CN102423806A - Preparation method of fine-particle-size cobalt-based alloy powder - Google Patents
Preparation method of fine-particle-size cobalt-based alloy powder Download PDFInfo
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Abstract
The invention relates to a preparation method of fine-particle-size cobalt-based alloy powder, which comprises the following steps: firstly, taking a metal material with a target component or an alloy material containing corresponding cobalt content; putting the selected raw materials into a crucible, and obtaining cobalt-based alloy powder by vacuum induction melting and inert gas atomization technologies; sieving or grading to obtain cobalt-base alloy powder with powder size of 1-45 μm. Solves the problems of high oxygen content of fine powder, poor loose ratio and fluidity, low powdering rate in spraying, low density and bonding strength of a coating and the like of the existing fine-grained cobalt-based alloy powder, and improves the quality of cobalt-based powder products.
Description
Technical field
The present invention relates to the alloy powder technical field, relate in particular to a kind of preparation method of fine grain Co-based alloy powder.
Background technology
At present, along with developing rapidly of industry such as Aero-Space, the energy, petrochemical industry, require material can adapt to higher environment temperature.The general name of a kind of alloy that cobalt-base alloys is made up of alloying elements such as cobalt and nickel, chromium, iron is a kind of alloy of high-temperature corrosion resistance commonly used.Use cobalt-base alloys in the aeronautical and space technology in a large number, cobalt-base alloys is more than 1038 ℃ the time, and the far ultra nickel-base alloy of its superiority can be applicable to high efficiency engine components.And along with the develop rapidly of surface protection technique, the method for preparing high-temperature protection coating with Co-based alloy powder has received common concern.
Use more having in the cobalt-base alloys powder: (1) cobalt chrome molybdenum silicon alloy powder, coating is worked under the high temperature strong corrosion medium well.Can be used for preparation technology of coating such as plasma spraying, supersonic spray coating.(2) cobalt chromium aluminium yttrium belongs to the cobalt-based supertherm, and bond strength is high, can do high temperature prime coat material.The coating of preparation is fine and close, and antioxygenic property is excellent, corrosion-resistant and cavitation erosion.Can be used for supersonic spray coating, detonation flame spraying or plasma spraying.Be mainly used in metallurgical roller; The anti-dross coating on heat-processing equipments such as high annealing furnace roller surface is made and is repaired, the adhesive transition layer of afterburning tube in the refractory coating of aeroengine rotor blade, guide vane and gas engine blade and jet engine combustion chamber and burner inner liner thermal barrier coating.(3) cobalt-chromium-tungsten alloy powder; Its coating has outstanding gasproof erosion, anti-scratch and antistrip performance; And have good shock resistance and vibration resistance performance and antisticking wearing and tearing and abrasive wear property; High-temperature behavior is good, and resistance to oxidation, is the cemented carbide powder of wearing and tearing of a kind of ability all kinds and corrosion and high-temperature oxydation; The working environment that mainly is applicable to scratch, peels off and weares and teares is used for the surfacing or the spraying of axle, forging tools, hot roll, turbine seal and seal valve, exhaust valve for internal combustion engine and the valve seat etc. of work under the high temperature.
Present China low oxygen content, the main dependence on import of fine-grained Co-based alloy powder, and be mainly used in high-end markets such as space flight, aviation.The preparation of fine granularity cobalt-base alloys powder need be taked the noble gas atomization process, mainly is divided into two kinds of big aerosolization and vacuum atomizings.The oxygen content in power of at present big aerosolization preparation is higher, has often added a large amount of deoxidiers and slag former in smelt stage in order to reduce oxygen content, and this brings higher impurity content to alloy powder again undoubtedly; Cause in the atomization process sphericity of powder poor; The pine that is in particular in alloy powder is than bad with flowability, and powder utilization is low in the spraying, and the density of coating and bond strength reduce; And adopt the Co-based alloy powder purity of vacuum induction melting noble gas atomization process preparation high; Alloying component is controlled easily, and oxygen content and impurity content are low, is the main preparation technology of preparation low oxygen content fine granularity Co-based alloy powder.
Compare homemade cobalt-base alloys powder with external product and mainly have following deficiency and gap: 1. alloying component control is unstable; The fine powder oxygen content is high; The oxygen content of the cobalt-based powder-45 μ m of present domestic development is generally all more than 500ppm; Oxygen content causes the oxide inclusions in the spray-on coating to increase apparently higher than external identical powder (external oxygen content 230-400ppm), and the density of coating and bond strength reduce; Limited the range of application of powder, the long-term dependence on import of cobalt-based powder that aero-engine is used.2. the powder recovery rate low (＜30%) of homemade Co-based alloy powder-45 μ m.For improving the production technology level of China's cobalt-based powder; Satisfy industrial demands such as aero-engine, substitute import, promote the application of thermal spraying high-temperaure coating high-performance powder; Be necessary to carry out the development work of homemade Co-based alloy powder and coating, dwindle and external gap in this field.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of fine grain Co-based alloy powder; The fine powder oxygen content that has solved present Co-based alloy powder is high, pine than and mobile bad, spraying in problems such as density and the bond strength of low, the coating of powder utilization is low, improved the quality of Co-based alloy powder product.
The objective of the invention is to realize through following technical scheme:
A kind of preparation method of fine grain Co-based alloy powder, said preparation method comprises:
1) gets the metal material of target component or contain the alloy material of corresponding cobalt content;
2) selected raw material is put into crucible, obtain Co-based alloy powder through vacuum induction melting, inert gas atomizer technology;
3) sieve or classification, prepare the Co-based alloy powder of powder size in the 1-45 mu m range.
The technological parameter of said inert gas atomizer is:
Atomization gas is nitrogen or argon gas, atomizing drift angle＜28 ° atomizing pressure＞3MPa.
The mass percent of said Co-based alloy powder composition is:
A) chromium: 10.0-40.0wt%, nickel: 1-12wt%, tungsten: 2-10wt%, carbon: 0.20-1.5wt%, cobalt: surplus;
Or, b) chromium: 4～20wt%, molybdenum: 20～30wt%, silicon: 2～8wt%, cobalt: surplus.
The main body granularity of said Co-based alloy powder is 1-45 μ m.
Its typical composition is the CoCrW alloy powder, powder formation rate >=55% in the 1-45 mu m range, and wherein 1-25 mu m range powder accounts for 15%-20%, and 25-45 mu m range powder accounts for 35%-40%.
Oxygen content≤the 0.02wt% of said Co-based alloy powder
Said preparation method also comprises:
Utilize prepared Co-based alloy powder to adopt supersonic spray coating technology to make cobalt chromium tungsten coating, the technological parameter of prepared cobalt chromium tungsten coating is:
Kerosene oil flow 600～1000L/h; Oxygen flow 15～30L/min; Powder feed rate 20～200g/min; Spray distance 100～400mm.
Technical scheme by the invention described above provides can find out that said preparation method comprises: at first get the metal material of target component or contain the alloy material of corresponding cobalt content; Selected raw material is put into the vacuum melting crucible, obtain the cobalt-chromium-tungsten alloy powder through vacuum induction melting, inert gas atomizer technology; Sieve or classification, prepare the Co-based alloy powder of powder size in the 1-45 mu m range.The fine powder oxygen content that has solved present Co-based alloy powder is high, pine than and mobile bad, spraying in problems such as density and the bond strength of low, the coating of powder utilization is low, improved the quality of Co-based alloy powder product.
Description of drawings
In order to be illustrated more clearly in the technical scheme of the embodiment of the invention; The accompanying drawing of required use is done to introduce simply in will describing embodiment below; Obviously, the accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skill in the art; Under the prerequisite of not paying creative work, can also obtain other accompanying drawings according to these accompanying drawings.
Preparation method's schematic flow sheet of the fine grain Co-based alloy powder that Fig. 1 provides for the embodiment of the invention;
The CoCrW alloy powder that utilizes that Fig. 2 enumerates for the embodiment of the invention is made the process chart of cobalt chromium tungsten coating.
The specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the invention, the technical scheme in the embodiment of the invention is carried out clear, intactly description, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on embodiments of the invention, those of ordinary skills belong to protection scope of the present invention not making the every other embodiment that is obtained under the creative work prerequisite.
The prepared fine grain Co-based alloy powder of the embodiment of the invention comprises cobalt and other alloying elements, is example with typical cobalt-chromium-tungsten alloy powder, and this alloy powder chemical formula is: CoCrNiW.
For instance, its quality can be chromium: 10.0-40.0wt% than composition, nickel: 1-12wt%, and tungsten: 2-10wt%, carbon: 0.20-0.90wt%, oxygen :≤0.04wt%, cobalt: surplus, shown in the table specific as follows:
| Element | Chromium | Nickel | Tungsten | Carbon | Oxygen | Cobalt |
| Composition range/wt% | 10.0-40.0 | 1-12 | 2-10 | 0.20-0.90 | ≤0.02 | Surplus |
Its granularity is: 1-45 μ m, and wherein, granularity refers to the size of particle, the granularity of spherical particles is represented with diameter usually; The main body granularity refers to that this particle size range powder accounts for more than the 50wt% of total amount.
Its typical composition is the CoCrW alloy powder, powder formation rate>=55% in the 1-45 mu m range, and wherein 1-25 mu m range powder accounts for 15%-20%, and 25-45 mu m range powder accounts for 35%-40%; And the oxygen content≤0.02wt% of said Co-based alloy powder.
To combine accompanying drawing that the embodiment of the invention is done to describe in detail further below, be illustrated in figure 1 as the said preparation method's of the embodiment of the invention schematic flow sheet, said method comprising the steps of:
Step 11: get the metal material of target component or contain the alloy material of corresponding cobalt content.
In this step, typical mass percent can be got in following ratio:
Chromium: 10.0-40.0wt%, nickel: 1-12wt%, tungsten: 2-10wt%, the carbon ferrochrome that activated carbon or broken electrode or carbon content are high: 0.20-0.90wt%, cobalt: surplus;
Except aforesaid way, can also choose in following ratio:
Chromium: 10.0-40.0wt%, nickel: 1-12wt%, tungsten: 2-10wt%, carbon: 0.20-0.90t%, cobalt: the cobalt Nicrotung of surplus.
In concrete implementation procedure, when choosing raw material metal, the charging sequence of said raw material metal is:
Put into the high carbon ferrochrome of cobalt and activated carbon or broken electrode or carbon content earlier, add tungsten, nickel and chromium again, add remaining cobalt at last again.
Step 12: selected raw material is put into crucible, obtain the cobalt-chromium-tungsten alloy powder through vacuum induction melting, inert gas atomizer technology.
In this step, the detailed process of above-mentioned inert gas atomizer comprises:
At first; Utilize the Frequency Induction Heating raw material; Be warming up to 1400～1700 ℃, under vacuum, be incubated 6～25 minutes, sample analysis after utilizing the abundant deoxidation of carbon and adding an amount of aluminium final deoxidizing; Add an amount of broken electrode or high carbon ferro-chrome adjustment carbon content to 0.20-0.90wt%, the mode that is employed in refining under the vacuum and inert gas atomizer prepares the cobalt-chromium-tungsten alloy powder.
Wherein atomization gas is nitrogen or argon gas, and the atomizing cone angle is 45～75 °, and atomizing pressure is 1～2.2MPa.Adopt recovery rate >=55% of CoCrW alloy powder-45 μ m of this method preparation.
Step 13: said alloy powder is sieved or classification, prepare the Co-based alloy powder of powder size in the 1-45 mu m range.
Through the resulting CoCrW alloy powder of above-mentioned preparation process; The fine powder oxygen content that has solved present CoCrW alloy powder is high, pine than and mobile bad, spraying in problems such as density and the bond strength of low, the coating of powder utilization is low, improved the quality of cobalt chromium tungsten CoCrW powder-product.
Further; Can also adopt the resulting CoCrW alloy powder of above-mentioned preparation process to make cobalt chromium tungsten coating; Specifically be to adopt supersonic spray coating technology to carry out; Be illustrated in figure 2 as the CoCrW alloy powder that utilizes that the embodiment of the invention enumerates and make the process chart of cobalt chromium tungsten coating, among Fig. 2:
At first, be specially: with specimen surface oil removing, blasting treatment in the exemplar surface preparation.
After drying above-mentioned prepared cobalt-chromium-tungsten alloy powder then, utilize supersonic spray coating technology that it is deposited on the exemplar surface, thereby prepare cobalt chromium tungsten coating;
Cobalt chromium tungsten coating to after the preparation is handled again, is specially: to the heat treatment of said cobalt chromium tungsten coating;
Finally obtain cobalt chromium tungsten coating goods.
In the concrete implementation procedure, utilize the technological parameter of supersonic spray coating prepared cobalt chromium tungsten coating to be: kerosene oil flow 600～1000L/h; Oxygen flow 15～30L/min; Powder feed rate 20～200g/min; Spray distance 100～400mm.
Through cobalt chromium tungsten coating hardness HR15T >=81 that said method makes, bond strength >=50MPa, oxide content are 0.8-1.5wt%, and 700 ℃ of anti-thermal shocks do not have cracking 20 times.
The above; Be merely the preferable specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, any technical staff who is familiar with the present technique field is in the technical scope that the present invention discloses; The variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (7)
1. the preparation method of a fine grain Co-based alloy powder is characterized in that, said preparation method comprises:
1) gets the metal material of target component or contain the alloy material of corresponding cobalt content;
2) selected raw material is put into crucible, obtain Co-based alloy powder through vacuum induction melting, inert gas atomizer technology;
3) sieve or classification, prepare the Co-based alloy powder of powder size in the 1-45 mu m range.
2. preparation method according to claim 1 is characterized in that, the technological parameter of said inert gas atomizer is:
Atomization gas is nitrogen or argon gas, atomizing drift angle＜28 °, atomizing pressure＞3MPa.
3. preparation method according to claim 1 is characterized in that, the mass percent of said Co-based alloy powder composition is:
A) chromium: 10.0-40.0wt%, nickel: 1-12wt%, tungsten: 2-10wt%, carbon: 0.20-1.5wt%, cobalt: surplus;
Or, b) chromium: 4～20wt%, molybdenum: 20～30wt%, silicon: 2～8wt%, cobalt: surplus.
4. according to claim 1 or 3 described preparation methods, it is characterized in that the main body granularity of said Co-based alloy powder is 1-45 μ m.
5. Co-based alloy powder according to claim 4; It is characterized in that its typical composition is the CoCrW alloy powder, powder formation rate >=55% in the 1-45 mu m range; Wherein 1-25 mu m range powder accounts for 15%-20%, and 25-45 mu m range powder accounts for 35%-40%.
6. Co-based alloy powder according to claim 4 is characterized in that, the oxygen content≤0.02wt% of said Co-based alloy powder.
7. preparation method according to claim 1 is characterized in that, said preparation method also comprises:
Utilize prepared Co-based alloy powder to adopt supersonic spray coating technology to make cobalt chromium tungsten coating, the technological parameter of prepared cobalt chromium tungsten coating is:
Kerosene oil flow 600～1000L/h; Oxygen flow 15～30L/min; Powder feed rate 20～200g/min; Spray distance 100～400mm.
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| CN104372205A (en) * | 2014-10-29 | 2015-02-25 | 沈阳黎明航空发动机(集团)有限责任公司 | CoCrW-base high-temperature alloy powder for engine turbine shroud ring wear-resistant coatings and preparation method thereof |
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| CN106119662A (en) * | 2016-07-28 | 2016-11-16 | 洛阳轴研科技股份有限公司 | A kind of cobalt-chromium-tungsten alloy material, the cobalt-chromium-tungsten alloy ball and preparation method thereof for ball-screw bearing, ball-screw bearing |
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| US20230127003A1 (en) * | 2021-01-27 | 2023-04-27 | National Tsing Hua University | High hardness and temperature-resistant alloy and article comprising the same |
| US11987865B2 (en) * | 2021-01-27 | 2024-05-21 | National Tsing Hua University | High hardness and temperature-resistant alloy and article comprising the same |
| US20240167142A1 (en) * | 2022-11-18 | 2024-05-23 | BGRIMM Technology Group,Ltd. | Dense thick alloy coating without layered organizational structure and preparation method thereof |
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