CN105903954A - Method for preparing tin-coated tungsten powder - Google Patents
Method for preparing tin-coated tungsten powder Download PDFInfo
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- CN105903954A CN105903954A CN201610482473.9A CN201610482473A CN105903954A CN 105903954 A CN105903954 A CN 105903954A CN 201610482473 A CN201610482473 A CN 201610482473A CN 105903954 A CN105903954 A CN 105903954A
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- powder
- tungsten
- mixed
- stannum
- tin
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Classifications
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- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
Abstract
The invention discloses a method for preparing metallurgical bonding tin-coated tungsten powder through low-temperature calcination. The method includes the specific steps that mixed alkalis with the melting temperature being lower than 300 DEG C is prepared at first; then, 100 parts of tungsten powder, 5-20 parts of tin powder and 5-50 parts of the mixed alkalis are put into a ball grinder by mass, a small amount of distilled water is added for wetting, and mixed powder is obtained after even mixing; afterwards, the dried mixed powder is calcined under the temperature condition of 300-750 DEG C till both the tin and mixed alkalis are fully smelted in the protective atmosphere; and finally, the product is cooled, cleaned to be neutral by distilled water, filtered and dried, and accordingly the tin-coated tungsten powder can be obtained. By the adoption of the method, the mixed alkalis serves as soldering flux calcination tungsten-tin powder, tungsten and tin can achieve metallurgical bonding, oxide on the surface of metal is removed, and the oxygen content in powder is greatly reduced. The method for preparing tin-coated tungsten particles is mild in condition, simple and easy to control.
Description
Technical field
The invention belongs to metal powder metallurgy field, obtain stannum coated tungsten powder end by relatively low sintering temperature
Structure, the stannum coated tungsten powder end obtained belongs to metal dust alloy.
Background technology
The structure of stannum cladding tungsten, due to the existence of the tin layers of top layer softness so that at the block preparing tungsten ashbury metal
The block of high-compactness it is readily obtained during body.The metal dust of stannum cladding tungsten has good sintering character, by
Existence in clad structure makes the combination properties such as the calorifics of tungsten tin composite material, mechanics get a promotion.Tungsten stannum
Alloy has a wide range of applications.The bullet that U.S. government's proposition tungsten-tin powder is swaged, replaces lead, is used for
The military miniweapon practiced shooting shoots.All production stages of tungsten stannum bullet are the most consistent with producing lead ammunition,
Tungsten can also reclaim, beneficially environment.Tungsten ashbury metal can be made into the cover body of armor-piercing bullet and petroleum perforation charge, stannum
Melt during jet, it is to avoid dissipating of tungsten particle subflow, beneficially raising are worn deeply.Tungsten ashbury metal is in ore deposit
Stone smelts cosolvent also has potential using value with low temperature transpiration material field.
Although tungsten ashbury metal has broad application prospects, but owing to the fusing point of two kinds of metals has big difference,
The method of tradition melting cannot produce tungsten tin alloy material, and (fusing point of tungsten is 3410 ± 20 DEG C.The fusing point of stannum is
232 DEG C, boiling point is 2260 DEG C).The method producing tungsten ashbury metal at present has, mechanical attrition method (Z.P.Xia, J.J.
Shen, Y.Q.Shen, et al.W Sn solid solution synthesized by mechanical alloying at
Room temperature, J.Alloys&Compounds, 2006), vacuum high-temperature is heated to more than 900 DEG C (A.
R.Saadatt and O.Nishikawai.Stability of gallium-,indium-,and tin-covered
Tungsten surfaces and formation of In-Wand Sn-W alloys, J.Applied Physics, 1976),
930 DEG C of heating (I.E.Petruninand L.L.Grzhimal'skii, Interaction of under hydrogen reducing atmosphere
Tungsten with copper, manganese, silver, and tin, Metal Science&Heat Treatment,
1969).Mechanical ball milling method time-consumingly length, energy consumption are big, large-scale production has certain limitations and carries out.High-temperature vacuum
Sintering and hydrogen sintering are higher to equipment requirements, there is also energy consumption big simultaneously, the problem that sintering process is complicated etc..
Summary of the invention
It is an object of the invention to provide a kind of low-temperature sintering mode to prepare the preparation side at stannum coated tungsten powder end
Method, to reach to produce simple, efficient, cheap, the big purpose of yield.
A kind of method preparing stannum coated tungsten powder end, specifically comprises the following steps that
(1) the configuration fusion temperature mixed base less than 300 DEG C；
(2) mixed powder: according to mass fraction meter, 100 parts of tungsten powders, 5-20 part glass putty and 5-50 part mixed base are put
In ball mill, then it is moistening to add distilled water, after mix homogeneously, obtains mixed powder, drying for standby；
(3) mixed powder calcining: under protective atmosphere, the mixed powder being dried step (2) obtained is placed in
Under 300-750 DEG C of temperature conditions, until stannum and mixed base the most fully melt；
Described protective atmosphere be in vacuum, noble gas, ammonia, hydrogen one or more mix
Close.
(4) clean system dry: take out after being cooled down by the product of step (3), clean to neutral with distilled water, cross and be filtered dry
Dry, i.e. obtain stannum coated tungsten powder end.
The know-why of the inventive method is as follows:
(1) add mixed base and slough the oxide of tungsten powder and glass putty surface.When heating, mixed base and tungsten powder table
The oxide in face forms tungstates (sodium tungstate, potassium tungstate, tungstate lithium), forms stannum with the oxide of tin surfaces
Hydrochlorate (sodium stannate, potassium stannate, lithium stannate), and then tungstates and stannate be melt-mixed again alkali dissolution.
The oxide layer of tungsten and tin surfaces just peeled off by mixed base, makes two kinds of metals all expose fresh metal surface, produces
Raw welding effect.After calcining, the tungstates and the stannate that are dissolved in mixed base are the most soluble in water, permissible
By washing by alkali, tungstates, these Impurity removals of stannate.
(2) in order to prevent from melting stannum the most just from tungsten powder outflow not glued with tungsten powder in calcination process, it is necessary to protect
Card mixed base is prior to stannum fusing or fusing Tong Bu with stannum, therefore it is necessary to make the fusing point of mixed base less than stannum fusing point
Or the fusing point of slightly above stannum.Therefore select the mixed base of low melting point, its fusing point is not higher than 300 DEG C, close to stannum fusing point
232℃.Typical mixed base is: the sodium hydroxide of sodium hydrate content 20%-96% and potassium hydroxide mixed base,
The sodium hydroxide of sodium hydrate content 47%-94% and Lithium hydrate mixed base, Lithium hydrate content 19%-56%'s
Lithium hydrate and potassium hydroxide mixed base.Can also be by Molten Salt Phase Diagrams configuration potassium, sodium, the hydroxide of lithium
Heterogeneous mixed base, or join with its carbonate (i.e. potassium carbonate, sodium carbonate, lithium carbonate) with above-mentioned hydroxide
Make heterogeneous mixed base, as long as guaranteeing that its melting point all can use less than 300 DEG C.
(3) heating and temperature control is between 300-750 DEG C.Lowest temperature is higher than stannum and the fusing point of mixed base, temperature
The degree upper limit is not higher than 750 DEG C, when producing substantial amounts of intermetallic compound dephasign higher than 750 DEG C of stannum and tungsten.This
Point is necessary explanation, is still difficult to find tungsten Sn intermetallic compound data at present from existing document, but
In present invention research, the high-temperature calcination more than 750 DEG C is found that substantial amounts of tungsten Sn intermetallic compound is miscellaneous really
Phase, the composition for these compound phases is determined the most further with crystal structure.
(4) the sintering soak time is by processing amount of powder regulation, so that homogeneous temperature in powder, it is ensured that stannum with mix
Alkali the most fully melts limit.Generally 20-120min.
(5) calcining uses the purpose of protective atmosphere to be to prevent tungsten, stannum from high temperature aoxidizing, therefore use vacuum,
Noble gas, ammonia, hydrogen are protective atmosphere, or use noble gas, ammonia, hydrogen mixed gas atmosphere
Anti-oxidation.
Beneficial effects of the present invention: 1) provided prepare stannum cladding tungsten particle method, mild condition, simple
Easily-controllable.By the lower sintering temperature provided, the alloy of stannum cladding tungsten particle can be prepared the most in a large number
Powder, preparation cost is cheap, it is simple to industrialized production.2) owing to have employed the oxygen of molten alkali removing metal surface
Compound, makes to have reached between tungsten powder and stannum real metallurgical binding, is different from the mechanical bond that ball milling prepares
Stannum bag tungsten powder.3) oxide of molten alkali removing metal surface is used, it is also possible to be substantially reduced oxygen content in powder.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure at the stannum coated tungsten powder end of the present invention.Wherein: ● for the diffraction of tungsten
Peak, ◆ for the diffraction maximum of stannum.
Fig. 2 is microscopic appearance (SEM) figure at the stannum coated tungsten powder end of the present invention.
Fig. 3 is microscopic appearance (SEM) figure at the stannum coated tungsten powder end of the present invention.
Fig. 4 is microscopic appearance (SEM) figure of the tungsten stannum combination interface of the present invention.
Fig. 5 is stannum coated tungsten powder end X-ray diffraction (XRD) figure of the heating-up temperature 800 DEG C of the present invention, in figure
Stannum diffraction maximum disappears, and intermetallic compound dephasign occurs.Wherein: ● for the diffraction maximum of tungsten,For tungsten tin metal
Between compound dephasign.
Detailed description of the invention
Below in conjunction with accompanying drawing and technical scheme, further illustrate the detailed description of the invention of the present invention.
The present invention provides a kind of method preparing stannum coated tungsten powder end at a relatively low sintering temperature, including following
Embodiment:
Embodiment 1
The preparation at stannum coated tungsten powder end: by the 200 mesh tungsten powders of 100g, the 200 mesh glass puttys of 10g, the hydrogen of 5g
Sodium oxide, the potassium hydroxide of 5g adds in ball grinder, adds a small amount of distilled water and moistens, takes out ball grinder very
Vacancy is managed, and rotating speed is set to 200r/min, ball milling 60min, and ball milling is logical argon cooling after terminating.Take out mixing
Powder, is dried.Then powder is put in pipe type sintering furnace.To carrying out evacuation process, pressure in boiler tube
Being extracted into 0.001MPa, be passed through the argon that purity is 99.9% and make pressure reach 0.08MPa, arranging the rate of heat addition is
5 DEG C/min, it is heated to 300 DEG C, furnace cooling after 300 DEG C of insulation 60min.Powder after sintering is taken out
Put in 500ml beaker, clean with distilled water.Solution after cleaning by PH detection paper, determines its alkali-free
After property, it is dried in atmosphere, i.e. obtains the alloy powder of stannum cladding tungsten.Fig. 1 is the XRD diffraction pattern of product
Picture, it can be seen that only two kinds of compositions of tungsten stannum in product, is not introduced into other impurity.Pass through SEM photograph
(Fig. 2, Fig. 3), it is observed that the structure of stannum cladding tungsten, region bright in figure is tungsten, and dark region is
Stannum.It is tightly combined by tungsten stannum interface seen from Fig. 4, has reached metallurgical seam.
Embodiment 2
According to the preparation method of embodiment 1, sintering temperature is controlled at 300-750 DEG C, and is incubated 60min.
Replacing protective atmosphere is the argon of vacuum, argon, hydrogen and a small amount of hydrogen of addition, and remaining step keeps constant,
All prepare the alloy powder of stannum cladding tungsten.
Embodiment 3
According to the preparation method of embodiment 1, by the 200 mesh tungsten powders of 100g, the 200 mesh glass puttys of 5-20g,
The sodium hydroxide of 5g, the potassium hydroxide of 5g adds in ball grinder.Remaining step keeps identical, prepares stannum cladding
The alloy powder of tungsten.
Embodiment 4
According to the preparation method of embodiment 1, add 5-50g sodium hydroxide and potassium hydroxide (sodium hydroxide weight
Content 20%-96%), remaining step keeps identical, prepares the alloy powder of stannum cladding tungsten.
Embodiment 5
According to the preparation method of embodiment 1, add 5-50g sodium hydroxide and Lithium hydrate (sodium hydroxide weight
Content is at 47%-94%), remaining step keeps identical, prepares the alloy powder of stannum cladding tungsten.
Embodiment 6
According to the preparation method of embodiment 1, add 5-50g potassium hydroxide and Lithium hydrate (Lithium hydrate content
19%-56%), remaining step keeps identical, prepares the alloy powder of stannum cladding tungsten.
Embodiment 7
Preparation method according to embodiment 1.It is incubated 20min-120min, remaining step at 300 DEG C during heating
Keep identical, prepare the alloy powder of stannum cladding tungsten.
Embodiment 8
Preparation method according to embodiment 1.Heating-up temperature, at 750 DEG C, is incubated 20min-120min, remaining
Step keeps identical, prepares the alloy powder of stannum cladding tungsten.When change heating-up temperature is to 800 DEG C, insulation
20min-120min, all occurs such as the tungsten Sn intermetallic compound dephasign of Fig. 5 in XRD figure.
Claims (6)
1. the method preparing stannum coated tungsten powder end, it is characterised in that step is as follows:
(1) the configuration fusion temperature mixed base less than 300 DEG C；
(2) mixed powder: according to mass fraction meter, 100 parts of tungsten powders, 5-20 part glass putty and 5-50 part mixed base are put
In ball mill, then it is moistening to add distilled water, after mix homogeneously, obtains mixed powder, drying for standby；
(3) mixed powder calcining: under protective atmosphere, the mixed powder being dried step (2) obtained is placed in
Under 300-750 DEG C of temperature conditions, until stannum and mixed base the most fully melt；
(4) clean system dry: take out after being cooled down by the product of step (3), clean to neutral with distilled water, cross and be filtered dry
Dry, i.e. obtain stannum coated tungsten powder end.
Method the most according to claim 1, it is characterised in that described protective atmosphere is vacuum, indifferent gas
One or more mixed gas in body, ammonia, hydrogen.
Method the most according to claim 1, it is characterised in that the described temperature mixed base less than 300 DEG C is
In potassium hydroxide, sodium hydroxide, Lithium hydrate, potassium carbonate, sodium carbonate, lithium carbonate two kinds or two kinds with
Upper mixed base.
4. according to the method described in claim 1 or 3, it is characterised in that described mixed base is sodium hydroxide and hydrogen
Potassium oxide mixture, wherein the percentage composition of sodium hydroxide is 20%～96%.
5. according to the method described in claim 1 or 3, it is characterised in that described mixed base is sodium hydroxide and hydrogen
Lithium oxide mixture, wherein sodium hydrate content is 47%～94%.
6. according to the method described in claim 1 or 3, it is characterised in that described mixed base is potassium hydroxide and hydrogen
Lithium oxide mixture, wherein Lithium hydrate content is 19%～56%.
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| CN201610482473.9A CN105903954B (en) | 2016-06-28 | 2016-06-28 | A kind of method for preparing tin coated tungsten powder end |
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| CN201610482473.9A CN105903954B (en) | 2016-06-28 | 2016-06-28 | A kind of method for preparing tin coated tungsten powder end |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112054181A (en) * | 2020-09-28 | 2020-12-08 | 珠海冠宇电池股份有限公司 | Lithium supplement agent and application thereof |
| WO2021018038A1 (en) * | 2019-07-26 | 2021-02-04 | 昆山卡德姆新材料科技有限公司 | Polymer material-coated metal powder, preparation method therefor and use thereof |
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| US5956560A (en) * | 1994-12-22 | 1999-09-21 | Osram Sylvania Inc. | Tungsten-copper composite powder |
| JP2003231902A (en) * | 2002-02-07 | 2003-08-19 | Murata Mfg Co Ltd | Production method for nickel powder, nickel powder, nickel paste, and laminated ceramic electronic part |
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| JP2015036444A (en) * | 2013-08-13 | 2015-02-23 | Jx日鉱日石金属株式会社 | Method for producing surface-treated metal powder |
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2016
- 2016-06-28 CN CN201610482473.9A patent/CN105903954B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5956560A (en) * | 1994-12-22 | 1999-09-21 | Osram Sylvania Inc. | Tungsten-copper composite powder |
| JP2003231902A (en) * | 2002-02-07 | 2003-08-19 | Murata Mfg Co Ltd | Production method for nickel powder, nickel powder, nickel paste, and laminated ceramic electronic part |
| CN101428345A (en) * | 2007-11-09 | 2009-05-13 | 北京有色金属研究总院 | Method of manufacturing ultrafine molybdenum powder or ultrafine tungsten powder surface clad metal copper |
| CN101274368A (en) * | 2008-04-30 | 2008-10-01 | 武汉理工大学 | Method for preparing nano-Cu uniformly coated Zn4Sb3 powder |
| JP2015036444A (en) * | 2013-08-13 | 2015-02-23 | Jx日鉱日石金属株式会社 | Method for producing surface-treated metal powder |
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| Z.P.XIA,ET AL: ""W-Sn solid solution synthesized by mechanical alloying at room temperature"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021018038A1 (en) * | 2019-07-26 | 2021-02-04 | 昆山卡德姆新材料科技有限公司 | Polymer material-coated metal powder, preparation method therefor and use thereof |
| CN112054181A (en) * | 2020-09-28 | 2020-12-08 | 珠海冠宇电池股份有限公司 | Lithium supplement agent and application thereof |
| CN112054181B (en) * | 2020-09-28 | 2023-01-24 | 珠海冠宇电池股份有限公司 | Lithium supplement agent and application thereof |
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