CN105903954B - A kind of method for preparing tin coated tungsten powder end - Google Patents
A kind of method for preparing tin coated tungsten powder end Download PDFInfo
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- CN105903954B CN105903954B CN201610482473.9A CN201610482473A CN105903954B CN 105903954 B CN105903954 B CN 105903954B CN 201610482473 A CN201610482473 A CN 201610482473A CN 105903954 B CN105903954 B CN 105903954B
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- mixed
- tin
- tungsten
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- mixed base
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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
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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
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
Abstract
A kind of method that the tin coated tungsten powder end of metallurgical binding is prepared the invention discloses low temperature calcination.Comprise the concrete steps that, the mixed base that fusion temperature is less than 300 DEG C is configured first；Then, 100 parts of tungsten powders, 5-20 parts of glass puttys and 5-50 parts of mixed bases are placed in ball mill according to mass fraction, plus a small amount of distilled water moistening, after being well mixed, obtain mixed powder；Again under protective atmosphere, dry mixed powder is fully melted under 300-750 DEG C of temperature conditionss, being fired to tin and mixed base；Finally product is cooled down, cleaned with distilled water to neutrality, filtration drying, tin coated tungsten powder end is obtained.Present invention mixed base calcines tungsten tin powder as brazing flux, can make to reach metallurgical binding between tungsten tin, be stripped of the oxide of metal surface, substantially reduce oxygen content in powder.What is provided prepares tin cladding tungsten particle method, mild condition, simple and easy to control.
Description
Technical field
The invention belongs to metal powder metallurgy field, the structure at tin coated tungsten powder end is obtained by relatively low sintering temperature,
The tin coated tungsten powder end obtained belongs to metal dust alloy.
Background technology
Tin coats the structure of tungsten, due to the presence of the soft tin layers in top layer so that hold when preparing the block of tungsten tin alloy
It is easy to get to the block of high-compactness.The metal dust of tin cladding tungsten has good sintering character, due to the presence of clad structure
So that the combination property such as the calorifics of tungsten tin composite material, mechanics gets a promotion.Tungsten tin alloy has a wide range of applications.The U.S.
The bullet that government's proposition is swaged with tungsten-tin powder, replaces lead, and the miniweapon practiced shooting for military affairs is shot.The institute of tungsten tin bullet
There is production stage almost consistent with production lead ammunition, tungsten can also be reclaimed, and be conducive to environment.Tungsten tin alloy can be made into armor-piercing bullet
With the cover body of petroleum perforation charge, tin melts during jet, it is to avoid the diverging of tungsten particle subflow, is conducive to raising to wear depth.Tungsten
Tin alloy also has potential application value in ore smelting cosolvent and low temperature transpiration material field.
It is due to that the fusing point of two kinds of metals has big difference although tungsten tin alloy has broad application prospects, tradition is molten
The method of refining can not produce tungsten tin alloy material, and (fusing point of tungsten is 3410 ± 20 DEG C.The fusing point of tin is 232 DEG C, and boiling point is 2260
℃).Producing the method for tungsten tin alloy 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), under hydrogen reducing atmosphere
930 DEG C of heating (I.E.Petruninand L.L.Grzhimal'skii, Interaction of tungsten with
Copper, manganese, silver, and tin, Metal Science＆Heat Treatment, 1969).Mechanical ball mill side
Time-consuming for method, energy consumption big, large-scale production has certain limitations progress.High-temperature vacuum sinter and hydrogen sintering to equipment requirement compared with
Height, while there is also energy consumption is big, the problem of sintering process complexity etc..
The content of the invention
It is an object of the invention to provide it is a kind of prepared with low-temperature sintering mode tin coated tungsten powder end preparation method, with up to
To production it is simple, efficiently, cheap, the big purpose of yield.
A kind of method for preparing tin coated tungsten powder end, is comprised the following steps that：
(1) mixed base that fusion temperature is less than 300 DEG C is prepared；
(2) powder is mixed：According to mass fraction meter, 100 parts of tungsten powders, 5-20 parts of glass puttys and 5-50 parts of mixed bases are placed in ball mill
In, then add distilled water moistening, after being well mixed, obtain mixed powder, drying for standby；
(3) mixed powder is calcined：Under protective atmosphere, the mixed powder for the drying that step (2) is obtained is placed in 300-750 DEG C
Under temperature conditionss, until tin and mixed base fully melt；
Described protective atmosphere is that one or both of vacuum, inert gas, ammonia, hydrogen are mixed above.
(4) cleaning system is dry：It will take out, be cleaned with distilled water to neutrality, filtration drying, i.e., after the product cooling of step (3)
Obtain tin coated tungsten powder end.
The technical principle of the inventive method is as follows：
(1) oxide that mixed base sloughs tungsten powder and glass putty surface is added.In heating, the oxygen of mixed base and tungsten powder surface
Compound formation tungstates (sodium tungstate, potassium tungstate, tungstate lithium), oxide formation stannate (sodium stannate, stannic acid with tin surfaces
Potassium, lithium stannate), and then tungstates and stannate are melt-mixed alkali soluble solution again.Mixed base has just peeled off the oxygen of tungsten and tin surfaces
Change layer, two kinds of metals is all exposed fresh metal surface, produce welding effect.After calcining, the tungsten in mixed base is dissolved in
Hydrochlorate and stannate are again soluble in water, can be by washing alkali, tungstates, stannate these impurity removal.
(2) for the just outflow from tungsten powder before preventing fusing tin and tungsten powder not glued in calcination process, it is necessary to assure mixed
Close alkali to melt prior to tin or fusing synchronous with tin, therefore it is necessary to make the fusing point of mixed base melt less than tin fusing point or slightly above tin
Point.Therefore the mixed base of low melting point is selected, its fusing point is not higher than 300 DEG C, close to 232 DEG C of tin fusing point.Typically mixed base is：Hydrogen-oxygen
Change sodium content 20%-96% sodium hydroxide and potassium hydroxide mixed base, sodium hydrate content 47%-94% sodium hydroxide with
Lithium hydroxide mixed base, lithium hydroxide content 19%-56% lithium hydroxide and potassium hydroxide mixed base.Can also be by fused salt phase
Figure configuration potassium, sodium, the multiphase mixed base of the hydroxide of lithium, or with above-mentioned hydroxide and its carbonate (i.e. potassium carbonate, carbonic acid
Sodium, lithium carbonate) multiphase mixed base is prepared, as long as ensuring that its melting point can be used less than 300 DEG C.
(3) heating and temperature control is between 300-750 DEG C.Lowest temperature is higher than tin and the fusing point of mixed base, temperature upper limit
Not higher than 750 DEG C, when substantial amounts of intermetallic compound dephasign can be produced higher than 750 DEG C of tin and tungsten.This point is necessary explanation,
Still it is difficult at present to find tungsten Sn intermetallic compound data from existing literature, but is more than in present invention research 750 DEG C of height
Temperature calcining is found that substantial amounts of tungsten Sn intermetallic compound dephasign really, for these compound phases composition and crystal structure just
Further determining.
(4) the sintering soak time is adjusted by processing amount of powder, so that temperature is uniform in powder, it is ensured that tin and mixed base all fill
Divide fusing limit.Generally 20-120min.
(5) calcining is to prevent tungsten, tin from aoxidizing at high temperature using the purpose of protective atmosphere, therefore uses vacuum, inertia
Gas, ammonia, hydrogen are protective atmosphere, or using inert gas, ammonia, the anti-oxidation of hydrogen mixed gas atmosphere.
Beneficial effects of the present invention：1) what is provided prepares tin cladding tungsten particle method, mild condition, simple and easy to control.It is logical
Cross provide lower sintering temperature, can largely prepare in a short time tin coat tungsten particle alloy powder, prepare it is with low cost,
It is easy to industrialized production.2) oxide of metal surface is removed as a result of molten alkali, makes to have reached between tungsten powder and tin very
Positive metallurgical binding, is different from mechanical bond tin bag tungsten powder made from ball milling.3) oxide of metal surface is removed using molten alkali,
Oxygen content in powder can also be substantially reduced.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) figure at the tin coated tungsten powder end of the present invention.Wherein：● it is the diffraction maximum of tungsten, ◆ be
The diffraction maximum of tin.
Fig. 2 is microscopic appearance (SEM) figure at the tin coated tungsten powder end of the present invention.
Fig. 3 is microscopic appearance (SEM) figure at the tin coated tungsten powder end of the present invention.
Fig. 4 is microscopic appearance (SEM) figure of the tungsten tin combination interface of the present invention.
Fig. 5 is tin diffraction maximum in last X-ray diffraction (XRD) figure of tin coated tungsten powder of 800 DEG C of the heating-up temperature of the present invention, figure
Disappear, intermetallic compound dephasign occur.Wherein：● it is the diffraction maximum of tungsten, ▼ is tungsten Sn intermetallic compound dephasign.
Embodiment
Below in conjunction with accompanying drawing and technical scheme, the embodiment of the present invention is further illustrated.
The present invention provides a kind of method for preparing tin coated tungsten powder end at a relatively low sintering temperature, including following implementation
Example：
Embodiment 1
The preparation at tin coated tungsten powder end：By 100g 200 mesh tungsten powders, 10g 200 mesh glass puttys, 5g sodium hydroxide, 5g's
Potassium hydroxide is added in ball grinder, plus a small amount of distilled water moistening, carries out vacuumize process to ball grinder, rotating speed is set to 200r/
Min, ball milling 60min, ball milling lead to argon gas cooling after terminating.Mixed-powder is taken out, is dried.Then powder is put into pipe type sintering furnace
In.To carrying out vacuumize process in boiler tube, pressure is extracted into 0.001MPa, and being passed through the argon gas that purity is 99.9% reaches pressure
0.08MPa, the setting rate of heat addition is 5 DEG C/min, is heated to 300 DEG C, the furnace cooling after 300 DEG C of insulation 60min.After sintering
Powder take out be put into 500ml beakers, cleaned with distilled water.The solution after cleaning is detected with PH test paper, determines it without alkalescence
Afterwards, dry in atmosphere, that is, obtain the alloy powder that tin coats tungsten.Fig. 1 is the XRD diffraction images of product, it can be seen that
There was only two kinds of compositions of tungsten tin in product, be not introduced into other impurities.By SEM photograph (Fig. 2, Fig. 3) it is observed that tin coats tungsten
Structure, the region become clear in figure is tungsten, and dark region is tin.It is tightly combined by the visible tungsten tin interfaces of Fig. 4, has reached smelting
Gold solder is closed.
Embodiment 2
According to the preparation method of embodiment 1, by sintering temperature control at 300-750 DEG C, and 60min is incubated.Change protection
Atmosphere is the argon gas of vacuum, argon gas, hydrogen with adding a small amount of hydrogen, and remaining step keeps constant, and the conjunction that tin coats tungsten is made
Bronze end.
Embodiment 3
According to the preparation method of embodiment 1, by 100g 200 mesh tungsten powders, 5-20g 200 mesh glass puttys, 5g hydroxide
Sodium, 5g potassium hydroxide is added in ball grinder.Remaining step keeps identical, and the alloy powder that tin coats tungsten is made.
Embodiment 4
According to the preparation method of embodiment 1,5-50g sodium hydroxides and potassium hydroxide (sodium hydroxide weight content are added
20%-96%), remaining step keeps identical, and the alloy powder that tin coats tungsten is made.
Embodiment 5
According to the preparation method of embodiment 1, (sodium hydroxide weight content exists for addition 5-50g sodium hydroxides and lithium hydroxide
47%-94%), remaining step keeps identical, and the alloy powder that tin coats tungsten is made.
Embodiment 6
According to the preparation method of embodiment 1,5-50g potassium hydroxide and lithium hydroxide (lithium hydroxide content 19%- are added
56%), remaining step keeps identical, and the alloy powder that tin coats tungsten is made.
Embodiment 7
According to the preparation method of embodiment 1.20min-120min is incubated during heating at 300 DEG C, remaining step keeps identical,
The alloy powder that tin coats tungsten is made.
Embodiment 8
According to the preparation method of embodiment 1.Heating-up temperature is incubated 20min-120min at 750 DEG C, and remaining step keeps phase
Together, the alloy powder that tin coats tungsten is made.When changing heating-up temperature to 800 DEG C, it is incubated in 20min-120min, XRD to go out
Now such as Fig. 5 tungsten Sn intermetallic compound dephasign.
Claims (6)
1. a kind of method for preparing tin coated tungsten powder end, it is characterised in that step is as follows：
(1) mixed base that fusion temperature is less than 300 DEG C is prepared；
(2) powder is mixed：According to mass fraction meter, 100 parts of tungsten powders, 5-20 parts of glass puttys and 5-50 parts of mixed bases are placed in ball mill,
Again plus distilled water moistening, be well mixed after, obtain mixed powder, drying for standby；
(3) mixed powder is calcined：Under protective atmosphere, the mixed powder for the drying that step (2) is obtained is placed in 300-750 DEG C of temperature
Under the conditions of, until tin and mixed base fully melt；
(4) cleaning system is dry：It will be taken out after the product cooling of step (3), cleaned to neutrality, filtration drying, that is, obtained with distilled water
Tin coated tungsten powder end.
2. according to the method described in claim 1, it is characterised in that described protective atmosphere is vacuum, inert gas, ammonia
Mixed gas more than one or both of gas, hydrogen.
3. according to the method described in claim 1, it is characterised in that mixed base of the described fusion temperature less than 300 DEG C is hydrogen
Two or more mixed bases in potassium oxide, sodium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, lithium carbonate.
4. the method according to claim 1 or 3, it is characterised in that described mixed base is sodium hydroxide and potassium hydroxide
The percentage composition of mixture, wherein sodium hydroxide is 20%~96%.
5. the method according to claim 1 or 3, it is characterised in that described mixed base is sodium hydroxide and lithium hydroxide
Mixture, wherein sodium hydrate content are 47%~94%.
6. the method according to claim 1 or 3, it is characterised in that described mixed base is potassium hydroxide and lithium hydroxide
Mixture, wherein lithium hydroxide content are 19%~56%.
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| CN110238388B (en) * | 2019-07-26 | 2021-07-27 | 昆山卡德姆新材料科技有限公司 | Metal powder wrapped by high polymer material and preparation method 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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| 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 |
| CN101274368A (en) * | 2008-04-30 | 2008-10-01 | 武汉理工大学 | Method for preparing nano-Cu uniformly coated Zn4Sb3 powder |
| 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 |
| 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 |
| CN104451226A (en) * | 2014-12-02 | 2015-03-25 | 中南大学 | Preparation method of micro-nano composite fine-grain tungsten material |
-
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 |
| CN104451226A (en) * | 2014-12-02 | 2015-03-25 | 中南大学 | Preparation method of micro-nano composite fine-grain tungsten material |
Non-Patent Citations (1)
| Title |
|---|
| "W-Sn solid solution synthesized by mechanical alloying at room temperature";Z.P.Xia,et al;《Journal of Alloys and Compounds》;20061120(第448期);210-214 * |
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