CN101569938B - Rare earth carbonic acid cobalt and nickel composite powder and production method thereof - Google Patents
Rare earth carbonic acid cobalt and nickel composite powder and production method thereof Download PDFInfo
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- CN101569938B CN101569938B CN2009101075856A CN200910107585A CN101569938B CN 101569938 B CN101569938 B CN 101569938B CN 2009101075856 A CN2009101075856 A CN 2009101075856A CN 200910107585 A CN200910107585 A CN 200910107585A CN 101569938 B CN101569938 B CN 101569938B
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Abstract
The invention relates to a rare earth carbonic acid cobalt and nickel composite powder and a production method thereof. The composite powder comprises rare earth elements and main components of carbonate and/or bicarbonate, cobalt and nickel, wherein the total mol content of cobalt and nickel is 30-60 % (mol), the mol content of carbonate and/or bicarbonate is 40-70% (mol), the mol ratio of cobalt and nickel is 0.9-1.1, and the weight parts of rare earth elements is 0.3-5%(wt) of the total weight of the cobalt and nickel. According to the invention, rare earth carbonic acid cobalt and nickel composite powder with finer granularity, higher alloying degree and better dispersivity of rare earth additive components at lower cost can be produced.
Description
Technical field
The present invention relates to the field of powder metallurgy, more particularly, the present invention relates to a kind of cobalt-nickel alloy powder and manufacture method thereof.
Background technology
In diamond tool and Hardmetal materials field, the CoNi alloy powder is used widely owing to its excellent adhesive property and strength character, and the rare earth adding ingredient can further improve processing characteristics, the mechanical property of CoNi alloy powder.
The manufacture method of traditional cobalt nickel composite powder comprises mechanical mixing and atomization, wherein: the CoNi alloy powder that mechanical mixing makes, alloying level is lower, the content of the face-centred cubic structure phase of complete alloying CoNi solid solution only is 60-80% in the composite powder that obtains, the hexagonal crystallographic texture phase content of non-alloying is up to 20-40%, and granularity is thicker; And,, cause its powder size also thicker because required fusion temperature is higher with the CoNi alloy powder that atomization prepares, generally surpass 5 μ m, and cost is higher, causes its application also to be restricted.And the dispersiveness of rare earth adding ingredient in classical production process gained composite powder is all relatively poor.
How further to improve the performance of cobalt-nickel alloy powder, the granularity of refinement cobalt-nickel alloy powder, improve the alloying level of cobalt-nickel alloy powder, increase the dispersiveness of composite powder middle rare earth adding ingredient, the production cost that reduces the cobalt-nickel alloy powder has extremely important technology and economic meaning.
Summary of the invention
Above-mentioned shortcoming at prior art, the objective of the invention is to provide a kind of rare earth carbonic acid cobalt and nickel composite powder and manufacture method thereof, it has following advantage: can be at lower cost, make that granularity is thinner, alloying level is higher, the dispersed better Rare-Earth Cobalt nickel composite powder of rare earth adding ingredient.
For this reason, one of technical solution of the present invention is a kind of rare earth carbonic acid cobalt and nickel composite powder, and this composite powder comprises rare earth element and main component, and main component is: carbonate and/or bicarbonate radical, cobalt and nickel; In the described main component: the molar content of cobalt nickel is 30-60% (mol), and the molar content of carbonate and/or bicarbonate radical is 40-70% (mol), cobalt: the mol ratio of nickel is 0.9-1.1; And the weight portion of rare earth element is the 0.3-5% (wt) of cobalt nickel gross weight.
Rare earth carbonic acid cobalt and nickel composite powder of the present invention, become a kind of brand-new presoma of Rare-Earth Cobalt nickel composite powder because of its distinctive composition proportioning: at first, only need to adopt simple chemical codeposition reaction just can make presoma of the present invention, then, only need under proper temperature by simple hydrogen reduction method, just can be then make required target powder: the Rare-Earth Cobalt nickel composite powder from presoma of the present invention.The target powder that makes like this has following overall merit: granularity is thin (＜1 μ m), and alloying effective (alloying does not contain the hexagonal structure phase fully) contain even distribution rare earth disperse phase, and production cost is lower.At present, the method for preparing the Rare-Earth Cobalt nickel composite powder by rare earth carbonic acid cobalt and nickel composite powder is not appeared in the newspapers.Therefore, product of the present invention has international and domestic leading water product, might become the developing direction of development of new high-performance cobalt nickel by powder.
Compared with prior art, the present invention has following outstanding advantage:
1, rare earth carbonic acid cobalt and nickel composite powder of the present invention, the weight portion ratio of rare earth wherein and cobalt nickel can reach 0.3-5%, and cobalt nickel ratio can reach 1: 1, thereby can give target powder extremely good physicochemical property.
2, rare earth carbonic acid cobalt and nickel composite powder of the present invention can adopt the chemical codeposition method to make, and rare earth is evenly distributed, and alloying is effective.
3, the preparation of powder-product of the present invention is simple, with low cost, is suitable for conventional production process.
Product of the present invention also comprises following optimization and concrete the improvement:
For the succession that makes full use of presoma obtains optimal target cobalt nickel by powder, in the described composite powder, the ratio of face-centered cubic phase crystal structure is 100%.Detect confirmation through XRD (X-ray diffraction): do not have six side's phases in the XRD diffraction maximum, the composition and the ratio of the phase of gained composite powder reach 100%.
Cooperate in order to obtain optimal target cobalt nickel by powder and optimised process, described rare earth element be yttrium, cerium, lanthanum wherein more than one.
Correspondingly, another technical solution of the present invention is a kind of manufacture method of rare earth carbonic acid cobalt and nickel composite powder as mentioned above, described manufacture method comprises the steps: A, the carbonate that adopts cobalt chloride, nickel chloride, rare earth chloride, sodium or ammonium or bicarbonate as raw material, and dissolving makes solution respectively; B, 4 kinds of solution are mixed make it to take place the chemical codeposition reaction; Solution obtains precipitating powder behind C, the separating reaction; D, will precipitate that powder washs, drying, make described rare earth carbonic acid cobalt and nickel composite powder.
As previously mentioned, because the peculiar composition proportioning of rare earth carbonic acid cobalt and nickel composite powder of the present invention, make a kind of presoma to adopt simple chemical codeposition to react to make the Rare-Earth Cobalt nickel composite powder, therefore, manufacture method step of the present invention is simple, mild condition, processing ease, equipment are common, but can make the presoma of the cobalt nickel composite powder that obtains function admirable at lower cost, thereby the transformation of ownership gets the cobalt nickel composite powder of function admirable at lower cost.
Cooperate for obtaining optimal target cobalt nickel by powder and optimised process, described rare earth chloride be yttrium chloride, cerium chloride, lanthanum chloride one of them.
For improving the efficient and the product quality of chemical codeposition reaction, method of the present invention also comprises following optimization and concrete the improvement:
Described steps A is preferably as follows one of 4 kinds of detailed processes:
A1, as the carbonate that adopts ammonium or sodium and yttrium chloride as raw material, the solution concentration of then preparing cobalt chloride is 1.0M, the solution concentration of nickel chloride is 1.0M, and the solution concentration of yttrium chloride is 0.004M-0.07M, and the solution concentration of the carbonate of ammonium or sodium is 2.006M-2.11M;
A2, be raw material as the carbonate that adopts ammonium or sodium and cerium chloride or lanthanum chloride, the solution concentration of then preparing cobalt chloride is 1.0M, the solution concentration of nickel chloride is 1.0M, cerium chloride or lanthanum chloride solution concentration are 0.0026 M-0.044M, and the solution concentration of the carbonate of ammonium or sodium is 2.004M-2.066M.
A3, be raw material as the bicarbonate and the yttrium chloride that adopt sodium or ammonium, the solution concentration of then preparing cobalt chloride is 1.5M, the solution concentration of nickel chloride is 1.5M, and yttrium chloride solution concentration is 0.05M-0.088M, and the solution concentration of the bicarbonate of sodium or ammonium is 2.015M-2.264M;
A4, be raw material as the bicarbonate that adopts sodium or ammonium and cerium chloride or lanthanum chloride, the solution concentration of then preparing cobalt chloride is 1.5M, the solution concentration of nickel chloride is 1.5M, cerium chloride or lanthanum chloride solution concentration are 0.0032M-0.056M, and the solution concentration of the bicarbonate of sodium or ammonium is 6.0096M-6.168M.
Among the described step B, keeping mixed solution pH value is 8.0～9.0, is heated to 50～90 ℃ after stirring, and constant temperature also constantly stirs, and finishes until the chemical codeposition reaction.
Among the described step D, the precipitation powder of cleaning placed 70～90 ℃ vacuum oven 1～1.5 hour.
Clearly, preparation technology of the present invention is simple, and is with low cost, is suitable for conventional production process.
The present invention will be further described below in conjunction with specific embodiment.
The specific embodiment
Embodiment 1: cobalt nickel: the weight portion ratio of yttrium=100: 0.3.
When adopting sodium carbonate or ammonium carbonate and yttrium chloride to be raw material, obtain solution consists of: the solution concentration of cobalt chloride is: 1.0M, the solution concentration of nickel chloride is: 1.0M, yttrium chloride solution concentration is: 0.004M, the solution concentration of sodium carbonate or ammonium carbonate is: 2.006M.
The above-mentioned solution for preparing heated respectively solid is dissolved fully, adjusting the pH value of solution value is 8.0～9.0, be heated to 50～90 ℃ after stirring, constant temperature also constantly stirs, treat that the chemical codeposition reaction is finished after, will precipitate powder and solution separating and filtering, wash with water purification, 70～90 ℃ vacuum oven 1～1.5 hour, (cobalt nickel: the weight portion ratio of yttrium=100: 0.3), its Fisher particle size was 0.6 μ m to make rare earth carbonic acid cobalt and nickel composite powder.
The powder that embodiment 1 makes, the Fisher particle size of the rare earth CoNi alloy powder that obtains after 450 ℃ of reduction is 0.6 μ m, the alloy powder structure all is the face-centered cubic phase.
Embodiment 2: cobalt nickel: the weight portion ratio of yttrium=100: 5.
When adopting sodium acid carbonate (carbonic hydroammonium) and yttrium chloride to be raw material, obtain solution consists of: the solution concentration of cobalt chloride is: 1.5M, the solution concentration of nickel chloride is: 1.5M, and yttrium chloride solution concentration is: 0.088M, the solution concentration of sodium acid carbonate (carbonic hydroammonium) is: 2.264M;
The above-mentioned A for preparing, B, C, D solution heated respectively solid is dissolved fully, adjusting the pH value of solution value is 8.0～9.0, be heated to 50～90 ℃ after stirring, constant temperature also constantly stirs, treat that the chemical codeposition reaction is finished after, will precipitate powder and solution separating and filtering, wash with water purification, 70～90 ℃ vacuum oven 1～1.5 hour, (cobalt nickel: the weight portion ratio of yttrium=100: 5), its Fisher particle size was 0.7 μ m to make rare earth carbonic acid cobalt and nickel composite powder.
The powder that embodiment 2 makes, the Fisher particle size of the rare earth CoNi alloy powder that obtains after 500 ℃ of reduction is 0.7 μ m, the alloy powder structure all is the face-centered cubic phase.
Embodiment 3: cobalt nickel: the weight portion ratio of cerium or lanthanum=100: 0.3.
When adopting sodium carbonate or ammonium carbonate and cerium chloride (lanthanum) to be raw material, obtain solution consists of: the solution concentration of cobalt chloride is: 1.0M, the solution concentration of nickel chloride is: 1.0M, cerium chloride (lanthanum) solution concentration is: 0.0026M, the solution concentration of sodium carbonate or ammonium carbonate is: 2.004M.
The above-mentioned solution for preparing heated respectively solid is dissolved fully, adjusting the pH value of solution value is 8.0～9.0, be heated to 50～90 ℃ after stirring, constant temperature also constantly stirs, treat that the chemical codeposition reaction is finished after, will precipitate powder and solution separating and filtering, wash with water purification, 70～90 ℃ vacuum oven 1～1.5 hour, (cobalt nickel: the weight portion ratio of cerium (lanthanum)=100: 0.3), its Fisher particle size was 0.6 μ m to make rare earth carbonic acid cobalt and nickel/cerium (lanthanum) composite powder.
The powder that embodiment 3 makes, the Fisher particle size of the rare earth CoNi alloy powder that obtains after 550 ℃ of reduction is 0.8 μ m, the alloy powder structure all is the face-centered cubic phase.
Embodiment 4: cobalt nickel: the weight portion ratio of cerium or lanthanum=100: 5.
When adopting sodium acid carbonate (carbonic hydroammonium) and cerium chloride (lanthanum) to be raw material, obtain solution consists of: the solution concentration of cobalt chloride is: 1.5M, the solution concentration of nickel chloride is: 1.5M, cerium chloride (lanthanum) solution concentration is: 0.056M, the solution concentration of sodium acid carbonate (carbonic hydroammonium) is: 6.168M.
The above-mentioned solution for preparing heated respectively solid is dissolved fully, adjusting the pH value of solution value is 8.0～9.0, be heated to 50～90 ℃ after stirring, constant temperature also constantly stirs, treat that the chemical codeposition reaction is finished after, will precipitate powder and solution separating and filtering, wash with water purification, 70～90 ℃ vacuum oven 1～1.5 hour, (cobalt nickel: the weight portion ratio of cerium (lanthanum)=100: 5), its Fisher particle size was 0.5 μ m to make rare earth carbonic acid cobalt and nickel/cerium (lanthanum) composite powder.
The powder that embodiment 4 makes, the Fisher particle size of the rare earth CoNi alloy powder that obtains after 600 ℃ of reduction is 0.9 μ m, the alloy powder structure all is the face-centered cubic phase.
Claims (8)
1. rare earth carbonic acid cobalt and nickel composite powder, it is characterized in that: this composite powder comprises rare earth element and main component, main component is: carbonate and/or bicarbonate radical, cobalt and nickel; In the described main component: the molar content of cobalt nickel is 30-60% (mol), and the molar content of carbonate and/or bicarbonate radical is 40-70% (mol), cobalt: the mol ratio of nickel is 0.9-1.1; And the weight portion of rare earth element is the 0.3-5% (wt) of cobalt nickel gross weight.
2. rare earth carbonic acid cobalt and nickel composite powder according to claim 1, it is characterized in that: the molar ratio of cobalt nickel is 1: 1 in the described composite powder.
3. rare earth carbonic acid cobalt and nickel composite powder according to claim 1 is characterized in that: described rare earth element be yttrium, cerium, lanthanum wherein more than one.
4. rare earth carbonic acid cobalt and nickel composite powder according to claim 1, it is characterized in that: the particle diameter of described composite powder is less than 1 μ m.
5. rare earth carbonic acid cobalt and nickel composite powder according to claim 1, it is characterized in that: the crystal structure of described composite powder is 100% face-centered cubic phase.
6. manufacture method as rare earth carbonic acid cobalt and nickel composite powder as described in one of claim 1-5, it is characterized in that: described manufacture method comprises the steps: A, the carbonate that adopts cobalt chloride, nickel chloride, rare earth chloride, sodium or ammonium or bicarbonate as raw material, and dissolving makes solution respectively; B, 4 kinds of solution are mixed make it to take place the chemical codeposition reaction; Solution obtains precipitating powder behind C, the separating reaction; D, will precipitate that powder washs, drying, make described rare earth carbonic acid cobalt and nickel composite powder.
7. as the manufacture method of rare earth carbonic acid cobalt and nickel composite powder as described in the claim 6, it is characterized in that: described rare earth chloride be yttrium chloride, cerium chloride, lanthanum chloride one of them.
8. as the manufacture method of rare earth carbonic acid cobalt and nickel composite powder as described in the claim 6, it is characterized in that: among the described step B, keeping mixed solution pH value is 8.0～9.0, is heated to 50～90 ℃ after stirring, constant temperature also constantly stirs, and finishes until the chemical codeposition reaction.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1160033A1 (en) * | 1999-11-19 | 2001-12-05 | Sakai Chemical Industrial Company Ltd. | Method for producing fine powder of metallic nickel comprised of fine spherical particles |
| CN101332506A (en) * | 2008-07-16 | 2008-12-31 | 深圳市格林美高新技术股份有限公司 | Rare-earth cobaltous carbonate powder and manufacture method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1160033A1 (en) * | 1999-11-19 | 2001-12-05 | Sakai Chemical Industrial Company Ltd. | Method for producing fine powder of metallic nickel comprised of fine spherical particles |
| CN101332506A (en) * | 2008-07-16 | 2008-12-31 | 深圳市格林美高新技术股份有限公司 | Rare-earth cobaltous carbonate powder and manufacture method thereof |
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| JP特开2003-277814A 2003.10.02 |
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