CN105798317A - Preparation method for polyhedral submicron tungsten powder - Google Patents
Preparation method for polyhedral submicron tungsten powder Download PDFInfo
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 50
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012065 filter cake Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 150000003657 tungsten Chemical class 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 239000002245 particle Substances 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 7
- 239000000243 solution Substances 0.000 abstract description 7
- 239000002243 precursor Substances 0.000 abstract description 5
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 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
-
- B22F1/0007—
Abstract
The invention belongs to the technical field of powder preparation, and particularly relates to a preparation method for polyhedral submicron tungsten powder. The preparation method includes the following steps that (1) soluble tungsten salt and a surface active agent are dissolved into water and stirred evenly, the pH is adjusted with acid to reach 2-4, then a solution A is obtained, and a reducing agent is dissolved in water to obtain a solution B; (2) after the solution A is heated to 50-90 DEG C, the solution B is poured in, a mixed solution with A and B is obtained, the volume ratio of the solution A to the solution B is 3:1-1:3, reaction is carried out for 1-6 h at the temperature kept at 50-90 DEG C, then the mixed solution is cooled to 10-30 DEG C, a tungsten oxide precursor filter cake is obtained after reaction products are subjected to solid-liquid separation, and impurities in the tungsten oxide precursor filter cake are removed through washing with water; tungsten oxide precursor powder is obtained after water in the washed filter cake is removed; and (3) the tungsten oxide precursor powder is subjected to heat treatment at a reducing atmosphere, and then the polyhedral submicron tungsten powder is obtained. The production process is simple, short, easy to control, small in equipment investment, and low in production cost. Prepared product particles are polyhedral, particle diameter distribution is narrow, and the degree of crystallinity is high.
Description
Technical field
The invention belongs to powder preparation technical field, the preparation method particularly relating to a kind of polyhedron Sub-micron Tungsten Powder.
Background technology
Tungsten is the rare metal of a kind of preciousness, is widely used as hard alloy, special steel and various tungsten product.In tungsten alloy, topmost raw material is tungsten powder, and the performance of the size alloy of its granularity plays critical effect.Significantly improving containing coarse grained alloy property containing fine grain alloy ratio, if alloy is containing ultra-fine grain, then performance can produce qualitative leap, reaches the unification of high intensity and high rigidity, thus extending its application.Meanwhile, tungsten application in these areas also has close relationship with the distribution of its pattern, granularity.
Ultra-fine and Sub-micron Tungsten Powder preparation method mainly has at present: (1) tungsten oxide reducing process, and this method is industrial common method, but shortcoming be yield poorly, cost height, cycle length, technology controlling and process complicated；(2) high-energy ball milling method, the method has that cost is low, yield is high and the advantage such as technique is simple, the applications less high in some purity to powder body and granularity requirements is very wide, but by the material grindings of 10 μm to micron order even submicron-grade superfine powder body, Ball-milling Time is very long, and the cost such as ball consumption, energy consumption increases accordingly；(3) spray drying method, instant heating chemical synthesis, ultrafine tungsten powder granule prepared by this method is spherical shell shape, and specific surface area is bigger, porosity is high, hydrogen in reduction process is conducive to enter the discharge with steam, thus reducing reduction temperature and shortening the recovery time, it is easy to prepare ultrafine tungsten powder, but production efficiency is low, equipment is complicated, and technology requires height, cost intensive；(4) freeze-drying, has the shortcomings such as production efficiency is low, equipment is complicated, cost intensive, it is difficult to realize large-scale production；(5) sol-gal process, can prepare purity height, even particle size distribution, ultrafine particle that chemism is high at low temperatures, but because it is readily incorporated other impurity elements, affect the performance of final products and be not widely used；(6) fused salt electrolysis process, tungsten powder prepared by this method is shaped as aspherical, and the powder agglomeration of preparation is serious, and production cost is higher；(7) self-propagating high-temperature synthesis, also known as conbustion synthesis, the method raw material is cheap, source is wide, production technology has the advantage such as efficient, energy-conservation and causes the most attention of countries in the world, but there is also a difficult problem for the aspects such as many Technologies in actual applications, as burning velocity and course of reaction are difficult to control to.
Sub-micron Tungsten Powder great majority prepared by said method are class ball-type and irregularly shaped, and particle size distribution is big, particle uniformity and poor dispersion.
Because above-mentioned defect, the design people, actively in addition research and innovation, to the preparation method founding a kind of polyhedron Sub-micron Tungsten Powder so that it is have more the value in industry.
Summary of the invention
For solving above-mentioned technical problem, the preparation method that it is an object of the invention to provide a kind of polyhedron Sub-micron Tungsten Powder, its production technology is briefly easily-controllable, equipment investment is few, production cost is low, the method being easily achieved industrialized production, and preparation product pellet be polyhedron-shaped, narrow diameter distribution, non-oxidizability are strong, degree of crystallinity is high.
The preparation method that the present invention proposes a kind of polyhedron Sub-micron Tungsten Powder, comprises the following steps:
(1) stirring soluble in water to solubility tungsten salt and surfactant, wherein the concentration of tungsten salt is 0.1～2.0mol/L, and the concentration of surfactant is 1.0～60.0g/L, obtains A liquid with acid for adjusting pH to 2～4；Dissolving reduce agent in water and obtain B liquid, wherein the concentration of reducing agent is 0.4～8.0mol/L；
(2) A liquid is heated after 50～90 DEG C, pour B liquid into, obtain A and B mixed solution, wherein A liquid is 3:1～1:3 with the volume ratio of B liquid, maintain the temperature at 50～90 DEG C of reaction 1～6h, being subsequently cooled to 10～30 DEG C, product obtains tungsten oxide presoma filter cake through solid-liquid separation, removes the impurity in filter cake through washing；Filter cake after washing removes moisture for dry 1～24 hour at 100～200 DEG C and obtains tungsten oxide presoma powder body；
(3) tungsten oxide presoma powder body is carried out heat treatment under reducing atmosphere, obtain polyhedron Sub-micron Tungsten Powder.
Further, in described step (1), in A liquid, the concentration of tungsten salt is 0.5～1.5mol/L, and the concentration of surfactant is 10.0～40g/L, pH is 2.5-3.5；In B liquid, the concentration of reducing agent is 1.0～6.0mol/L；In described step (2), A liquid is 2:1～1:2 with the volume ratio of B liquid.
Further, the solubility tungsten salt in described step (1) includes one or more in sodium tungstate, potassium tungstate or ammonium metatungstate.
Further, the surfactant in described step (1) includes one or more in polyvinylpyrrolidone, polyacrylic acid, oleic acid, Polyethylene Glycol, polyvinyl alcohol.
Further, the acid in described step (1) includes one or more in sulphuric acid, hydrochloric acid or nitric acid.
Further, the reducing agent in described step (1) includes sodium borohydride and the one in the mixture of hydrazine hydrate or the mixture of ethylenediamine, potassium borohydride and hydrazine hydrate or ethylenediamine.
Further, in described step (3), reducing atmosphere includes the one in the mixing gas of hydrogen, hydrogen and noble gas.
Further, described step (3) heat treatment temperature is 500～900 DEG C, and the recovery time is 1～6 hour, and the flow of reducing gas is 30～300mL/min.
Further, the method cooled down in described step (2) for add water in reactant liquor.
Further, in described step (2), the mode of the solid-liquid separation of product includes the one during vacuum filters or be centrifugal.
By such scheme, the preparation method that the present invention at least has the advantage that the polyhedron Sub-micron Tungsten Powder that the present invention proposes, its production technology is briefly easily-controllable, equipment investment is few, production cost is low, the method being easily achieved industrialized production, and preparation product pellet be polyhedron-shaped, narrow diameter distribution, non-oxidizability are strong, degree of crystallinity is high.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention, and can be practiced according to the content of description, below with presently preferred embodiments of the present invention and coordinate accompanying drawing describe in detail as after.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the tungsten powder of the embodiment of the present invention 1 preparation；
Fig. 2 is the SEM figure of the tungsten powder of the embodiment of the present invention 4 preparation.
Detailed description of the invention
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is described in further detail.Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.
Embodiment 1
The preparation method of a kind of polyhedron Sub-micron Tungsten Powder, comprises the following steps:
(1) by 0.15mol sodium tungstate and 3.0g polyvinylpyrrolidone (PVP) Homogeneous phase mixing soluble in water and be adjusted to pH with dilute hydrochloric acid and 3.0 obtain 300mLA liquid；0.25mol hydrazine hydrate and 0.05mol sodium borohydride are mixed and soluble in water obtains 300mLB liquid；
(2) A liquid heats to 90 DEG C, and B liquid is poured into A liquid, and temperature of reaction system maintains 90 DEG C of reaction 1h, is subsequently adding cold water and is cooled to room temperature (10～30 DEG C)；Product being performing centrifugal separation on, filter cake removes the impurity in filter cake through washing, by Wastewater Concentrated；Filter cake after washing removes moisture for dry 10 hours at 150 DEG C and obtains tungsten oxide presoma powder body；
(3) the tungsten oxide presoma powder body obtained being placed directly within tube furnace, then logical hydrogen reduces, and the flow controlling hydrogen is 30mL/min, and heat treatment temperature is 500 DEG C, and the time is 6 hours, obtains polyhedron Sub-micron Tungsten Powder.
Fig. 1 is the scanning electron microscope (SEM) photograph of the tungsten powder of preparation in the present embodiment, from the figure, it can be seen that the particle diameter of this tungsten powder is 400nm.
Embodiment 2
The preparation method of a kind of polyhedron Sub-micron Tungsten Powder, comprises the following steps:
(1) by 0.25mol potassium tungstate and 5.0g polyvinyl alcohol (PVA) Homogeneous phase mixing soluble in water and be adjusted to pH with dilute sulfuric acid and 2.5 obtain 250mLA liquid；1.0mol ethylenediamine and 0.1mol potassium borohydride are mixed and soluble in water obtains 350mLB liquid；
(2) A liquid heats to 60 DEG C, and B liquid is poured into A liquid, and temperature of reaction system maintains 60 DEG C of reaction 3h, is subsequently adding cold water and is cooled to room temperature (10～30 DEG C)；Product being filtered through vacuum, filter cake removes the impurity in filter cake through washing, by Wastewater Concentrated；Filter cake after washing removes moisture for dry 24 hours at 100 DEG C and obtains tungsten oxide presoma powder body；
(3) the tungsten oxide presoma powder body obtained being placed directly within tube furnace, then logical reducing gas reduces, H in reducing gas2With N2Volume ratio is 3:1, and control gas flow is 60mL/min, and heat treatment temperature is 700 DEG C, and the time is 5 hours, obtains polyhedron Sub-micron Tungsten Powder.
Embodiment 3
The preparation method of a kind of polyhedron Sub-micron Tungsten Powder, comprises the following steps:
(1) by 0.3mol sodium tungstate and 8.0g Polyethylene Glycol (PEG) Homogeneous phase mixing soluble in water and be adjusted to pH with dust technology and 2.5 obtain 200mLA liquid；0.80mol hydrazine hydrate and 0.06mol sodium borohydride are mixed and soluble in water obtains 400mLB liquid；
(2) A liquid heats to 70 DEG C, and B liquid is poured into A liquid, and temperature of reaction system maintains 70 DEG C of reaction 2h, is subsequently adding cold water and is cooled to room temperature (10～30 DEG C)；Product being filtered through vacuum, filter cake removes the impurity in filter cake through washing, by Wastewater Concentrated；Filter cake after washing removes moisture for dry 15 hours at 120 DEG C and obtains tungsten oxide presoma powder body；
(3) the tungsten oxide presoma powder body obtained being placed directly within tube furnace, then logical reducing gas reduces, H in reducing gas2Being 1:1 with the volume ratio of Ar, control gas flow is 100mL/min, and heat treatment temperature is 800 DEG C, and the time is 4 hours, obtains polyhedron Sub-micron Tungsten Powder.
Embodiment 4
The preparation method of a kind of polyhedron Sub-micron Tungsten Powder, comprises the following steps:
(1) by 0.3mol ammonium metatungstate and 6.0g polyvinylpyrrolidone (PVP) Homogeneous phase mixing soluble in water and be adjusted to pH with dilute hydrochloric acid and 3.5 obtain 400mLA liquid；1.15mol ethylenediamine and 0.05mol sodium borohydride are mixed and soluble in water obtains 200mLB liquid；
(2) A liquid heats to 50 DEG C, and B liquid is poured into A liquid, and temperature of reaction system maintains 50 DEG C of reaction 6h, is subsequently adding cold water and is cooled to room temperature (10～30 DEG C)；Product being performing centrifugal separation on, filter cake removes the impurity in filter cake through washing, by Wastewater Concentrated；Filter cake after washing removes moisture for dry 1 hour at 200 DEG C and obtains tungsten oxide presoma powder body；
(3) the tungsten oxide presoma powder body obtained being placed directly within tube furnace, then logical hydrogen reduces, and the flow controlling hydrogen is 200mL/min, and heat treatment temperature is 900 DEG C, and the time is 1 hour, obtains polyhedron Sub-micron Tungsten Powder.
Fig. 2 is the scanning electron microscope (SEM) photograph of the tungsten powder of preparation in this enforcement, from the figure, it can be seen that the particle diameter of this tungsten powder is 800nm.
Embodiment 5
The preparation method of a kind of polyhedron Sub-micron Tungsten Powder, comprises the following steps:
(1) by 0.45mol sodium tungstate and 10.5g polyacrylic acid (PAA) Homogeneous phase mixing soluble in water and to be adjusted to pH value with dust technology be 3.0 obtain 350mLA liquid；1.0mol ethylenediamine and 0.08mol potassium borohydride are mixed and soluble in water obtains 250mLB liquid；
(2) A liquid heats to 80 DEG C, and B liquid is poured into A liquid, and temperature of reaction system maintains 80 DEG C of reaction 4h, is subsequently adding cold water and is cooled to room temperature (10～30 DEG C)；Product being filtered through vacuum, filter cake removes the impurity in filter cake through washing, by Wastewater Concentrated；Filter cake after washing removes moisture for dry 4 hours at 180 DEG C and obtains tungsten oxide presoma powder body；
(3) the tungsten oxide presoma powder body obtained being placed directly within tube furnace, then logical reducing gas reduces, H in reducing gas2And N2Volume ratio be 1:1, control gas flow is 300mL/min, and heat treatment temperature is 600 DEG C, and the time is 3 hours, obtains polyhedron Sub-micron Tungsten Powder.
In sum, the preparation method of the polyhedron Sub-micron Tungsten Powder that the present invention proposes, have the advantage that
(1) shortcoming overcoming prior art, by chemical preparation tungsten oxide presoma, then direct-reduction atmosphere heat treatment tungsten oxide presoma prepares polyhedron Sub-micron Tungsten Powder, its production technology is briefly easily-controllable, equipment investment is few, and production cost is low, it is easy to accomplish industrialized production；The controlled production of tungsten powder pattern is realized by regulating the pH of tungsten salt；Also adopting tipping, the method is easy and simple to handle, adopts tipping to carry out redox reaction, the time of each tungsten oxide granular precursor nucleation and growth can be made to keep consistent, be suitable for large-scale industrial production；
(2) hydrazine hydrate or ethylenediamine is adopted to prepare tungsten oxide presoma response speed as reducing agent slow, percent reduction is low, and the present invention comes Substitute For Partial hydrazine hydrate or ethylenediamine with the stronger sodium borohydride of reproducibility or potassium borohydride, both reaction rate had been significantly improved, reduce again the consumption of reducing agent, improve production efficiency, reduce production cost, and prepared tungsten powder purity is high, has wide practical use in industrial circle；
(3) adopting chemical preparation tungsten oxide presoma, not only cheaper starting materials is easy to get, and greatly reduces preparation temperature, reduces cost of material and energy consumption.
(4) Sub-micron Tungsten Powder prepared by the present invention has polyhedral structure, and particle surface is smooth, and size tunable and narrow diameter distribution, non-oxidizability are strong, good dispersion, particle mean size are 400～800nm；This tungsten powder can be widely applied to the fields such as hard alloy, Aero-Space, electronics industry.
The above is only the preferred embodiment of the present invention; it is not limited to the present invention; should be understood that; for those skilled in the art; under the premise without departing from the technology of the present invention principle; can also making some improvement and modification, these improve and modification also should be regarded as protection scope of the present invention.
Claims (10)
1. the preparation method of a polyhedron Sub-micron Tungsten Powder, it is characterised in that: comprise the following steps:
(1) stirring soluble in water to solubility tungsten salt and surfactant, wherein the concentration of tungsten salt is 0.1～2.0mol/L, and the concentration of surfactant is 1.0～60.0g/L, obtains A liquid with acid for adjusting pH to 2～4；Dissolving reduce agent in water and obtain B liquid, wherein the concentration of reducing agent is 0.4～8.0mol/L；
(2) A liquid is heated after 50～90 DEG C, pour B liquid into, obtain A and B mixed solution, wherein A liquid is 3:1～1:3 with the volume ratio of B liquid, maintain the temperature at 50～90 DEG C of reaction 1～6h, being subsequently cooled to 10～30 DEG C, product obtains tungsten oxide presoma filter cake through solid-liquid separation, removes the impurity in filter cake through washing；Filter cake after washing removes moisture for dry 1～24 hour at 100～200 DEG C and obtains tungsten oxide presoma powder body；
(3) tungsten oxide presoma powder body is carried out heat treatment under reducing atmosphere, obtain polyhedron Sub-micron Tungsten Powder.
2. the preparation method of polyhedron Sub-micron Tungsten Powder according to claim 1, it is characterised in that: in described step (1), in A liquid, the concentration of tungsten salt is 0.5～1.5mol/L, and the concentration of surfactant is 10.0～40g/L, pH is 2.5-3.5；In B liquid, the concentration of reducing agent is 1.0～6.0mol/L；In described step (2), A liquid is 2:1～1:2 with the volume ratio of B liquid.
3. the preparation method of polyhedron Sub-micron Tungsten Powder according to claim 1, it is characterised in that: the solubility tungsten salt in described step (1) includes one or more in sodium tungstate, potassium tungstate or ammonium metatungstate.
4. the preparation method of polyhedron Sub-micron Tungsten Powder according to claim 1, it is characterised in that: the surfactant in described step (1) includes one or more in polyvinylpyrrolidone, polyacrylic acid, oleic acid, Polyethylene Glycol, polyvinyl alcohol.
5. the preparation method of polyhedron Sub-micron Tungsten Powder according to claim 1, it is characterised in that: the acid in described step (1) includes one or more in sulphuric acid, hydrochloric acid or nitric acid.
6. the preparation method of polyhedron Sub-micron Tungsten Powder according to claim 1, it is characterised in that: the reducing agent in described step (1) includes sodium borohydride and the one in the mixture of hydrazine hydrate or the mixture of ethylenediamine, potassium borohydride and hydrazine hydrate or ethylenediamine.
7. the preparation method of polyhedron Sub-micron Tungsten Powder according to claim 1, it is characterised in that: in described step (3), reducing atmosphere includes the one in the mixing gas of hydrogen, hydrogen and noble gas.
8. the preparation method of polyhedron Sub-micron Tungsten Powder according to claim 1, it is characterised in that: described step (3) heat treatment temperature is 500～900 DEG C, and the recovery time is 1～6 hour, and the flow of reducing gas is 30～300mL/min.
9. the preparation method of polyhedron Sub-micron Tungsten Powder according to claim 1, it is characterised in that: in described step (2), the method for cooling for add water in reactant liquor.
10. the preparation method of polyhedron Sub-micron Tungsten Powder according to claim 1, it is characterised in that: in described step (2), the mode of the solid-liquid separation of product includes the one during vacuum filters or be centrifugal.
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| CN112846211A (en) * | 2020-12-31 | 2021-05-28 | 崇义章源钨业股份有限公司 | High-compact-strength tungsten powder and preparation method thereof |
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