CN103056377A - Method for manufacturing nanometer tungsten/cobalt carbide composite powder - Google Patents
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Abstract
The invention discloses a method for manufacturing nanometer tungsten/cobalt carbide composite powder. The method is characterized by comprising technological steps of firstly, dissolving, by mass, 55-92% of water-soluble tungsten salt, 3-40% of water-soluble cobalt salt, 3-6% of water-soluble carburizing and nodulizing agents and 0.1-2% of water-soluble composite grain growth inhibitors into water with the mass 3-5 times that of a mixture of the water-soluble tungsten salt, the water-soluble cobalt salt, the water-soluble carburizing and nodulizing agents and the water-soluble composite grain growth inhibitors to prepare mixed aqueous solution; secondly, adding carbon nano-tubes (CNT) accounting for 1-10% of the total mass of the aqueous solution into the mixed aqueous solution obtained in the first step and enabling the carbon nano-tubes to be uniformly mixed in the mixed aqueous solution; thirdly, performing quick low-temperature spray drying for mixed aqueous solution obtained in the second step to obtain precursor powder of ultrafine tungsten and cobalt composite salt; and fourthly, performing reduction synthesis and carbon conditioning at the temperature ranging from 900 DEG C to 1000 DEG C for the precursor powder obtained in the third step to prepare tungsten/cobalt carbide composite powder materials with nanostructures.
Description
Technical field
The present invention relates to a kind of preparation technology of nanostructured tungsten carbide/cobalt composite powder, especially relate to a kind of scale industrialization preparation of multiduty nanostructured tungsten carbide/cobalt composite powder, be mainly used in the preparation of ultra-fine nano-powder, particularly the preparation technology of nanometer tungsten based composite powder series material and method field.
Background technology
The refractory metal tungsten alloy has the physical and mechanical property of a series of excellences, has very widely purposes in the fields such as defence and military, Aero-Space, electronic information, the energy, metallurgy and Mechanical Processing Industry, occupies an important position in national economy.The W-Co carbide alloy has the wearability that high hardness, intensity are become reconciled, and is a kind of adamantine hard material that is only second to, and is widely used as the machining instrument, is called as " tooth of modern industry ".Thereby such alloy material has been subject to the great attention of countries in the world, become one of the most active research field of material supply section educational circles.
Along with the development that science and technology is maked rapid progress, also more and more high to the requirement of material; Adapt with it, employing new technology with novel preparation process is the developing direction of the multi-functional tungsten sill of research and development novel high-performance.Because nano material has the incomparable property of many traditional materials, so that it becomes one to improving the promising research direction of tool of material property.
Traditional cemented carbide powder production procedure: ammonium paratungstate (APT)-WO
3-W-WC-batching-shaping--sintering, technical process is various, each operation has the possibility that makes contaminated and dirtyization of raw material, and repeatedly repeatedly pyroprocess can make the grain size of final products wayward, WO wherein
3Reduction and carbonisation, batching mechanical milling process and sintering process all need to consume a large amount of energy, this not only makes the production cycle of carbide alloy series of products elongated, product quality is wayward, also so that production cost and energy consumption become very high.
CNT (CNT) has very high Young's modulus, and has very high thermal conductivity, electrical conductivity and chemical inertness.Add CNT (CNT) in matrix material or the coating new composite of formation, can improve significantly mechanics and the electric property of composite.Nano powder of tungsten carbide is then with the dual good characteristic of superhard material and nano particle, if can with CNT (CNT) compound use, will produce extremely far-reaching influence to field of new.
Various superfines preparation methods and technology being are all are being researched and developed energetically so that further develop more high performance Hardmetal materials in countries in the world at present.Wherein more strengthen fund input and technical research dynamics aspect the high-performance preparation technology of superfine nano structure WC-Co composite powder and coating material thereof, developing the process at some preparation nano WC-Co composite powder ends.
At present, the preparation technology of WC-Co dusty material mainly contains:
(1), uses fixed bed or rotary furnace etc. that the oxide of tungsten is reduced under hydrogen atmosphere and become high purity tungsten, prepared high purity tungsten and carbon dust are carried out mixing and ball milling, can make WC powder finally by crossing high temperature cabonization, WC powder and metal Co powder evenly be mixed carry out mechanical ball and grind and to prepare the WC-Co powder; Oxide and the carbon dust of tungsten are mixed mutually, and by rotary furnace direct-reduction carbonization in the hydrogen atmosphere under the hot conditions, can make the WC powder, thereby the WC powder mixes with the metal Co powder and carries out ball milling and make the WC-Co powder.
The method is the preparation method of traditional WC-Co cemented carbide powder, and it is inhomogeneous that the shortcoming of this conventional method is that W mixes with Co, and carburizing temperature height and energy consumption are high, are difficult to prepare nano level super fine composite powder.
(2), in the people's such as Zhang Zongtao patent of invention (patent No. ZL 97106622.1), mention the preparation method at a kind of nano WC-Co composite powder end, with water miscible tungstenic, cobalt salt class and macromolecular organic compound are prepared precursor solution as reaction raw materials jointly, thereby chemical reaction can occur precursor solution generates sediment, the sediment surface that forms is coated with the hydrophobic film layer of one deck paraffin class, and remove wherein moisture and other organic groups by reducing agent such as inferior sodium phosphate etc., form at last and only contain tungsten, cobalt, the mixture of carbon just can obtain the nano WC-Co composite powder end with this mixture through carbonization treatment.
This technique is owing to used a large amount of macromolecular organic compounds and reducing agent, so technical process is stricter to the requirement of production equipment, and the purity of product is difficult to control.
(3), at first the raw material of tungstenic cobalt is made the composite oxide power of tungstenic, cobalt element with spray-drying, again the tungsten cobalt/cobalt oxide powder that makes is put into fluidized-bed reactor, at certain temperature conditions and H
2/ CO/CO
2Carry out continuous reduction and carbonization reaction in the atmosphere, can make the WC-Co composite powder.Or tungsten cobalt compound and grain growth inhibitor are prepared the powder of composite oxides via spray pyrolysis, this composite oxide power in fluidized-bed reactor, is prepared nano-structure WC-Co composite powder through techniques such as reduction and carbonization, additional carbonization and accent carbon.
The method production cost is high, the difficult control of technical process.
(4), with the tungstenic salt with contain the cobalt salt class and jointly make mixed solution, mixed solution carries out spray-drying process in spray drying tower can obtain the composite oxide power presoma, this precursor powder after calcining and carbon dust mix and to carry out ball milling, in hydrogen atmosphere, carry out at last reduction and carbonization and just can obtain nanoscale WC-Co composite powder.
The method has been used hydrogen atmosphere and carbon dust mixing and ball milling in reduction and carbonization technique, so that the carbon content of the composite powder of preparing is wayward.And in this technique, have tungsten oxide and cobalt oxide, thereby in redox reaction, can generate hydrate, finally can make particle be easy to agglomeration.
Summary of the invention
The invention solves deficiency and the defective in prior art and the technique and provide a kind of process route easy, by adding CNT (CNT) to water-soluble tungsten salt, water soluble cobaltous salt, water-soluble carburizing nodulizer and Water Soluble Compound grain growth inhibitor mixed aqueous solution, can realize that scale industrialization prepares the new technology that ultrafine gain size is used nanostructured superfine WC-Co composite powder body material.
For realizing above purpose, the present invention by the following technical solutions: a kind of preparation method of nanometer tungsten carbide/Co composite powder is characterized in that comprising following processing step:
Step 1: with mass fraction percentage be the Water Soluble Compound grain growth inhibitor of the water-soluble carburizing nodulizer of water soluble cobaltous salt, 3-6% of water-soluble tungsten salt, the 3-40% of 55-92% and 0.1-2% to be dissolved in quality be in the 3-5 water doubly, be mixed with mixed aqueous solution;
Step 2: add the CNT (CNT) of step 1 aqueous solution gross mass 1%-10% in the mixed aqueous solution that obtains to step 1, stirred 30～60 minutes with 10～30 rev/mins speed, can mix;
Step 3: with the quick low temperature spray drying of mixed aqueous solution process that obtains in the step 2, described low temperature drying intake air temperature is 150 ~ 200 ℃, and air outlet temperature only is 70～90 ℃, can obtain ultra-fine tungsten cobalt complex salt precursor powder;
Step 4: the presoma powder that obtains in the step 3 is synthesized and accent carbon through reducing under the 900-1000 ℃ of temperature conditions, prepare the tungsten carbide/cobalt composite powder material with nanostructured.
Under better status of implementation, described water-soluble tungsten salt adopts ammonium metatungstate (AMT) or ammonium paratungstate (APT) a kind of or its mixture wherein.
Under better status of implementation, described water soluble cobaltous salt is Co (NO3)
2, cobalt acetate, cobalt oxalate or CoCl
2Wherein one or more mixing.
Under better status of implementation, described water-soluble carburizing nodulizer comprises that a kind of or two or more macromolecule organic binder bonds in polyethylene glycol (PEG), polyvinyl alcohol (PVA), starch, the sugar mix mutually.Water-soluble carburizing nodulizer plays reduction and carburization in the reduction of powder, carbonisation, another effect is to increase solution viscosity, improves Surface Tension of Liquid Drops, is convenient to make spherical powder.
Under better status of implementation, described Water Soluble Compound grain growth inhibitor is water-soluble chromic salts or vanadic salts.
Under better status of implementation, be added with the CNT (CNT) of 3%-8% in the aqueous solution of described step 2.
Under better status of implementation, described step 4 with hydrogen as reduction protection atmosphere, with methane or CO/CO
2Be carbon potential atmosphere, under 900-1000 ℃ hot conditions, reduce synthetic and accent carbon.
The present invention has following beneficial effect:
1, (ammonium metatungstate (AMT) or ammonium paratungstate (APT) carry out the preparation of nano composite powder as the fundamental reaction raw material and by solwution method, have avoided present and have prepared many unfavorable factors that the conventional method of superfines produces because generally carrying out mixing and ball milling with all solid state material to use the tungsten of highly-water-soluble/cobalt salt class; The same compound grain growth inhibitor with highly-water-soluble that adopts is compared creative with the process of directly adding before solid-state inhibitor.
2, described preparation technology uses highly-water-soluble tungsten salt, cobalt salt as the primitive reaction raw material, the compound grain growth inhibitor that adds in addition also is water miscible, carbon source also adopts liquid carbon source, it is more abundant that reaction is carried out, powder grain obtains further refinement, compares creative with the process of directly adding before solid-state inhibitor.
3, described water-soluble carburizing nodulizer comprises that a kind of or two or more macromolecule organic binder bonds in polyethylene glycol (PEG), polyvinyl alcohol (PVA), starch, the sugar mix mutually.Described water-soluble carburizing nodulizer plays reduction and carburization in the reduction of powder, carbonisation, another effect is to increase solution viscosity, improves Surface Tension of Liquid Drops, is convenient to make spherical powder.Described water-soluble carburizing nodulizer can reduce processing cost and effective protection of the environment, meets the construction of resource-conserving and friendly environment society.
4, in the primitive reaction raw material, added an amount of CNT (CNT), can prepare multiduty superfine nano WC/Co composite powder, made product have simultaneously the dual good characteristic of CNT (CNT) and nanometer tungsten carbide, of many uses.Adding CNT (CNT) in the raw materials technology is another innovative point of the present invention.This technique can be produced nanometer tungsten carbide-CNT (CNT) composite powder material; Present this composite powder material is mainly used in the modification of composite deposite technology.Single use nano powder of tungsten carbide or CNT (CNT) all can weaken the integrated application performance of composite deposite to a certain extent; Such as the simple variation that may cause ductility of electrodeposited film with nano tungsten carbide during as the wild phase of composite deposite, otherwise, when simple use CNT (CNT) is as the composite deposite wild phase equally the wearing and tearing of coating are aggravated greatly, then can significantly improve bulk strength, toughness and the coefficient of friction of coating when CNT (CNT) and nanometer tungsten carbide use jointly.
5, in the preparation technology of above-described nano composite powder, mixed aqueous solution carries out drying and granulating with spray drying tower and obtains the complex salt precursor powder, uses elevated-temperature seal fluidization synthetic furnace to carry out last carbonizing reduction treatment process.
6, can effectively stop the excessive grain overgrowing owing in step 1, add grain growth inhibitor in the reaction raw materials, thereby grain graininess and the distribution thereof of control grain refinement, goods, so the kind selection of crystallizing inhibitor, addition manner and interpolation time are most important to the raising of properties of product.In technical scheme proposed by the invention, abandoned the interpolation using method of traditional solid-state crystallizing inhibitor, the water miscible compound crystallizing inhibitor of creationary employing (comprise water-soluble vanadic salts/chromic salts, such as ammonium dichromate, ammonium metavanadate, VC/Cr
3C
2Or V
2O
5/ Cr
3O
5Deng), so that grain growth inhibitor can be diffused into each intergranule more uniformly, be present between crystal boundary or be dissolved in the Binder Phase, thereby can more effectively stop grain growth, make crystal grain obtain further refinement.
7, use the prepared nanostructured tungsten carbide/cobalt composite powder of above-mentioned technique to have the particle size distribution narrow range, regular shape, uniformity and good fluidity, crystal grain is tiny, the mean grain size characteristics such as between 40～60nm.
In sum, the present invention is that a kind of process route is simple, and properties of product are good, product granularity is even and crystal grain is tiny, is fit to very much to carry out the preparation method of the nano-structure WC-Co composite powder of industrialization large-scale production.
Description of drawings
Fig. 1 is preparation technology's flow chart of the present invention.
The specific embodiment
Below in conjunction with the drawings and specific embodiments to the further explaination of the present invention.
Example 1:
Step 1: with the ammonium metatungstate (AMT) of 55kg, the Co (NO3) of 40kg
2, the polyethylene glycol (PEG) of 3kg and the water-soluble vanadic salts of 2kg be dissolved in the water that quality is 300kg, is mixed with mixed aqueous solution;
Step 2: add the CNT (CNT) of 1kg in the mixed aqueous solution that obtains to step 1, stirred 30 minutes with 10 rev/mins speed, can mix;
Step 3: with the quick low temperature spray drying of mixed aqueous solution process that obtains in the step 2, described low temperature drying intake air temperature is 150 ℃, and air outlet temperature only is 70 ℃, can obtain ultra-fine tungsten cobalt complex salt precursor powder;
Step 4: the presoma powder that obtains in the step 3 is synthesized and accent carbon through reducing under 900 ℃ of temperature conditions, prepare the tungsten carbide/cobalt composite powder material with nanostructured.
Obtain the mean grain size of tungsten carbide/cobalt composite powder material between 50～60nm by example 1.
Example 2:
Step 1: the ammonium paratungstate (APT) of 92kg, the cobalt oxalate of 3kg, the polyvinyl alcohol (PVA) of 3kg and the water-soluble vanadic salts of 2kg are dissolved in the water of 400kg, are mixed with mixed aqueous solution;
Step 2: add the CNT (CNT) of 3kg in the mixed aqueous solution that obtains to step 1, stirred 40 minutes with 20 rev/mins speed, can mix;
Step 3: with the quick low temperature spray drying of mixed aqueous solution process that obtains in the step 2, described low temperature drying intake air temperature is 200 ℃, and air outlet temperature only is 90 ℃, can obtain ultra-fine tungsten cobalt complex salt precursor powder;
Step 4: the presoma powder that obtains in the step 3 is synthesized and accent carbon through reducing under 900 ℃ of temperature conditions, prepare the tungsten carbide/cobalt composite powder material with nanostructured.
Obtain the mean grain size of tungsten carbide/cobalt composite powder material between 45～55nm by example 2.
Example 3:
Step 1: with the ammonium paratungstate (APT) of 62kg, the CoCl of 30kg
2, the starch of 6kg and the water-soluble chromic salts of 2kg be dissolved in the water of 500kg, is mixed with mixed aqueous solution;
Step 2: add the CNT (CNT) of 8kg in the mixed aqueous solution that obtains to step 1, stirred 60 minutes with 30 rev/mins speed, can mix;
Step 3: with the quick low temperature spray drying of mixed aqueous solution process that obtains in the step 2, described low temperature drying intake air temperature is 180 ℃, and air outlet temperature only is 80 ℃, can obtain ultra-fine tungsten cobalt complex salt precursor powder;
Step 4: the presoma powder that obtains in the step 3 is synthesized and accent carbon through reducing under 1000 ℃ of temperature conditions, prepare the tungsten carbide/cobalt composite powder material with nanostructured.
Obtain the mean grain size of tungsten carbide/cobalt composite powder material between 40～50nm by example 3.
Example 4:
Step 1: 70kg ammonium paratungstate (APT), the cobalt acetate of 25kg, the sugar of 4.9kg and the water-soluble chromic salts of 0.1kg of inciting somebody to action are dissolved in the water of 400kg, are mixed with mixed aqueous solution;
Step 2: add the CNT (CNT) of 10kg in the mixed aqueous solution that obtains to step 1, stirred 60 minutes with 30 rev/mins speed, can mix;
Step 3: with the quick low temperature spray drying of mixed aqueous solution process that obtains in the step 2, described low temperature drying intake air temperature is 200 ℃, and air outlet temperature only is 70 ℃, can obtain ultra-fine tungsten cobalt complex salt precursor powder;
Step 4: with the presoma powder that obtains in the step 3 with hydrogen as reduction protection atmosphere, with methane or CO/CO
2Be carbon potential atmosphere, through reducing synthetic under 900 ℃ of temperature conditions and transferring carbon, prepare the tungsten carbide/cobalt composite powder material with nanostructured.
Obtain the mean grain size of tungsten carbide/cobalt composite powder material between 40～50nm by example 4.
Example 5:
Step 1: with the ammonium metatungstate (AMT) of 65kg, the CoCl of 30kg
2, polyethylene glycol (PEG) and starch mixture 4kg and 1kg water-soluble vanadic salts be dissolved in the water of 500kg, be mixed with mixed aqueous solution;
Step 2: add the CNT (CNT) of 7kg in the mixed aqueous solution that obtains to step 1, stirred 50 minutes with 20 rev/mins speed, can mix;
Step 3: with the quick low temperature spray drying of mixed aqueous solution process that obtains in the step 2, described low temperature drying intake air temperature is 180 ℃, and air outlet temperature only is 80 ℃, can obtain ultra-fine tungsten cobalt complex salt precursor powder;
Step 4: with the presoma powder that obtains in the step 3 with hydrogen as reduction protection atmosphere, with methane or CO/CO
2Be carbon potential atmosphere, through reducing synthetic under 900 ℃ of temperature conditions and transferring carbon, prepare the tungsten carbide/cobalt composite powder material with nanostructured.
Obtain the mean grain size of tungsten carbide/cobalt composite powder material between 40～50nm by example 5.
Preparation technique and process that the multiple tungsten carbide/cobalt of this superfine nano closes powder have creativeness as described below, are that those skilled in the art are non-obvious.According to above embodiment, draw to draw a conclusion:
(1), fully changed the production technology of the domestic Solid raw materials mixing and ball milling method that generally adopts before, but adopt full water-soluble tungsten/cobalt salt class raw material to carry out solution mixing method, reaching the mutual mixing of multicomponent on ion concentration, thereby realize that powder preparation liquefied, distributed components, component consist of the purpose of Composite.
(2), in raw material, added an amount of CNT (CNT) innovatively, make that Uniform Dispersion has a certain amount of CNT (CNT) in the nano composite powder of producing; This new technology not only can be prepared the nano WC-Co composite powder end that ultrafine gain size uses, and simultaneously can also output can be used for nanometer tungsten carbide-CNT (CNT) composite deposite modified powder material of composite deposite modification technology; This material has the dual premium properties of nanometer tungsten carbide and CNT (CNT) simultaneously, can greatly strengthen bulk strength and the toughness of coating material.
(3), abandoned the at present Mechanical Crushing methods such as the consistent pressed powder mutual mixed grinding crush method of using or mechanical ball-milling method, adopt solwution method and through high-pressure fog rapid draing, can realize the nanometer refinement to powder grain;
(4), changed the aging method that traditional use fixed bed carries out reduction and carbonization fully, the use elevated-temperature seal fluidization synthetic furnace of novelty carries out the reduction and carbonization operation, impel powder more to disperse and give full play to the effect of grain growth inhibitor, prevented that the mutual contact of powder from growing up and intergranular bonding, reunion.
(5), changed the hydrogen atmosphere reducing process of using before, and adopt activated carbon to carry out reduction reaction, so can not produce the hydrate of tungsten, the deposition of energy establishment powder grain is grown up, and the in-situ carburization of the gas carburization of powder surface and inside is two-way carrying out simultaneously, greatly accelerate carburizing reagent speed, reduced cost.
The technology of preparing of this nanostructured composite granule and process thereof can realize the low nano combined tungsten carbide/cobalt dusty material that drops into, prepares to extensive industrialization; The composite granule good fluidity of producing, particle size distribution is narrow, the pattern rule, crystal grain is tiny.
More than the preparation method of a kind of nanometer tungsten carbide/Co composite powder provided by the present invention is described in detail, herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, for one of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (7)
1. the preparation method of a nanometer tungsten carbide/Co composite powder is characterized in that comprising following processing step:
Step 1: with mass fraction percentage be the Water Soluble Compound grain growth inhibitor of the water-soluble carburizing nodulizer of water soluble cobaltous salt, 3-6% of water-soluble tungsten salt, the 3-40% of 55-92% and 0.1-2% to be dissolved in quality be in the 3-5 water doubly, be mixed with mixed aqueous solution;
Step 2: add the CNT (CNT) of step 1 aqueous solution gross mass 1%-10% in the mixed aqueous solution that obtains to step 1, stirred 30～60 minutes with 10～30 rev/mins speed, can mix;
Step 3: with the quick low temperature spray drying of mixed aqueous solution process that obtains in the step 2, described low temperature drying intake air temperature is 150 ~ 200 ℃, and air outlet temperature only is 70～90 ℃, can obtain ultra-fine tungsten cobalt complex salt precursor powder;
Step 4: the presoma powder that obtains in the step 3 is synthesized and accent carbon through reducing under the 900-1000 ℃ of temperature conditions, prepare the tungsten carbide/cobalt composite powder material with nanostructured.
2. the preparation method of a kind of nanometer tungsten carbide/Co composite powder according to claim 1; It is characterized in that described water-soluble tungsten salt adopts ammonium metatungstate (AMT) or ammonium paratungstate (APT) a kind of or its mixture wherein.
3. the preparation method of a kind of nanometer tungsten carbide/Co composite powder according to claim 1; It is characterized in that described water soluble cobaltous salt is Co (NO3)
2, cobalt acetate, cobalt oxalate or CoCl
2Wherein one or more mixing.
4. the preparation method of a kind of nanostructured tungsten carbide/cobalt composite powder according to claim 1; It is characterized in that described water-soluble carburizing nodulizer comprises that a kind of or two or more macromolecule organic binder bonds in polyethylene glycol (PEG), polyvinyl alcohol (PVA), starch, the sugar mix mutually.
5. the preparation method of a kind of nanometer tungsten carbide/Co composite powder according to claim 1; It is characterized in that described Water Soluble Compound grain growth inhibitor is water-soluble chromic salts or vanadic salts.
6. the preparation method of a kind of nanometer tungsten carbide/Co composite powder according to claim 1; It is characterized in that being added with in the aqueous solution of described step 2 CNT (CNT) of 3%-8%.
7. the preparation method of a kind of nanometer tungsten carbide/Co composite powder according to claim 1; It is characterized in that described step 4 with hydrogen as reduction protection atmosphere, with methane or CO/CO
2Be carbon potential atmosphere, under 900-1000 ℃ hot conditions, reduce synthetic and accent carbon.
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| WO2015169132A1 (en) * | 2014-05-09 | 2015-11-12 | 湖南顶立科技有限公司 | Method for preparing wc-co powder used for thermal spraying |
| CN104338935A (en) * | 2014-10-30 | 2015-02-11 | 赣州有色冶金研究所 | Method for simply and rapidly preparing nano WC-Co composite powder |
| CN107570722A (en) * | 2017-09-04 | 2018-01-12 | 深圳职业技术学院 | A kind of preparation method of 3D printing material |
| CN107570722B (en) * | 2017-09-04 | 2019-03-29 | 深圳职业技术学院 | A kind of preparation method of 3D printing material |
| CN108326319A (en) * | 2018-03-07 | 2018-07-27 | 合肥工业大学 | A kind of preparation method being granulated WC-Co hot spray powders |
| CN108326319B (en) * | 2018-03-07 | 2021-06-08 | 合肥工业大学 | Preparation method of granulated WC-Co thermal spraying powder |
| CN109128141A (en) * | 2018-09-30 | 2019-01-04 | 合肥工业大学 | A kind of preparation method of nanometer WC-Co composite powder |
| CN109972018A (en) * | 2019-05-10 | 2019-07-05 | 赣州有色冶金研究所 | A kind of WC-Co-RE composite powder and the preparation method and application thereof |
| CN114990405A (en) * | 2022-06-15 | 2022-09-02 | 李凌祥 | High-performance superfine hard alloy and preparation method thereof |
| CN114990405B (en) * | 2022-06-15 | 2022-12-06 | 李凌祥 | High-performance superfine hard alloy and preparation method thereof |
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