CN105798317B - A kind of preparation method of polyhedron Sub-micron Tungsten Powder - Google Patents
A kind of preparation method of polyhedron Sub-micron Tungsten Powder Download PDFInfo
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- CN105798317B CN105798317B CN201610197358.7A CN201610197358A CN105798317B CN 105798317 B CN105798317 B CN 105798317B CN 201610197358 A CN201610197358 A CN 201610197358A CN 105798317 B CN105798317 B CN 105798317B
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012065 filter cake Substances 0.000 claims abstract description 24
- 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 24
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 150000003657 tungsten Chemical class 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 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 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 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
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 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
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 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
- 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
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 239000002245 particle Substances 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 6
- 239000008188 pellet Substances 0.000 abstract description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000002171 ethylene diamines Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000006872 improvement Effects 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
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010189 synthetic method Methods 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 present invention relates to a kind of preparation method of polyhedron Sub-micron Tungsten Powder, comprise the following steps：(1) stir soluble tungsten salt and surfactant are soluble in water, A liquid is obtained with acid for adjusting pH to 2~4；Dissolve reduce agent in water and obtain B liquid；(2) A liquid is heated to after 50~90 DEG C, pours into B liquid, obtain A and B mixed solutions, the volume ratio of wherein A liquid and B liquid is 3:1~1:3,50~90 DEG C of 1~6h of reaction are maintained the temperature at, 10~30 DEG C is subsequently cooled to, reaction product obtains tungsten oxide presoma filter cake through separation of solid and liquid, the impurity in filter cake is removed through washing；Filter cake after washing removes moisture and obtains tungsten oxide presoma powder；(3) tungsten oxide presoma powder is heat-treated under reducing atmosphere, polyhedron Sub-micron Tungsten Powder is produced, the production technology is briefly easily-controllable, and equipment investment is few, production cost is low and the product pellet for preparing is in polyhedron-shaped, and particle diameter distribution is narrow, crystallinity is high.
Description
Technical field
The invention belongs to powder preparing technical field, more particularly to a kind of preparation method of polyhedron Sub-micron Tungsten Powder.
Background technology
Tungsten is a kind of valuable rare metal, is widely used as hard alloy, special steel and various tungsten products.In tungsten alloy most
Main raw material is tungsten powder, and the size of its granularity serves critical to the performance of alloy.Containing fine grain alloy ratio containing thick
The alloy property of particle is significantly improved, if alloy contains ultra-fine grain, performance can produce qualitative leap, reach high intensity and height
The unification of hardness, so as to extend its application field.Meanwhile, the application of tungsten in these areas also with its pattern, granularity
Distribution has close relationship.
Ultra-fine at present and Sub-micron Tungsten Powder preparation method mainly has：(1) tungsten oxide reducing process, the method is industrial conventional
Method, but have the disadvantage to yield poorly, cost height, cycle length, technology controlling and process it is complicated；(2) high-energy ball milling method, this method has cost
Low, yield is high and the advantages of simple technique, very wide in the less high applications of some purity and granularity requirements to powder, but
By 10 μm of material grinding to micron order even submicron-grade superfine powder, Ball-milling Time is very long, the cost phase such as ball consumption, energy consumption
It should increase；(3) spray drying process, i.e. heat chemistry synthetic method, the method prepare ultrafine tungsten powder particle be in spherical shell shape, specific surface area compared with
Greatly, porosity is high, is conducive to hydrogen in reduction process into the discharge with vapor, to be reduced so as to reduce reduction temperature and shorten
Time, it is easy to prepare ultrafine tungsten powder, but low production efficiency, equipment are complicated, and technical requirements are high, costly；(4) it is freeze-dried
Method, has the shortcomings that low production efficiency, equipment are complicated, costly, it is difficult to realize large-scale production；(5) sol-gal process, can
Purity height, the ultrafine particle that particle diameter distribution is uniform, chemism is high are prepared at low temperature, but because it is readily incorporated other impurities member
Element, influences the performance of final products and is not widely used；(6) fused salt electrolysis process, tungsten powder shape prepared by this method
For aspherical, the powder of preparation is reunited seriously, and production cost is higher；(7) self-propagating high-temperature synthesis, also known as conbustion synthesis,
This method raw material is cheap, and source is wide, production technology have the advantages that efficiently, the most attention that saves and cause countries in the world, but
Also there is the problem in terms of many technologies in actual applications, such as burning velocity and course of reaction are difficult to control to.
Most of Sub-micron Tungsten Powder prepared by the above method is in class ball-type and irregular shape, and size distribution is big, particle
Uniformity and poor dispersion.
In view of above-mentioned defect, the design people is actively subject to research and innovation, to found a kind of polyhedron sub-micron tungsten
The preparation method of powder, makes it with more the value in industry.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of preparation method of polyhedron Sub-micron Tungsten Powder,
Its production technology is briefly easily-controllable, and equipment investment is few, and production cost is low, it is easy to accomplish the method for industrialized production, and the production prepared
Product particle is in polyhedron-shaped, and particle diameter distribution is narrow, inoxidizability is strong, crystallinity is high.
The present invention proposes a kind of preparation method of polyhedron Sub-micron Tungsten Powder, comprises the following steps：
(1) stir soluble tungsten salt and surfactant are soluble in water, wherein the concentration of tungsten salt be 0.1~
2.0mol/L, the concentration of surfactant is 1.0~60.0g/L, and A liquid is obtained with acid for adjusting pH to 2~4；Dissolve reduce agent in
Water obtains B liquid, and the wherein concentration of reducing agent is 0.4~8.0mol/L；
(2) A liquid is heated to after 50~90 DEG C, pours into B liquid, obtain A and B mixed solutions, wherein A liquid and B liquid volume
Than for 3:1~1:3,50~90 DEG C of 1~6h of reaction are maintained the temperature at, 10~30 DEG C are subsequently cooled to, reaction product is through solid-liquid point
From tungsten oxide presoma filter cake is obtained, the impurity in filter cake is removed through washing；Filter cake after washing dries 1 at 100~200 DEG C~
Remove moisture within 24 hours and obtain tungsten oxide presoma powder；
(3) tungsten oxide presoma powder is heat-treated under reducing atmosphere, produces polyhedron Sub-micron Tungsten Powder.
Further, in the step (1), in A liquid the concentration of tungsten salt be 0.5~1.5mol/L, surfactant it is dense
Spend for 10.0~40g/L, pH is 2.5-3.5；The concentration of reducing agent is 1.0~6.0 mol/L in B liquid；A in the step (2)
The volume ratio of liquid and B liquid is 2:1~1:2.
Further, the soluble tungsten salt in the step (1) includes one kind in sodium tungstate, potassium tungstate or ammonium metatungstate
Or it is a variety of.
Further, the surfactant in the step (1) include polyvinylpyrrolidone, it is polyacrylic acid, oleic acid, poly-
One or more in ethylene glycol, polyvinyl alcohol.
Further, the acid in the step (1) includes the one or more in sulfuric acid, hydrochloric acid or nitric acid.
Further, the reducing agent in the step (1) includes sodium borohydride and hydrazine hydrate or mixture, the boron of ethylenediamine
Hydrofining and one kind in the mixture of hydrazine hydrate or ethylenediamine.
Further, reducing atmosphere includes one in the mixed gas of hydrogen, hydrogen and inert gas in the step (3)
Kind.
Further, step (3) heat treatment temperature is 500~900 DEG C, and the recovery time is 1~6 hour, also Primordial Qi
The flow of body is 30~300mL/min.
Further, the method for cooling is to be added water into reaction solution in the step (2).
Further, the mode of the separation of solid and liquid of product includes one kind in vacuum filter or centrifugation in the step (2).
By such scheme, the present invention at least has advantages below：The system of polyhedron Sub-micron Tungsten Powder proposed by the present invention
Preparation Method, its production technology is briefly easily-controllable, and equipment investment is few, and production cost is low, it is easy to accomplish the method for industrialized production, and system
Standby product pellet is in polyhedron-shaped, and particle diameter distribution is narrow, inoxidizability is strong, 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 specification, below with presently preferred embodiments of the present invention and coordinate accompanying drawing describe in detail as after.
Brief description of the drawings
Fig. 1 is the SEM figures of tungsten powder prepared by the embodiment of the present invention 1；
Fig. 2 is the SEM figures of tungsten powder prepared by the embodiment of the present invention 4.
Embodiment
With reference to the accompanying drawings and examples, the embodiment to the present invention is described in further detail.Implement below
Example is used to illustrate the present invention, but is not limited to the scope of the present invention.
Embodiment 1
A kind of preparation method of polyhedron Sub-micron Tungsten Powder, comprises the following steps：
(1) uniform mix 0.15mol sodium tungstates and 3.0g polyvinylpyrrolidones (PVP) are soluble in water and use watery hydrochloric acid
It is adjusted to pH and obtains 300mL A liquid for 3.0；0.25mol hydrazine hydrates and 0.05mol sodium borohydrides are mixed into soluble in water obtain
300mL B liquid；
(2) A liquid is heated to 90 DEG C, and B liquid is poured into A liquid, and temperature of reaction system maintains 90 DEG C of reaction 1h, then added
Cold water is cooled to room temperature (10~30 DEG C)；Reaction product is centrifuged, filter cake removes the impurity in filter cake through washing, will be useless
Water is focused on；Filter cake after washing dries 10 hours removing moisture at 150 DEG C and obtains tungsten oxide presoma powder；
(3) obtained tungsten oxide presoma powder is placed directly within tube furnace, then leads to hydrogen and reduced, control hydrogen
Flow be 30mL/min, heat treatment temperature be 500 DEG C, the time be 6 hours, produce polyhedron Sub-micron Tungsten Powder.
Fig. 1 is the scanning electron microscope (SEM) photograph of the tungsten powder prepared in the present embodiment, from the figure, it can be seen that the particle diameter of the tungsten powder is
400nm。
Embodiment 2
A kind of preparation method of polyhedron Sub-micron Tungsten Powder, comprises the following steps：
(1) by 0.25mol potassium tungstates and 5.0g polyvinyl alcohol (PVA) it is soluble in water it is uniform mix and be adjusted to dilute sulfuric acid
PH obtains 250mL A liquid for 2.5；1.0mol ethylenediamines and 0.1mol potassium borohydrides are mixed and soluble in water obtain 350mL B liquid；
(2) A liquid is heated to 60 DEG C, and B liquid is poured into A liquid, and temperature of reaction system maintains 60 DEG C of reaction 3h, then added
Cold water is cooled to room temperature (10~30 DEG C)；By reaction product through vacuum filter, filter cake removes the impurity in filter cake through washing, will be useless
Water is focused on；Filter cake after washing dries 24 hours removing moisture at 100 DEG C and obtains tungsten oxide presoma powder；
(3) obtained tungsten oxide presoma powder is placed directly within tube furnace, then leads to reducing gas and reduced, reduced
H in gas2With N2Volume ratio is 3:1, it is 60mL/min to control gas flow, and heat treatment temperature is 700 DEG C, and the time is 5 hours,
Produce polyhedron Sub-micron Tungsten Powder.
Embodiment 3
A kind of preparation method of polyhedron Sub-micron Tungsten Powder, comprises the following steps：
(1) by 0.3mol sodium tungstates and 8.0g polyethylene glycol (PEG) it is soluble in water it is uniform mix and be adjusted to dust technology
PH obtains 200mL A liquid for 2.5；0.80mol hydrazine hydrates and 0.06mol sodium borohydrides are mixed and soluble in water obtain 400mL B liquid；
(2) A liquid is heated to 70 DEG C, and B liquid is poured into A liquid, and temperature of reaction system maintains 70 DEG C of reaction 2h, then added
Cold water is cooled to room temperature (10~30 DEG C)；By reaction product through vacuum filter, filter cake removes the impurity in filter cake through washing, will be useless
Water is focused on；Filter cake after washing dries 15 hours removing moisture at 120 DEG C and obtains tungsten oxide presoma powder；
(3) obtained tungsten oxide presoma powder is placed directly within tube furnace, then leads to reducing gas and reduced, reduced
H in gas2Volume ratio with Ar is 1:1, it is 100mL/min to control gas flow, and heat treatment temperature is 800 DEG C, and the time is 4 small
When, produce polyhedron Sub-micron Tungsten Powder.
Embodiment 4
A kind of preparation method of polyhedron Sub-micron Tungsten Powder, comprises the following steps：
(1) uniform mix 0.3mol ammonium metatungstates and 6.0g polyvinylpyrrolidones (PVP) are soluble in water and use dilute salt
Acid is adjusted to pH and obtains 400mL A liquid for 3.5；1.15mol ethylenediamines and 0.05mol sodium borohydrides are mixed into soluble in water obtain
200mL B liquid；
(2) A liquid is heated to 50 DEG C, and B liquid is poured into A liquid, and temperature of reaction system maintains 50 DEG C of reaction 6h, then added
Cold water is cooled to room temperature (10~30 DEG C)；Reaction product is centrifuged, filter cake removes the impurity in filter cake through washing, will be useless
Water is focused on；Filter cake after washing dries 1 hour removing moisture at 200 DEG C and obtains tungsten oxide presoma powder；
(3) obtained tungsten oxide presoma powder is placed directly within tube furnace, then leads to hydrogen and reduced, control hydrogen
Flow be 200mL/min, heat treatment temperature be 900 DEG C, the time be 1 hour, produce polyhedron Sub-micron Tungsten Powder.
Fig. 2 is the scanning electron microscope (SEM) photograph of the tungsten powder prepared in the present embodiment, from the figure, it can be seen that the particle diameter of the tungsten powder is
800nm。
Embodiment 5
A kind of preparation method of polyhedron Sub-micron Tungsten Powder, comprises the following steps：
(1) by 0.45mol sodium tungstates and 10.5g polyacrylic acid (PAA) it is soluble in water it is uniform mix and adjusted with dust technology
It is 3.0 to obtain 350mLA liquid for pH value；1.0mol ethylenediamines and 0.08mol potassium borohydrides are mixed and soluble in water obtain 250mL B
Liquid；
(2) A liquid is heated to 80 DEG C, and B liquid is poured into A liquid, and temperature of reaction system maintains 80 DEG C of reaction 4h, then added
Cold water is cooled to room temperature (10~30 DEG C)；By reaction product through vacuum filter, filter cake removes the impurity in filter cake through washing, will be useless
Water is focused on；Filter cake after washing dries 4 hours removing moisture at 180 DEG C and obtains tungsten oxide presoma powder；
(3) obtained tungsten oxide presoma powder is placed directly within tube furnace, then leads to reducing gas and reduced, reduced
H in gas2And N2Volume ratio be 1:1, it is 300mL/min to control gas flow, and heat treatment temperature is 600 DEG C, and the time is 3 small
When, produce polyhedron Sub-micron Tungsten Powder.
In summary, the preparation method of polyhedron Sub-micron Tungsten Powder proposed by the present invention, with advantages below：
(1) shortcoming of prior art is overcome, tungsten oxide presoma is prepared by chemical reduction method, gas is then reduced directly
Polyhedron Sub-micron Tungsten Powder is made in atmosphere heat-treatment oxidation tungsten presoma, and its production technology is briefly easily-controllable, and equipment investment is few, is produced into
This is low, it is easy to accomplish industrialized production；The controllable production of tungsten powder pattern is realized by adjusting the pH of tungsten salt；Also use and topple over
Method, this method is easy to operate, carries out redox reaction using tipping, can make each tungsten oxide granular precursor nucleation and life
The long time is consistent, and is adapted to large-scale industrial production；
(2) tungsten oxide presoma reaction speed is prepared slowly as reducing agent using hydrazine hydrate or ethylenediamine, percent reduction is low, and this
Partially hydrated hydrazine or ethylenediamine are substituted with the stronger sodium borohydride of reproducibility or potassium borohydride in invention, has both been significantly improved anti-
Speed is answered, the consumption of reducing agent is reduced again, production efficiency is improved, production cost is reduced, and prepared tungsten powder is pure
Degree is high, has wide practical use in industrial circle；
(3) tungsten oxide presoma is prepared using chemical reduction method, not only raw material is cheap and 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, size tunable and particle diameter point
Cloth is narrow, inoxidizability is strong, good dispersion, particle mean size are 400~800nm；The tungsten powder can be widely applied to hard alloy, aviation
The fields such as space flight, electronics industry.
Described above is only the preferred embodiment of the present invention, is not intended to limit the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is some improvement and
Modification, these improvement and modification also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of polyhedron Sub-micron Tungsten Powder, it is characterised in that：Comprise the following steps：
(1) stir soluble tungsten salt and surfactant are soluble in water, wherein the concentration of tungsten salt is 0.1~2.0mol/
L, the concentration of surfactant is 1.0~60.0g/L, and A liquid is obtained with acid for adjusting pH to 2~4；Dissolve reduce agent in water and obtain B
The concentration of liquid, wherein reducing agent is 0.4~8.0mol/L；
(2) A liquid is heated to after 50~90 DEG C, pours into B liquid, obtain A and B mixed solutions, the volume ratio of wherein A liquid and B liquid is
3:1~1:3,50~90 DEG C of 1~6h of reaction are maintained the temperature at, 10~30 DEG C are subsequently cooled to, reaction product is obtained through separation of solid and liquid
To tungsten oxide presoma filter cake, the impurity in filter cake is removed through washing；Filter cake after washing is small in 100~200 DEG C of dryings 1~24
When remove moisture obtain tungsten oxide presoma powder；
(3) tungsten oxide presoma powder is heat-treated under reducing atmosphere, produces 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 the step (1),
The concentration of tungsten salt is 0.5~1.5mol/L in A liquid, and the concentration of surfactant is 10.0~40g/L, and pH is 2.5-3.5；B liquid
The concentration of middle reducing agent is 1.0~6.0mol/L；The volume ratio of A liquid and B liquid is 2 in the step (2):1~1:2.
3. the preparation method of polyhedron Sub-micron Tungsten Powder according to claim 1, it is characterised in that：In the step (1)
Soluble tungsten salt include sodium tungstate, potassium tungstate or ammonium metatungstate in one or more.
4. the preparation method of polyhedron Sub-micron Tungsten Powder according to claim 1, it is characterised in that：In the step (1)
Surfactant include polyvinylpyrrolidone, polyacrylic acid, oleic acid, polyethylene glycol, polyvinyl alcohol in one or more.
5. the preparation method of polyhedron Sub-micron Tungsten Powder according to claim 1, it is characterised in that：In the step (1)
Acid include sulfuric acid, hydrochloric acid or nitric acid in one or more.
6. the preparation method of polyhedron Sub-micron Tungsten Powder according to claim 1, it is characterised in that：In the step (1)
Reducing agent include mixture, potassium borohydride and the hydrazine hydrate or the mixture of ethylenediamine of sodium borohydride and hydrazine hydrate or ethylenediamine
In one kind.
7. the preparation method of polyhedron Sub-micron Tungsten Powder according to claim 1, it is characterised in that：In the step (3)
Reducing atmosphere includes one kind in the mixed gas of hydrogen, hydrogen and inert gas.
8. the preparation method of polyhedron Sub-micron Tungsten Powder according to claim 1, it is characterised in that：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 the step (2)
The method of cooling is to be added water into reaction solution.
10. the preparation method of polyhedron Sub-micron Tungsten Powder according to claim 1, it is characterised in that：In the step (2)
The mode of the separation of solid and liquid of product includes one kind in vacuum filter or centrifugation.
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