CN102560618B - Method for preparing tungsten single crystal - Google Patents
Method for preparing tungsten single crystal Download PDFInfo
- Publication number
- CN102560618B CN102560618B CN201210047526.6A CN201210047526A CN102560618B CN 102560618 B CN102560618 B CN 102560618B CN 201210047526 A CN201210047526 A CN 201210047526A CN 102560618 B CN102560618 B CN 102560618B
- Authority
- CN
- China
- Prior art keywords
- single crystal
- tungsten
- electrode
- crystal growing
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention provides a method for preparing a tungsten single crystal. An electrochemical method is utilized to prepare the tungsten single crystal in a fused salt. The method takes fused Na2WO4 and WO3 as a fused salt medium and, takes a high-purity polycrystal tungsten plate as a counter electrode and taking common metal such as copper and steel, or nonmetal such as graphite as a substrate for growing the single crystal as well as a working electrode, and comprises the following steps of: applying a current under an air atmosphere at 700-1000 DEG C; and adjusting the current and the electroplating time, thereby obtaining the tungsten single crystal. The method provided by the invention has the advantages of simple technological method, simple equipment demand, convenience in operation, low cost, and easiness in control of synthesizing conditions.
Description
Technical field
The present invention relates to a kind of preparation method of tungsten monocrystalline.
Background technology
Tungsten has high fusing point, boiling point, high intensity, hardness, and very little electronics overflows merit and good chemical stability.Tungsten monocrystalline is a kind of hi-tech type material, have without crystal boundary, grain boundary defects few, heat to power output efficiency height waits excellent properties, makes it be widely applied in the field such as aerospace, space technology, and along with the development of space science and technology, its Application Areas also will constantly expand.As Space power sources aspect, tungsten monocrystalline as the emtting electrode coated material of thermionic energy converters, vapour pressure feature lower under there is excellent mechanical behavior under high temperature, high temperature, excellent high temperature microtexture stability and surface heat electron emission capability.Tungsten monocrystalline still manufactures the ideal material of armour piercing shot bullet core.
At present, the preparation method of tungsten monocrystalline mainly contains territory, electro-beam floating zone smelting process, molten drop plasma arc melting method and strain-annealing method etc.These method complicated operations, apparatus expensive, and to environmental requirement harshness (high vacuum).In addition, determine that an important indicator of tungsten single crystal product article quality is purity level, tungsten monocrystalline purity prepared by prior art and interior tissue not ideal.And present method can from being obtained tungsten monocrystalline by electrochemical process step melting salt, method is simple, equipment requirements is simple, easy to operate, with low cost, and synthesis condition is easy to control, and is a kind of novel method preparing tungsten monocrystalline.
Summary of the invention
The object of the present invention is to provide the preparation method of new tungsten monocrystalline.
A preparation method for tungsten monocrystalline, is characterized in that, described in be prepared in and carry out in melting salt, step comprises:
The configuration of 1.1 fused-salt mediums: described fused-salt medium is Na
2wO
3-WO
3, according to molar percentage, get the Na of 50% ~ 90%
2wO
3with 10% ~ 50% WO
3mix after abundant drying, put into crucible, in air atmosphere, be warmed up to 700 ~ 1000 DEG C;
1.2 single crystal growing matrixes and the surface preparation to electrode: single crystal growing matrix and the sand paper to electrode surface different thicknesses carry out surface finish, then polishing, obtain smooth surface, then use acetone and deionized water ultrasonic cleaning respectively, remove greasy dirt and the impurity on surface;
1.3 apply electric current adjustment current parameters and electroplating time in air atmosphere: the electric current of applying is pulse or direct current, and range of current is 10mA.cm
-2~ 200 mA.cm
-2, electroplating time is more than 5 hours.
Further, described single crystal growing matrix is metal or graphite, is High Purity Polycrystalline tungsten plate to electrode.
Further, described single crystal growing base shape has sharp-pointed corner angle at least, and angle is less than 180 degree, and other corner angle are polished into arc; Described graphite surface need carry out activation treatment, makes surface conduction.
Further, described single crystal growing matrix and working electrode shape are the taper of tetragon or trilateral, other Polygonss or one end wedge angle, and the angle at a reserved angle is be less than the sharp comer of 90 degree.
Further, the dutycycle of described pulse plating is 10% ~ 90%, and the cycle is more than 1 millisecond.
The invention has the advantages that, all is simple to operation, required advantages of nontoxic raw materials, pollution-free, low price, and by electrochemical method, electric current, dutycycle, cycle and time are controlled, can allow tungsten nucleus on matrix, be less than the local preferential growth of 90 degree of acute angles, obtain the single-crystal tungsten of controlled dimensions size.
Embodiment
Embodiment 1:
The Na of 50% is taken according to molar percentage
2wO
3with 50% WO
3, then put into the moisture that drying oven drying removes crystal water and absorption.Fully mix in rear loading crucible, in electric furnace, be warmed up to 700 DEG C make the abundant melting of salt.Single crystal growing matrix selects copper, and cutting into trilateral, is tungsten plate to electrode, all uses the sand papering surface of different thicknesses, then polishing, until surperficial no marking, and the defects such as hole.Stay an angle in six angles of copper, angle is 60 degree, and all the other five angles change into circular arc on sand paper, the greasy dirt on the copper handled well and tungsten acetone and deionized water ultrasonic cleaning surface and the impurity of adhesion.The copper handled well and tungsten plate are linked on electrode, put into the Na of melting
2wO
3with WO
3in.Apply DC current density 100 mA.cm
-2electric current, 20 hours conduction time.
Embodiment 2:
The Na of 75% is taken according to molar percentage
2wO
3with 25% WO
3, then put into the moisture that drying oven drying removes crystal water and absorption.Fully mix in rear loading crucible, in electric furnace, be warmed up to 900 DEG C make the abundant melting of salt.Single crystal growing matrix selects copper alloy, and cutting into square, is tungsten plate to electrode, all uses the sand papering surface of different thicknesses, then polishing, until surperficial no marking, and the defects such as hole.Stay an angle in eight angles of copper alloy, angle is 90 degree, and all the other seven angles change into circular arc on sand paper, and the copper handled well and tungsten use the greasy dirt on acetone and deionized water ultrasonic cleaning surface and the impurity of adhesion again.The copper alloy handled well and tungsten plate are linked on electrode, put into the Na of melting
2wO
3with WO
3the pulse current density of middle applying is 10 mA.cm
-2electric current, dutycycle 25%, cycle 10ms, 60 hours conduction time.
Embodiment 3:
The Na of 80% is taken according to molar percentage
2wO
3with 20% WO
3, then put into the moisture that drying oven drying removes crystal water and absorption.Fully mix in rear loading crucible, in electric furnace, be warmed up to 1000 DEG C make the abundant melting of salt.Single crystal growing matrix selects steel, and cutting into pentagon, is tungsten plate to electrode, all uses the sand papering surface of different thicknesses, then polishing, until surperficial no marking, and the defects such as hole.Stay an angle in ten angles of steel, angle is 108 degree, and all the other nine angles change into circular arc on sand paper, and the steel handled well and tungsten use the greasy dirt on acetone and deionized water ultrasonic cleaning surface and the impurity of adhesion again.The steel handled well and tungsten plate are linked on electrode, put into the Na of melting
2wO
3with WO
3the DC current density of middle applying is 30 mA.cm
-2electric current, 80 hours conduction time.
Embodiment 4:
The Na of 87.5% is taken according to molar percentage
2wO
3with 12.5% WO
3, then put into the moisture that drying oven drying removes crystal water and absorption.Fully mix in rear loading crucible, in electric furnace, be warmed up to 800 DEG C make the abundant melting of salt.Single crystal growing matrix selects copper alloy, and cutting into taper shape, is tungsten plate to electrode, all uses the sand papering surface of different thicknesses, then polishing, until surperficial no marking, and the defects such as hole.Use the greasy dirt on acetone and deionized water ultrasonic cleaning surface and the impurity of adhesion again.The copper alloy handled well and tungsten plate are linked on electrode, put into the Na of melting
2wO
3with WO
3the pulse current density of middle applying is 50 mA.cm
-2electric current, dutycycle 50%, cycle 4ms, 100 hours conduction time.
Embodiment 5:
The Na of 90% is taken according to molar percentage
2wO
3with 10% WO
3, then put into the moisture that drying oven drying removes crystal water and absorption.Fully mix in rear loading crucible, in electric furnace, be warmed up to 900 DEG C make the abundant melting of salt.Single crystal growing matrix selects steel, and cutting into trilateral, is tungsten plate to electrode, all uses the sand papering surface of different thicknesses, then polishing, until surperficial no marking, and the defects such as hole.Stay an angle in six angles of steel, angle is 60 degree, and all the other five angles change into circular arc on sand paper, then uses the greasy dirt on acetone and deionized water ultrasonic cleaning surface and the impurity of adhesion.The steel handled well and tungsten plate are linked on electrode, put into the Na of melting
2wO
3with WO
3the DC current density of middle applying is 200 mA.cm
-2electric current, 120 hours conduction time.
Claims (4)
1. a preparation method for tungsten monocrystalline, is characterized in that, described in be prepared in and carry out in melting salt, step comprises:
The configuration of 1.1 fused-salt mediums: described fused-salt medium is Na
2wO
3-WO
3, according to molar percentage, get the Na of 50% ~ 90%
2wO
3with 10% ~ 50% WO
3mix after abundant drying, put into crucible, in air atmosphere, be warmed up to 700 ~ 1000 DEG C;
1.2 single crystal growing matrixes and the surface preparation to electrode: single crystal growing matrix and the sand paper to electrode surface different thicknesses carry out surface finish, then polishing, obtain smooth surface, then use acetone and deionized water ultrasonic cleaning respectively, remove greasy dirt and the impurity on surface;
1.3 apply electric current adjustment current parameters and electroplating time in air atmosphere: the electric current of applying is pulse or direct current, and current density range is 10mA.cm
-2~ 200mA.cm
-2, electroplating time is more than 5 hours;
Described single crystal growing base shape has sharp-pointed corner angle at least, and angle is less than 180 degree, and other corner angle are polished into arc.
2. method according to claim 1, is characterized in that: described single crystal growing matrix is metal or graphite, is High Purity Polycrystalline tungsten plate to electrode.
3. method according to claim 2, is characterized in that: described graphite surface need carry out activation treatment, makes surface conduction.
4. method according to claim 1, is characterized in that: the dutycycle of described pulse plating is 10% ~ 90%, and the cycle is more than 1 millisecond.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210047526.6A CN102560618B (en) | 2012-02-28 | 2012-02-28 | Method for preparing tungsten single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210047526.6A CN102560618B (en) | 2012-02-28 | 2012-02-28 | Method for preparing tungsten single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102560618A CN102560618A (en) | 2012-07-11 |
| CN102560618B true CN102560618B (en) | 2014-12-24 |
Family
ID=46407167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210047526.6A Expired - Fee Related CN102560618B (en) | 2012-02-28 | 2012-02-28 | Method for preparing tungsten single crystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102560618B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106654861A (en) * | 2016-10-31 | 2017-05-10 | 西北核技术研究所 | High-voltage gas switch electrode and preparation method thereof |
| CN114744073A (en) * | 2022-01-26 | 2022-07-12 | 深圳黑晶光电科技有限公司 | Method for realizing metallization of solar cell and crystalline silicon solar cell |
-
2012
- 2012-02-28 CN CN201210047526.6A patent/CN102560618B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 双向脉冲电镀工艺参数对Na2WO4-ZnO-WO3熔盐镀钨层织构的影响;马瑞新等;《材料科学与工艺》;20091231;第17卷(第6期);第754-756,760页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102560618A (en) | 2012-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109722674B (en) | Two-dimensional layered WS prepared by molten salt electrochemical stripping method2Method of producing a material | |
| CN102534630B (en) | Porous titanium nitride nanotube array film and preparation method thereof | |
| CN102409363B (en) | Method for preparing titanium with fused salt electrolysis process | |
| CN105197952A (en) | Preparation of nano single crystal lanthanum hexaboride and application of nano single crystal lanthanum hexaboride in electron microscope filament preparation | |
| CN102560618B (en) | Method for preparing tungsten single crystal | |
| CN102185020B (en) | Manufacturing method for front electrode of crystalline silicon solar battery | |
| CN102304725B (en) | Electrolytic cathode containing titanium boride-carbon coating, and preparation method thereof | |
| CN111484042A (en) | Crystalline state L i3OCl inorganic lithium ion conductor and preparation method and application thereof | |
| CN110923750A (en) | Preparation method of high-entropy alloy | |
| CN100517572C (en) | Polycrystalline silicon thin film and preparation method of component thereof | |
| CN105543516B (en) | The method that aluminothermic reduction titanium dioxide prepares aluminium titanium mother alloy in fused-salt medium | |
| CN107236989B (en) | Quinary rare earth boride single crystal hot cathode material and preparation method thereof | |
| CN104550991B (en) | A kind of preparation method of titanium-aluminium alloy superfines | |
| CN104032252B (en) | A kind of preparation method of Al85Ni10La5 amorphous alloy coating | |
| CN109666946B (en) | Two-dimensional layered MoS prepared by molten salt electrochemical intercalation method2Method of producing a material | |
| CN106187151A (en) | A kind of aluminum doped yttrium zinc oxide ceramic target and preparation method thereof | |
| CN102424986B (en) | Method for preparation of titanium-tungsten alloy through molten salt electrolysis | |
| CN107768621A (en) | A kind of preparation method of LiFePO4/graphene/carbon composite positive pole | |
| CN110120514B (en) | Three-dimensional porous Co-C3N4Preparation method of (1) | |
| CN106011943B (en) | A kind of method that pure ferroalloy and carbide-derived carbon are prepared using carbon ferroalloy simultaneously as raw material | |
| CN109468657B (en) | Preparation method of anode plate for electrolyzing manganese dioxide | |
| CN1011247B (en) | Rare-earth hexaboronide synthesized by melted salt electrolysis technique | |
| Cao et al. | High temperature electrochemical synthesis of tungsten boride from molten salt | |
| CN113215591B (en) | Molten salt electrochemical method for preparing silicon dioxide nanotubes and silicon nanotubes without additional addition of inducer | |
| CN114875422B (en) | Method for efficiently and environmentally preparing tungsten carbide powder by fused salt electrolysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141224 Termination date: 20190228 |