CN100546740C - A kind of super-fine cobalt powder and manufacturing process thereof - Google Patents
A kind of super-fine cobalt powder and manufacturing process thereof Download PDFInfo
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- CN100546740C CN100546740C CNB2007100759290A CN200710075929A CN100546740C CN 100546740 C CN100546740 C CN 100546740C CN B2007100759290 A CNB2007100759290 A CN B2007100759290A CN 200710075929 A CN200710075929 A CN 200710075929A CN 100546740 C CN100546740 C CN 100546740C
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Abstract
The present invention relates to a kind of super-fine cobalt powder and manufacturing process thereof, this technology comprises the steps: the powder of cobalt carbonate or cobalt oxalate is placed in the high-energy ball milling jar, according to the weight of powder, adds the abrading-ball that grinds dispersant and carbide alloy respectively in varing proportions; To vacuumize in the ball grinder, feed argon shield then; The sealing ball grinder is controlled the ball grinder rotating speed, is carried out high-energy ball milling, and ball milling obtains the powder of ultra-fine cobalt carbonate or ultra-fine cobalt oxalate after a period of time; With the powder of the ultra-fine cobalt carbonate that obtains or cobalt oxalate at H
2Reduce in the atmosphere, obtain the cobalt powder of oxygen content≤0.5%, Fisher particle size＜0.6 μ m.Super-fine cobalt powder finished product of the present invention can effectively improve the quality of hart metal product, and its production technology is simple, with low cost, is suitable for conventional production.
Description
Technical field
The present invention relates to a kind of Hardmetal materials, more particularly, the present invention relates to a kind of super-fine cobalt powder and manufacture method thereof.
Background technology
Ultra-fine cemented carbide has excellent performance, is the important directions of carbide alloy development.Produce ultra-fine cemented carbide and must add ultra-fine Co powder.Therefore, the ultra-fine Co powder of high-quality is one of important source material of producing ultra-fine cemented carbide.Exploitation contains ultra-fine Co powder, and to the hart metal product of preparation high, precision and frontier, it is significant to improve China's CEMENTED CARBIDE PRODUCTION industrial level.
At present, because the domestic production technical merit falls behind, compare with the developed country level, the hart metal product of China is second-rate, and most of properties of product are still on the low side, belongs to low technical content and low value-added primary product, service life is shorter, and average price more developed country hangs down 20～100% approximately.This one of them main cause is, the cobalt powder granularity that domestic enterprise adds in superfine hard alloy raw material is thicker, usually its Fisher particle size is greater than 0.6 μ m, and the preparation of ultra-fine cemented carbide requires coupling high-quality super-fine cobalt powder (for example Fisher particle size less than 0.6 μ m, oxygen content≤0.5%) just may obtain better serviceability.
Summary of the invention
Above-mentioned shortcoming at prior art, the objective of the invention is to provide a kind of super-fine cobalt powder and manufacturing process thereof, it has following advantage: this super-fine cobalt powder finished product can effectively improve the quality of hart metal product, and its production technology is simple, with low cost, is suitable for conventional production.
For this reason, one of technical solution of the present invention is a kind of manufacturing process of super-fine cobalt powder, and this manufacturing process comprises the steps:
Steps A places the powder of cobalt carbonate or cobalt oxalate in the high-energy ball milling jar, according to the weight of powder, adds the abrading-ball that grinds dispersant and carbide alloy respectively in varing proportions;
Step B will vacuumize in the ball grinder, feeds argon shield then;
Step C, the sealing ball grinder is controlled the ball grinder rotating speed, is carried out high-energy ball milling, and ball milling obtains the powder of ultra-fine cobalt carbonate or ultra-fine cobalt oxalate after a period of time;
Step D, with the powder of the ultra-fine cobalt carbonate that obtains or cobalt oxalate at H
2Reduce in the atmosphere, obtain the cobalt powder of oxygen content≤0.5%, Fisher particle size＜0.6 μ m.
Compared with prior art; preparation technology of the present invention adopts the high-energy ball milling machine equipment; material powder and peculiar grinding dispersant are made mechanical mixture according to a certain ratio; under inert gas shielding; adopt the carbide alloy abrading-ball; grind for a long time in the material powder work to technical grade: the rotary machine in the ball mill can pass to material powder; and material powder is under the collision repeatedly of ball-milling medium; withstand shocks; shear; friction and compress the effect of multiple power; experience pulverizing repeatedly; extruding; crystal damage; courses such as crystal reconstruct and coldwelding, thus the ultrafine particle powder formed.Confirm through test, add cobalt powder of the present invention and can make the hardness and the bending strength of carbide alloy block material significantly improve.And preparation technology of the present invention is simple, and is with low cost, is suitable for conventional production process, except that high-energy ball milling equipment, common electric reduction furnace, do not need other extras.
The concrete improvement and the advantage of process of the present invention also comprise:
In the described steps A, the control powder: the part by weight that grinds dispersant is 100: 0.5～2, and the control powder: the part by weight of abrading-ball is 1: 5～20.Can make powder be able to sufficient dispersion, grind fully like this.
The present invention adopts market to be easy to get and proper raw material, equipment are produced: in the described steps A, the material trade mark of described carbide alloy abrading-ball is YG10; Described cobalt carbonate or cobalt oxalate powder are raw material of industry level, and its Fei Shi particle mean size is 0.5～20 μ m.
Described ball radius is φ 6～φ 30mm, and wherein φ 6 is 1.5-2.5 with the part by weight of φ 30mm abrading-ball: 1.Can make that like this powder is able to fully, high-efficient grinding.
In the described steps A, described grinding dispersant is amphipathic stearic acid.Described grinding dispersant is a stearic acid.Process using stearic acid of the present invention is as the grinding dispersant, and preferred stearic acid.Because it is a kind of amphipathic organic acid, remove and have the surface-active effect, the carboxylic acid group of its end group almost has stronger coordination with all metal ions, moreover, stearic fusing point lower (about 70 ℃), the stearate acid of watery fusion can be used as the solvent of metal oxide, hydroxide, nitrate or organic carboxylate etc., makes each metal ion species reach highly uniform and stable mixing in its liquid phase.Process of the present invention has made full use of even, the stable dual immixture that stearic acid has compounding ingredient and surfactant concurrently, avoided fully in mechanical milling process with water as dispersant, thereby prevented the hydrolytic precipitation phenomenon of metal ion effectively, improved the efficient and the Technological adaptability of the inventive method greatly.
For reducing the oxidation side reaction, guaranteeing best spheroidal graphite effect, among the described step B, ball grinder is evacuated to 10
-2～10
-5Pa, the pressure of the protection argon gas of feeding is 10
2～10
3Pa; Among the described step C, control ball grinder rotating speed is that 300～500 rev/mins, ball milling time are 20～50 hours.
Among the described step D, described reduction temperature is 450-500 ℃, the time of described restoring operation: 1.2-1.6 hour.Compare 500-550 ℃ of conventional reduction temperature, restoring operation temperature of the present invention is low 50 ℃, compares 1.5-2 hour conventional reduction time, restoring operation time decreased of the present invention 20%, thereby restoring operation of the present invention can reduce energy consumption, raise the efficiency.
The super-fine cobalt powder that the inventive method makes is with cobalt carbonate (CoCO
3) or cobalt oxalate (CoC
2O
42H
2O) powder is that raw material makes, and described super-fine cobalt powder is high-energy ball milling, the H of described powder through the carbide alloy abrading-ball
2Make after the gas reduction.
The Fisher particle size of described super-fine cobalt powder＜0.6 μ m, its oxygen content≤0.5%.
Super-fine cobalt powder product of the present invention has following advantage:
1, cobalt powder Fisher particle size of the present invention is less than 0.6 μ m, and oxygen content≤0.5%, in contrast: present national Specification: the average Fisher particle size of super-fine cobalt powder is 1-1.5 μ m, and the average Fisher particle size scope of the superfine cobalt powder of domestic external enwergy volume shipment is 0.65-1.0 μ m; Average Fisher particle size yet there are no report less than the volume shipment of the cobalt powder of 0.60 μ m and oxygen content≤0.50%.Therefore, at present the cobalt powder quality index that makes of technology of the present invention still belongs to leading at home and abroad.
2, the preparation technology of product of the present invention is simple, is suitable for conventional equipment production, and is with low cost.
3, the ultra-fine cemented carbide product of preparing with super-fine cobalt powder of the present invention, its wearability and hardness, bending strength all improves a lot with fracture toughness: make carbide alloy with common cobalt powder and compare, make the mutually made carbide alloy block material of bonding with super-fine cobalt powder of the present invention, its wearability improves 10～30%, HRA improves 0.5～2, bending strength improves 5～20%, fracture toughness improves 10～20%, can be widely used in carbide alloy and make cutter, drilling tool, mould, measurer and various wear part.
The present invention will be further described below in conjunction with specific embodiment.
The specific embodiment
Embodiment 1:
1, be that the grinding dispersant of the technical grade cobalt carbonate powder and 1% (wt) of 10 μ m adds in the high-energy ball milling jar with particle mean size, in (weight ratio) powder: the ratio of ball=1: 10 adds YG10 carbide alloy abrading-ball, ball radius is φ 6～φ 30 mm, and φ 6: φ 30 (wt)=2: 1;
3, ball grinder is evacuated to 10
-3Pa feeds argon shield, and argon pressure is 10
3Pa;
4, will be full of the ball batch can sealing of argon gas tight after, begin to carry out high-energy ball milling, equipment is planetary high-energy ball mill, control ball grinder rotating speed is that 300 rev/mins, ball milling time are 40 hours, obtains ultra-fine cobalt carbonate and micro-ultra-fine mixed oxidization cobalt powder as CoO, Co
2O
3, Co
3O
4Deng.
5, with ultra-fine cobalt carbonate at H
2Middle reduction, the control reduction temperature is 460 ℃, restoring operation was kept 1.4 hours, obtained the cobalt powder of oxygen content=0.45%, Fisher particle size=0.55 μ m.
The Co powder finished product that present embodiment obtains through with after commercial ultrafine WC powder mixes, obtains the carbide alloy mixed-powder of WC90%-Co10%, through compacting, dewaxing and sintering process, makes the ultra-fine cemented carbide block materials.Compare with the ultra-fine cemented carbide block materials that same ratio is made with using thick Co powder (0.65-1.0 μ m), the hart metal product hardness that present embodiment makes improves 0.5HRA, and bending strength improves 5%.
Embodiment 2:
1, be that the grinding dispersant of the technical grade cobalt oxalate powder and 1% (wt) of 2 μ m adds in the high-energy ball milling jar with particle mean size, in (weight ratio) powder: the ratio of ball=1: 15 adds YG10 carbide alloy abrading-ball, ball radius is φ 6～φ 30mm, and φ 6: φ 30 (wt)=2: 1;
3, ball grinder is evacuated to 10
-3Pa feeds argon shield, and argon pressure is 10
3Pa;
4, will be full of the ball batch can sealing of argon gas tight after, begin to carry out high-energy ball milling, equipment is planetary high-energy ball mill, and control ball grinder rotating speed is that 350 rev/mins, ball milling time are 50 hours, obtain ultra-fine oxalic acid cobalt powder, and micro-ultra-fine mixed oxidization cobalt powder (as: CoO, Co
2O
3, Co
3O
4Deng).
5, with ultra-fine oxalic acid cobalt powder at H
2Middle reduction, the control reduction temperature is 480 ℃, restoring operation was kept 1.5 hours, obtained the cobalt powder of oxygen content=0.5%, Fisher particle size=0.45 μ m.
The Co powder finished product that present embodiment obtains through with after commercial ultrafine WC powder mixes, obtains the carbide alloy mixed-powder of WC90%-Co10%, through compacting, dewaxing and sintering process, makes the ultra-fine cemented carbide block materials.Compare with the ultra-fine cemented carbide block materials that same ratio is made with using thick Co powder (0.65-1.0 μ m), the hart metal product hardness that present embodiment makes improves 1HRA, and bending strength improves 15%.
Embodiment 3:
1, be that the grinding dispersant of the technical grade cobalt carbonate powder and 1.5% (wt) of 5 μ m adds in the high-energy ball milling jar with particle mean size, in (weight ratio) powder: the ratio of ball=1: 15 adds YG10 carbide alloy abrading-ball, ball radius is φ 6～φ 30 mm, and φ 6: φ 30 (wt)=1.5: 1;
3, ball grinder is evacuated to 0.5 * 10
-3Pa feeds argon shield, and argon pressure is 5 * 10
2Pa;
4, will be full of the ball batch can sealing of argon gas tight after, begin to carry out high-energy ball milling, equipment is planetary high-energy ball mill, control ball grinder rotating speed is that 400 rev/mins, ball milling time are 45 hours, obtains ultra-fine cobalt carbonate and micro-ultra-fine mixed oxidization cobalt powder as CoO, Co
2O
3, Co
3O
4Deng.
5, with ultra-fine cobalt carbonate at H
2Middle reduction, the control reduction temperature is 480 ℃, restoring operation was kept 1.6 hours, obtained the cobalt powder of oxygen content=0.45%, Fisher particle size=0.45 μ m.
The Co powder finished product that present embodiment obtains through with after commercial ultrafine WC powder mixes, obtains the carbide alloy mixed-powder of WC90%-Co10%, through compacting, dewaxing and sintering process, makes the ultra-fine cemented carbide block materials.Compare with the ultra-fine cemented carbide block materials that same ratio is made with using thick Co powder (0.65-1.0 μ m), the hart metal product wearability that present embodiment makes improves 25%, and hardness improves 1.5HRA, bending strength raising 20%, and fracture toughness improves 18%.
Embodiment 4:
1, be that the grinding dispersant of the technical grade cobalt carbonate powder and 0.5% (wt) of 15 μ m adds in the high-energy ball milling jar with particle mean size, in (weight ratio) powder: the ratio of ball=1: 20 adds YG10 carbide alloy abrading-ball, ball radius is φ 6～φ 30mm, and φ 6: φ 30 (wt)=2.5: 1;
3, ball grinder is evacuated to 10
-4Pa feeds argon shield, and argon pressure is 5 * 10
2Pa;
4, will be full of the ball batch can sealing of argon gas tight after, begin to carry out high-energy ball milling, equipment is planetary high-energy ball mill, control ball grinder rotating speed is that 450 rev/mins, ball milling time are 50 hours, obtains ultra-fine cobalt carbonate and micro-ultra-fine mixed oxidization cobalt powder as CoO, Co
2O
3, Co
3O
4Deng.
5, with ultra-fine cobalt carbonate at H
2Middle reduction, the control reduction temperature is 460 ℃, restoring operation was kept 1.3 hours, obtained the cobalt powder of oxygen content=0.5%, Fisher particle size=0.55 μ m.
The Co powder finished product that present embodiment obtains through with after commercial ultrafine WC powder mixes, obtains the carbide alloy mixed-powder of WC90%-Co10%, through compacting, dewaxing and sintering process, makes the ultra-fine cemented carbide block materials.Compare with the ultra-fine cemented carbide block materials that same ratio is made with using thick Co powder (0.65-1.0 μ m), the hart metal product wearability that present embodiment makes improves 15%, and hardness improves 1.0HRA, bending strength raising 10%, and fracture toughness improves 15%.
Claims (8)
1, a kind of manufacturing process of super-fine cobalt powder, this manufacturing process comprises the steps:
Steps A places the powder of cobalt carbonate or cobalt oxalate in the high-energy ball milling jar, according to the weight of powder, adds the abrading-ball that grinds dispersant and carbide alloy respectively in varing proportions;
Step B will vacuumize in the ball grinder, feeds argon shield then;
Step C, the sealing ball grinder is controlled the ball grinder rotating speed, is carried out high-energy ball milling, and ball milling obtains the powder of ultra-fine cobalt carbonate or ultra-fine cobalt oxalate after a period of time;
Step D, with the powder of the ultra-fine cobalt carbonate that obtains or cobalt oxalate at H
2Reduce in the atmosphere, obtain the super-fine cobalt powder of oxygen content≤0.5%, Fisher particle size＜0.6 μ m.
2, the manufacturing process of super-fine cobalt powder as claimed in claim 1 is characterized in that: in the described steps A, the control powder: the part by weight that grinds dispersant is 100: (0.5～2), the control powder: the part by weight of abrading-ball is 1: (5～20).
3, the manufacturing process of super-fine cobalt powder as claimed in claim 1 is characterized in that: in the described steps A, the material trade mark of described carbide alloy abrading-ball is YG10; Described cobalt carbonate or cobalt oxalate powder are raw material of industry level, and its Fei Shi particle mean size is 0.5～20 μ m.
4, the manufacturing process of super-fine cobalt powder as claimed in claim 3 is characterized in that: described ball radius is φ 6～φ 30mm, and wherein φ 6 is (1.5-2.5) with the part by weight of φ 30mm abrading-ball: 1.
5, the manufacturing process of super-fine cobalt powder as claimed in claim 1 is characterized in that: in the described steps A, described grinding dispersant is amphipathic stearic acid.
6, the manufacturing process of super-fine cobalt powder as claimed in claim 5 is characterized in that: described stearic acid is a stearic acid.
7, the manufacturing process of super-fine cobalt powder as claimed in claim 1 is characterized in that: among the described step B, ball grinder is evacuated to 10
-2～10
-5Pa, the pressure of the protection argon gas of feeding is 10
2～10
3Pa; Among the described step C, control ball grinder rotating speed is that 300～500 rev/mins, ball milling time are 20～50 hours.
8, the manufacturing process of super-fine cobalt powder as claimed in claim 1 is characterized in that: among the described step D, described reduction temperature is 450-500 ℃, the time of described restoring operation: 1.2-1.6 hour.
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| CN100546740C true CN100546740C (en) | 2009-10-07 |
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| CN101559493B (en) * | 2009-02-23 | 2012-08-08 | 南京寒锐钴业股份有限公司 | Method for preparing super-fine cobalt powder |
| CN101780545B (en) * | 2010-01-18 | 2013-03-27 | 深圳市格林美高新技术股份有限公司 | Low-oxygen content submicron cobalt powder and cobalt oxalate precursor and manufacturing method thereof |
| CN101745644B (en) * | 2010-03-09 | 2012-04-04 | 南京寒锐钴业有限公司 | Method for preparing cobalt powder |
| CN102000830B (en) * | 2010-11-18 | 2012-07-04 | 深圳市格林美高新技术股份有限公司 | Superfine cobalt alloy powder and preparation method thereof |
| CN102886526B (en) * | 2011-07-19 | 2015-04-29 | 深圳市格林美高新技术股份有限公司 | Reduction method for preparing superfine cobalt powder by hydrazine hydrate |
| CN102909366B (en) * | 2011-08-01 | 2015-01-14 | 深圳市格林美高新技术股份有限公司 | Method and device for preparing coating cobalt powder |
| CN102909383B (en) * | 2011-08-03 | 2015-08-05 | 深圳市格林美高新技术股份有限公司 | The preparation method of extra-fine nickel powder or cobalt powder |
| CN102728846B (en) * | 2012-07-12 | 2014-04-16 | 重庆文理学院 | Method for preparing nanometer cobalt powders with spherical face-centered cubic structures by using mechano-chemical method |
| CN104722766B (en) * | 2013-12-18 | 2017-07-18 | 格林美股份有限公司 | A kind of high density cobalt powder and its synthetic method |
| CN105397101A (en) * | 2015-10-27 | 2016-03-16 | 株洲硬质合金集团有限公司 | Spherical porous nanometer cobalt powder and preparation method thereof |
| CN106346021B (en) * | 2016-09-27 | 2018-08-10 | 南京寒锐钴业股份有限公司 | A kind of method that high pressure hydrogen reduction prepares cobalt powder |
| CN107649689A (en) * | 2017-11-07 | 2018-02-02 | 宇辰新能源材料科技无锡有限公司 | A kind of preparation method of super-fine cobalt powder |
| CN108526477B (en) * | 2018-05-03 | 2021-11-23 | 南京寒锐钴业股份有限公司 | Preparation method of WC-Co hard alloy mixture |
| CN109692969A (en) * | 2019-03-04 | 2019-04-30 | 江苏萌达新材料科技有限公司 | A kind of preparation method of hypoxemia superfine spherical cobalt powder |
| CN111922355A (en) * | 2020-06-30 | 2020-11-13 | 荆门市格林美新材料有限公司 | Preparation method of superfine cobalt powder |
| CN112974833A (en) * | 2021-02-02 | 2021-06-18 | 安徽寒锐新材料有限公司 | Cobalt powder and preparation method and preparation device thereof |
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