CN101559494A - Core-shell structure type tungsten carbide-cobalt hard alloy raw material powder and preparation method thereof - Google Patents
Core-shell structure type tungsten carbide-cobalt hard alloy raw material powder and preparation method thereof Download PDFInfo
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- CN101559494A CN101559494A CNA2009100594846A CN200910059484A CN101559494A CN 101559494 A CN101559494 A CN 101559494A CN A2009100594846 A CNA2009100594846 A CN A2009100594846A CN 200910059484 A CN200910059484 A CN 200910059484A CN 101559494 A CN101559494 A CN 101559494A
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Abstract
The invention provides a method for preparing core-shell structure type tungsten carbide-cobalt composite powder. Hard phase tungsten carbide in the composition powder is completely and evenly coated by binding phase metal cobalt to form a core-shell structure. The method comprises the steps of: performing ultrasonic dispersion on tungsten carbide powder; then adding the tungsten carbide powder into a cobalt-containing reducing solution; adjusting the pH value of the solution, and controlling the temperature; then adding a reducer solution in a dripping mode; reducing an even cobalt coating layer on the surface of hard phase tungsten carbide powder; and forming the core-shell structure type tungsten carbide-cobalt composite powder. Hard alloy raw material powder obtained by adopting the method has high dispersivity; a hard phase and a binding phase have even distribution so as to ensure that the powder is easy for alloying; and obtained hard alloy has high obdurability.
Description
Technical field
The invention belongs to the preparation field of hard alloy raw material powder, relate to a kind of liquid phase reduction and prepare hard alloy raw material powder, particularly the preparation method of core-shell structure type tungsten carbide tungsten-cobalt composite powder.
Background technology
The traditional preparation process method of Talide is with tungsten carbide (WC) powder and metallic cobalt (Co) powder mixing and ball milling, and cold moudling is last densified by liquid-phase sintering under 1400 ℃ temperature.Because the restriction of this physics mixing method of ball milling, hard phase (WC) and bonding be (Co) skewness and be prone to " cobalt pond " and crystal grain phenomenon such as grow up unusually when sintering, the obdurability of the alloy of deterioration sintering mutually; And by sintering, the character of alloy structure has inheritance to the character of raw meal, and the quality of raw meal can influence the granularity of alloying pellet, the compactness and the uniformity of alloy structure greatly, thereby influences the obdurability of carbide alloy.
A kind of core-shell structure type tungsten carbide tungsten provided by the invention-cobalt hard alloy composite powder preparation method, the metal bonding that can effectively overcome the existence in the ball mill mixing mode is mixed problem of non-uniform mutually and between the hard phase, provides guarantee for obtaining the high-performance rigid alloy.
Summary of the invention
The present invention be directed to the deficiency that exists on traditional hard alloy raw material powder technology of preparing, a kind of core-shell structure type tungsten carbide tungsten-cobalt that adopts liquid phase reduction to prepare polymolecularity (WC is a shell for nuclear, Co) cemented carbide powder is provided, eliminates the hard phase and the method for skewness mutually that bonds in the carbide alloy.
The present invention relates to a kind of nucleocapsid structure type cemented carbide powder, it is characterized in that the tungsten carbide in this cemented carbide powder is evenly coated by metallic cobalt fully, and above-mentioned metallic cobalt is prepared by liquid phase reduction.
Technical scheme of the present invention comprises following processing step:
1. tungsten-carbide powder preliminary treatment: ball-milling treatment tungsten-carbide powder 2～10h, again the tungsten-carbide powder behind the ball milling is placed beaker, add water and mix, ultrasonic dispersion 1～10h obtains tungsten carbide suspension;
2. the preparation of reducing solution: the soluble-salt and the water that will contain cobalt mix by a certain percentage as reducing solution;
3. liquid-phase reduction reaction: heating reducing solution to 50～100 ℃ in water bath, and the pH value of regulating reducing solution is between 10～13.Then pretreated pottery tungsten carbide suspension is poured in the reducing solution, constantly stirred, the mode that drips adds reductant solution continuously, and liquid color to be restored is colourless and when not having bubble and emitting, reaction finishes;
4. post processing: after reaction finishes, be incubated 1～2h, filter out sediment then, also wash to neutral, last vacuum oven 1～10h at 50～100 ℃ obtains by the core-shell structure type tungsten carbide tungsten powder of the even coating of metallic cobalt.
It is at least a in cobalt chloride, cobalt nitrate, the cobalt oxalate containing the cobalt soluble-salt in the above-mentioned nucleocapsid structure type cemented carbide powder preparation, and concentration range is 0.1～1.2mol/L;
What be used in the preparation of above-mentioned nucleocapsid structure type cemented carbide powder regulating reducing solution pH value is NaOH solution, and concentration is 0.5～1.0mol/L;
Reductant solution is at least a in hydrazine solution, ortho phosphorous acid sodium solution, the sodium borohydride solution in the above-mentioned nucleocapsid structure type cemented carbide powder preparation.
Compare with existing cemented carbide powder technology of preparing, the invention has the advantages that: preparation technology is simple, is swift in response, and nucleocapsid structure is complete; The hard alloy raw material powder of preparation has polymolecularity, and Co evenly distributes in WC, makes raw meal be easy to alloying in the liquid-phase sintering process, helps obtaining the carbide alloy of high-strength tenacity.
The specific embodiment
Embodiment 1
With 10g ultrafine WC ultrasound suspending in 50ml water 2 hours, regulate WC pH of suspension to 13 with NaOH solution after, suspension is placed 80 ℃ of water-baths, add CoCl again by 4g
26H
2The cobalt source solution that O, 2gNaOH and 30ml water are mixed with, treat temperature constant after, drip 15ml hydrazine solution (80%) in stirring condition following half an hour, be added dropwise to complete back insulation 1h, filtration washing, 55 ℃ of vacuum drying 2h obtain nucleocapsid structure type WC-Co composite powder.
Embodiment 2
With 10g ultrafine WC ultrasound suspending in 50ml water 2 hours, regulate WC pH of suspension to 12 with NaOH solution after, suspension is placed 85 ℃ of water-baths, add CoCl again by 4g
26H
2The cobalt source solution that O, 2gNaOH and 30ml water are mixed with, treat temperature constant after, drip 15ml hydrazine solution (80%) in stirring condition following half an hour, be added dropwise to complete back insulation 1h, filtration washing, 55 ℃ of vacuum drying 4h obtain nucleocapsid structure type WC-Co composite powder.
Embodiment 3
With 10g ultrafine WC ultrasound suspending in 50ml water 5 hours, regulate WC pH of suspension to 11 with NaOH solution after, suspension is placed 85 ℃ of water-baths, add CoCl again by 6g
26H
2The cobalt source solution that O, 3g NaOH and 45ml water are mixed with, treat temperature constant after, drip 25ml hydrazine solution (80%) in stirring condition following half an hour, be added dropwise to complete back insulation 1h, filtration washing, 60 ℃ of vacuum drying 4h obtain nucleocapsid structure type WC-Co composite powder.
Embodiment 4
With 10g ultrafine WC ultrasound suspending in 50ml water 2 hours, regulate WC pH of suspension to 11 with NaOH solution after, suspension is placed 85 ℃ of water-baths, add CoCl again by 6g
26H
2The cobalt source solution that O, 3g NaOH and 45ml water are mixed with, treat temperature constant after, drip 10ml ortho phosphorous acid sodium solution (0.5mol/L) in stirring condition following half an hour, be added dropwise to complete back insulation 1h, filtration washing, 60 ℃ of vacuum drying 4h obtain nucleocapsid structure type WC-Co composite powder.
Embodiment 5
With 10g ultrafine WC ultrasound suspending in 50ml water 5 hours, regulate WC pH of suspension to 11 with NaOH solution after, suspension is placed 85 ℃ of water-baths, add CoCl again by 6g
26H
2The cobalt source solution that O, 3gNaOH and 45ml water are mixed with, treat temperature constant after, drip 8ml sodium borohydride solution (0.8mol/L) in stirring condition following half an hour, be added dropwise to complete back insulation 1h, filtration washing, 60 ℃ of vacuum drying 4h obtain nucleocapsid structure type WC-Co composite powder.
Claims (5)
1. the production method of a core-shell structure type tungsten carbide tungsten-cobalt composite powder, it is characterized in that: with a certain amount of ultrafine WC ultrasound suspending in water, regulate WC pH of suspension to 10～13, suspension is placed 50～100 ℃ water-bath, add a certain amount of solubility cobalt salt again as the cobalt source, after treating temperature constant, stirring condition slowly drips a certain amount of reductant solution down, is added dropwise to complete back insulation 1～2h, filtration washing, 50～100 ℃ of vacuum drying obtain core-shell structure type tungsten carbide tungsten-cobalt composite powder.
2. the production method of a kind of core-shell structure type tungsten carbide tungsten-cobalt composite powder as claimed in claim 1 is characterized in that the solubility cobalt salt as cobalt source solution is at least a in cobalt chloride, cobalt nitrate, the cobalt oxalate, and cobalt salt concentration is 0.1～1.2mol/L.
3. the production method of a kind of core-shell structure type tungsten carbide tungsten-cobalt composite powder as claimed in claim 1 is characterized in that the WC and the ratio of the amount of substance of Co are 2: 1～5: 1.
4. the production method of a kind of core-shell structure type tungsten carbide tungsten-cobalt composite powder as claimed in claim 1, it is characterized in that reductant solution is at least a in hydrazine solution, ortho phosphorous acid sodium solution, the sodium borohydride solution, reducing agent is 2: 1～10: 1 with the ratio of the amount of substance of cobalt.
5. the production method of a kind of core-shell structure type tungsten carbide tungsten-cobalt composite powder as claimed in claim 1, what it is characterized in that being used for regulating reducing solution pH value is NaOH solution, concentration is 0.5～1.0mol/L.
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Cited By (13)
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| CN101920336A (en) * | 2010-09-19 | 2010-12-22 | 哈尔滨工业大学 | Preparation method of rare-earth modified Co-cladded wolfram carbide hard alloy composite powder |
| CN102554260A (en) * | 2012-02-20 | 2012-07-11 | 株洲硬质合金集团有限公司 | Application of EDTA (ethylene diamine tetraacetic acid) in W-Co composite oxide powder |
| CN103341641A (en) * | 2013-07-24 | 2013-10-09 | 厦门大学 | Preparing method for CoSb3 thermoelectric nanometer powder materials |
| CN106011925A (en) * | 2016-06-28 | 2016-10-12 | 北方工业大学 | Preparation method of sponge structure type Ni-W-Fe alloy based WC @ Pt core-shell structure particle electrode material |
| CN106956007A (en) * | 2017-03-23 | 2017-07-18 | 洛阳理工学院 | A kind of graded composite cutter material and preparation method |
| CN107866578A (en) * | 2017-11-07 | 2018-04-03 | 盾构及掘进技术国家重点实验室 | A kind of method and system for improving shield cutter Cemented Carbide Properties |
| CN107937788A (en) * | 2017-12-06 | 2018-04-20 | 昆山长鹰硬质合金有限公司 | The preparation method of the rare metal-modified nanocrystalline WC hard alloy of nanometer |
| CN109487266A (en) * | 2018-12-13 | 2019-03-19 | 郑州机械研究所有限公司 | A kind of rotary tillage cutter high-bearing capacity wear-resistant coating |
| CN110026551A (en) * | 2019-05-31 | 2019-07-19 | 湖南工业大学 | A kind of method that freezing prepares cobalt package tungsten carbide powder |
| CN110125438A (en) * | 2019-05-31 | 2019-08-16 | 湖南工业大学 | A kind of method that liquid-phase reduction prepares ultra-fine cemented carbide composite powder |
| CN113857474A (en) * | 2021-09-01 | 2021-12-31 | 河海大学 | Preparation method of WC surface-coated Co powder added with Ce element |
| CN114131036A (en) * | 2021-12-03 | 2022-03-04 | 安徽工业大学 | Low-cost preparation method of functionalized micro-nano particle reinforcement |
| CN115746592A (en) * | 2022-11-15 | 2023-03-07 | 河北邯峰发电有限责任公司 | Ultrahigh-hardness anti-corrosion wear-resistant laser cladding layer composite microstructure powder, composite material and preparation method of composite microstructure powder |
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2009
- 2009-06-02 CN CNA2009100594846A patent/CN101559494A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920336B (en) * | 2010-09-19 | 2011-12-28 | 哈尔滨工业大学 | Preparation method of rare-earth modified Co-cladded wolfram carbide hard alloy composite powder |
| CN101920336A (en) * | 2010-09-19 | 2010-12-22 | 哈尔滨工业大学 | Preparation method of rare-earth modified Co-cladded wolfram carbide hard alloy composite powder |
| CN102554260A (en) * | 2012-02-20 | 2012-07-11 | 株洲硬质合金集团有限公司 | Application of EDTA (ethylene diamine tetraacetic acid) in W-Co composite oxide powder |
| CN102554260B (en) * | 2012-02-20 | 2013-07-10 | 株洲硬质合金集团有限公司 | Application of EDTA (ethylene diamine tetraacetic acid) in W-Co composite oxide powder |
| CN103341641A (en) * | 2013-07-24 | 2013-10-09 | 厦门大学 | Preparing method for CoSb3 thermoelectric nanometer powder materials |
| CN106011925A (en) * | 2016-06-28 | 2016-10-12 | 北方工业大学 | Preparation method of sponge structure type Ni-W-Fe alloy based WC @ Pt core-shell structure particle electrode material |
| CN106956007B (en) * | 2017-03-23 | 2019-04-30 | 洛阳理工学院 | A kind of graded composite cutter material and preparation method |
| CN106956007A (en) * | 2017-03-23 | 2017-07-18 | 洛阳理工学院 | A kind of graded composite cutter material and preparation method |
| CN107866578A (en) * | 2017-11-07 | 2018-04-03 | 盾构及掘进技术国家重点实验室 | A kind of method and system for improving shield cutter Cemented Carbide Properties |
| CN107937788A (en) * | 2017-12-06 | 2018-04-20 | 昆山长鹰硬质合金有限公司 | The preparation method of the rare metal-modified nanocrystalline WC hard alloy of nanometer |
| CN107937788B (en) * | 2017-12-06 | 2019-11-22 | 昆山长鹰硬质合金有限公司 | The preparation method of the rare metal-modified nanocrystalline WC hard alloy of nanometer |
| CN109487266A (en) * | 2018-12-13 | 2019-03-19 | 郑州机械研究所有限公司 | A kind of rotary tillage cutter high-bearing capacity wear-resistant coating |
| CN110026551A (en) * | 2019-05-31 | 2019-07-19 | 湖南工业大学 | A kind of method that freezing prepares cobalt package tungsten carbide powder |
| CN110125438A (en) * | 2019-05-31 | 2019-08-16 | 湖南工业大学 | A kind of method that liquid-phase reduction prepares ultra-fine cemented carbide composite powder |
| CN110026551B (en) * | 2019-05-31 | 2021-02-19 | 湖南工业大学 | Method for preparing cobalt-coated tungsten carbide powder by freezing |
| CN113857474A (en) * | 2021-09-01 | 2021-12-31 | 河海大学 | Preparation method of WC surface-coated Co powder added with Ce element |
| CN114131036A (en) * | 2021-12-03 | 2022-03-04 | 安徽工业大学 | Low-cost preparation method of functionalized micro-nano particle reinforcement |
| CN115746592A (en) * | 2022-11-15 | 2023-03-07 | 河北邯峰发电有限责任公司 | Ultrahigh-hardness anti-corrosion wear-resistant laser cladding layer composite microstructure powder, composite material and preparation method of composite microstructure powder |
| CN115746592B (en) * | 2022-11-15 | 2024-03-19 | 河北邯峰发电有限责任公司 | Ultra-high hard corrosion-resistant wear-resistant laser cladding layer composite microstructure powder, composite material and preparation method thereof |
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