome the weak point of prior art, adopt colloidal sol-spray-drying-thermal reduction to prepare W base composite powder, this powder has fine size, distributed components, characteristics that purity is high, have good sintering activity, satisfied preparation has the armor-piercing bullet of high-penetration performance, broken first property of medicine cover material, electric contact material, electrode material, requirement that microelectronics Packaging is heat sink.
The present invention is for achieving the above object, and the technical scheme of employing is:
1. the constituent of composite powder is: (100-χ) W-χ (Ni, Fe, Co, Cu, Cr, Mo), and χ is 2-12wt%, and main component is W, and alloying element is made up of among Ni, Fe, Co, Cu, Cr, the Mo etc. two or more.
At first in each slaine crystalline solid, add entry, be mixed with the corresponding metal salting liquid and add entry preparation mixing salt solution with each metal salt solution mixed preparing or after will each slaine crystalline solid mixing, adding acid or alkali rapid mixing again stirs, the control pH value is less than 4 or greater than 10, and add the 0.1-5% surfactant, obtain translucent colloidal sol body; Then 200-350 ℃ of following spray-drying, spray-drying speed is 20000～30000 rev/mins, preparation nano-scale oxide composite powder or complex salt composite powder presoma; Through ball milling and ultrasonic dispersion, obtain the powder of individual particle granularity less than 100nm; Once reduce recovery time 30～120min then at 400-600 ℃; And then carry out secondary reduction at 650-1000 ℃ again, recovery time 30～120min obtains granularity less than 100nm nanophase tungsten base composite powder, and protective atmosphere is H
2Or cracked ammonium.
The slaine of tungsten is metatungstate or paratungstate, and the soluble metallic salt of nickel, iron, copper or cobalt is their chlorate, sulfate, nitrate or oxalates.
Surfactant is a stearic acid, polyethylene glycol, urea, N, N dimethyl formamide, OP emulsifying agent, soil temperature-20, dodecyl sodium sulfate etc.
The acid that adds is HCl, HNO
3Or oxalic acid.
The alkali that adds is NaOH, KOH or ammoniacal liquor.
This method is applicable to preparation nanometer W-Ni-Cu, W-Cu, W-Ni-Co or W-Co composite powder.
Advantage of the present invention and good effect are embodied in:
1. compare with conventional tungsten powder, granularity is thinner, and powder size reduces more than 20 times, reaches 100nm
2. compare with each element mixed-powders such as conventional W, Ni, Fe, Cu, Co, the powder component distributing is more even, adopts solution to mix each element and reaches the degree that the molecular level level is mixed.
3. compare with conventional powder, powder composition purity height, powder sintered activity is big, and sintering temperature is low, and sintered products is more fine and close, reaches more than 99%, and the grain structure of alloy is thinner, has improved the intensity of alloy, and suitable preparation has the requirement of high-performance products.
4. with the present existing method for preparing nanometer powder as: mechanical alloying, freeze drying, chemical colloidal sol-preparing gel is ultra-fine or manocrystalline powders is compared, tool has an enormous advantage: compare with mechanical alloying, the minimizing powder is reunited and is mingled with, overcome the shortcoming of the very irregular and formability difference of mechanical alloying powder shape, adopt the powder shape spherical in shape of colloidal sol---spray-drying---thermal reduction preparation, powder flowbility is good, formability is good; Compare with freeze-drying, overcome the harshness and the long shortcoming of sublimation drying of technology controlling and process; With colloidal sol---the gel phase ratio, reduced the cumbersome and few shortcoming of preparation powder of process and technology.Colloidal sol---spray-drying---thermal reduction is fit to prepared in batches nanophase tungsten base composite powder.
With the tungsten base composite powder of this method preparation, powder particle is spherical in shape, and granularity is less than 100nm, and the powder non-oxidation is mingled with, the good dispersion of powder, and composition is even, and the formability of powder and sintering character are good.
The specific embodiment
Embodiment one:
To produce composition is that 90W-7Ni-3Fe nanophase tungsten base composite powder is an example.
1. take by weighing the ammonium metatungstate (3 (NH of 122.1g
4)
2O12WO
3.3H
2O), 34.5g nickel nitrate crystal (Ni (NO
3)
26H
2O) and 21.6g ferric nitrate crystal (Fe (NO
3)
39H
2O);
2. adding distilled water 397.8ml, 50.5ml, 34.3ml, to be mixed with mass percent in described slaine crystalline solid respectively be 30% salting liquid;
3. described each metal salt solution rapid mixing is stirred, add small amount of H NO
3Mix, the control pH value is 3, obtains transparent nearly colloidal sol body;
4. add 2g polyethylene glycol (PEG), make the powder good dispersion to prevent from the solution to occur precipitation;
5. nearly the colloidal sol body carries out spray-drying, and spray-drying speed is 30000 rev/mins, and the spray-drying temperature is 350 ℃, obtains the complex salt powder or the composite oxide power presoma of tungsten, nickel, iron; This moment, aggregate powder of AI/Yt was hollow egg shell ball shape, and granularity is 0.5-1.0 μ m;
6. through ball milling and ultrasonic dispersion, this powder is made up of several single granules; Single powder granule granularity is less than 100nm;
7. with the powder presoma at H
2Once reduce under the reducing atmosphere, reduction temperature is 500 ℃, insulation 90min;
8. for the first time reduction back powder carries out secondary reduction under 800 ℃, and temperature retention time is 90min, takes out powder after cooling to room temperature with the furnace;
9. powder is carried out X-Ray diffraction analysis, grain size analysis, BET specific surface, morphology analysis and chemical composition analysis:
X-Ray diffraction result shows the powder that makes with the present invention by W phase and γ-(Ni, Fe) two phase compositions, and W phase grain size is 20-50nm;
Results of grain size analysis shows that the Fisher particle size of powder agglomerates is 0.8 μ m;
The BET specific surface is analyzed granularity and is shown BET powder size 80nm;
ESEM morphology analysis result shows powder shape spherical in shape, and the individual particle granularity is less than 100nm;
Chemical composition analysis shows that the powder oxygen content is 0.2%, and each element powders component distributing is very even.
Embodiment two
To produce 95W-3.5Ni-1.5Fe nanophase composite powder is example.
1. take by weighing metal, ammonium paratungstate (APT, 5 (NH in proportion
4)
2O
12WO
35H
2O), nickel chloride crystal (NiCl
2.H
2O), frerrous chloride crystal (FeCl
24H
2O) 134.8g, 7.7g, 4.1g;
2. the distilled water that adds 650.6ml, 17.5ml, 11.5ml respectively is mixed with mass percent concentration respectively in described slaine crystalline solid be 20% solution;
3. fast described each metal salt solution is mixed and stir, adding less ammonia control pH value is 10, obtains translucent colloidal sol body;
4. add 0.9g polyethylene glycol (PEG) and mix, prevent precipitation and powder is uniformly dispersed;
5. colloid is carried out spray-drying, spray-drying speed is 25000 rev/mins, and the spray-drying temperature is 200 ℃, obtains the complex salt powder presoma of tungsten, nickel, iron, and this moment, powder was an aggregate; Be the hollow ball shape, granularity is less than 1.0 μ m, and powder is made up of several granules;
6. through ball milling and ultrasonic dispersion, obtain the powder of single granule granularity less than 100nm;
7. the powder presoma is once reduced under cracked ammonium atmosphere, reduction temperature is 550 ℃, and temperature retention time is 60min;
8. the powder after will once reducing carries out secondary reduction under 900 ℃, atmosphere is cracked ammonium, and temperature retention time is 120min; With the stove cooling, treat to take out powder after furnace temperature is reduced to room temperature.
9. powder is carried out X-Ray diffraction analysis, grain size analysis, the analysis of BET specific surface, morphology analysis and chemical composition analysis:
X-Ray diffraction result show powder by W mutually with γ-(Ni, Fe) mutually, two phase compositions, W phase grain size is 20-50nm;
Results of grain size analysis shows that the Fisher particle size of powder agglomerates is 1.0 μ m;
The BET specific surface is analyzed granularity and is shown BET powder size 70nm;
The ESEM morphology analysis shows powder shape spherical in shape, and the granule granularity is less than 100nm;
Chemical composition analysis shows that the oxygen content of powder is 0.2%, and does not have other impurity, and is lower than the oxygen content of conventional powder, the purity height, and each element powders component distributing is very even.
Claims (7)
1. the method for preparing nanophase tungsten base composite powder with colloidal sol one spray-drying-thermal reduction, it is to adopt soluble metal salt crystal that the slaine crystalline solid of tungsten adds nickel, iron, copper or cobalt to be mixed with one of at least solution, through mixing, add surfactant, add acid or alkali, the control pH value, stir fast, adopt spray-drying, ball milling then, be prepared from through secondary reduction again, it is characterized in that:
At first in each slaine crystalline solid, add entry, be mixed with the corresponding metal salting liquid, and with each metal salt solution mixed preparing or with adding entry preparation mixing salt solution after each slaine crystalline solid mixing, add acid or alkali rapid mixing again and stir, the control pH value is less than 4 or greater than 10; And add the 0.1-5% surfactant, obtain translucent colloidal sol body; Then 200-350 ℃ of following spray-drying, spray-drying speed is 20000～30000 rev/mins, preparation nano-scale oxide composite powder or complex salt composite powder presoma; Through ball milling and ultrasonic dispersion, obtain the powder of individual particle granularity less than 100nm; Once reduce recovery time 30～120min then at 400-600 ℃; And then carry out secondary reduction at 650-1000 ℃ again, recovery time 30～120min obtains granularity less than 100nm nanophase tungsten base composite powder; Protective atmosphere is H
2Or cracked ammonium.
2. the method for preparing nanophase tungsten base composite powder with colloidal sol-spray-drying-thermal reduction according to claim 1, it is characterized in that: the slaine of tungsten is metatungstate or paratungstate, and the soluble metallic salt of nickel, iron, copper or cobalt is their chlorate, sulfate, nitrate or oxalates.
3. according to claim 1ly prepare the method for nanophase tungsten base composite powder with colloidal sol-spray-drying-thermal reduction, it is characterized in that: surfactant is a stearic acid, polyethylene glycol, urea, N, N dimethyl formamide, OP emulsifying agent, soil temperature-20, dodecyl sodium sulfate.
4. according to claim 1ly prepare the method for nanophase tungsten base composite powder with colloidal sol-spray-drying-thermal reduction, it is characterized in that: the acid of adding is HCl, HNO
3Or oxalic acid; The alkali that adds is NaOH, KOH or ammoniacal liquor.
5. according to claim 1ly prepare the method for nanophase tungsten base composite powder with colloidal sol-spray-drying-thermal reduction, it is characterized in that: this method is applicable to preparation nanometer W-Ni-Cu, W-Cu, W-Ni-Co or W-Co composite powder.
6. prepare the method for nanometer tungsten base composite powder with colloidal sol-spray-drying-thermal reduction, it is characterized in that:
1. by W-Ni-Fe=90: 7: 3 component ratios take by weighing ammonium metatungstate, 34.5g nickel nitrate crystal and the 21.6g ferric nitrate crystal of 122.1g;
2. adding distilled water 397.8ml, 50.5ml, 34.3ml, to be mixed with mass percent in described slaine crystalline solid respectively be 30% salting liquid;
3. described each metal salt solution rapid mixing is stirred; Add small amount of H NO
3Mix, the control pH value is 3, obtains transparent nearly colloidal sol body;
4. add the 2g polyethylene glycol, prevent to occur precipitation in the solution and make the powder good dispersion that obtains;
5. solution is carried out spray-drying, spray-drying speed is 30000 rev/mins, and the spray-drying temperature is 350 ℃; Obtain the complex salt powder or the composite oxide power presoma of tungsten, nickel, iron; This moment, aggregate powder of AI/Yt was hollow egg shell ball shape, and granularity is 0.5-1.0 μ m, and this powder is made up of several single granules;
6. through ball milling and ultrasonic dispersion, single powder granule granularity is less than 100nm;
7. with this powder presoma at H
2Once reduce under the reducing atmosphere, reduction temperature is 500 ℃, insulation 90min;
8. the powder after the reduction for the first time carries out secondary reduction under 800 ℃, and temperature retention time is 90min, takes out powder after cooling to room temperature with the furnace.
7. prepare the method for nano based composite powder with colloidal sol one spray-drying-thermal reduction, it is characterized in that:
1. by W-Ni-Fe=95: component ratio took by weighing ammonium paratungstate, nickel chloride crystal, frerrous chloride crystal 134.8g, 7.7g, 4.1g in 3.5: 1.5;
2. the distilled water that adds 650.6ml, 17.5ml, 11.5ml respectively is mixed with mass percent concentration respectively in described slaine crystalline solid be 20% solution;
3. fast described each metal salt solution is mixed and stir, adding less ammonia control pH value is 10, obtains translucent colloidal sol body;
4. add the 0.9g polyethylene glycol and mix, prevent precipitation and the powder of preparation is uniformly dispersed;
5. colloid is carried out spray-drying, spray-drying speed is 25000 rev/mins, and the spray-drying temperature is 300 ℃; Obtain the complex salt powder presoma of tungsten, nickel, iron, this moment, powder was an aggregate, was the hollow ball shape, and granularity is less than 1.0 μ m, and powder is made up of several granules;
6. through ball milling and ultrasonic dispersion, obtain the powder of single granule granularity less than 100nm;
7. then this powder presoma is not once reduced in cracked ammonium atmosphere, reduction temperature is 550 ℃, and temperature retention time is 60min;
8. the powder after will once reducing again adopts secondary reduction down at 900 ℃, and atmosphere is cracked ammonium, and temperature retention time is 120min; With the stove cooling, treat to take out powder after furnace temperature is reduced to room temperature.
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