CN103056376A - Method for preparing spherical nanostructure tungsten/cobalt carbide compound powder - Google Patents
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Abstract
The invention discloses a method for preparing spherical nanostructure tungsten/cobalt carbide compound powder by waste hard alloy. The method is characterized by including the steps of firstly, oxidizing and crushing waste tungsten/cobalt carbide material to obtain tungsten/cobalt compound oxide powder; secondly, dissolving 93-96% of the tungsten/cobalt compound oxide powder obtained in the step 1, 3-6% of water-soluble carburization spheroidizing agent and 0.1-2% of water-soluble compound grain growth inhibitor in water with 3-5 times of mass to obtain mixed water solution; thirdly, subjecting the mixed water solution obtained in the step 2 to fast spray-drying to obtain intermediate with evenly distributed components; and fourthly, subjecting the intermediate obtained in the step 3 to reduction, synthesis and carbon regulation at 900-1000 DEG C to obtain the nanostructure spherical tungsten/cobalt carbide compound powder.
Description
Technical field
The present invention relates to a kind of method for preparing spherical nanostructure tungsten carbide/cobalt composite powder, relate in particular to a kind of method of utilizing the residual carbide alloy that gives up in the industry to prepare spherical nanostructure tungsten carbide/cobalt composite powder.
Background technology
The WC-Co carbide alloy of nanostructured ultra-fine grain has high rigidity, high-intensity good serviceability, mainly can be used to make surface-mounted integrated circuit microbit, dot-matrix printer, printing syringe needle, whole aperture knife tool, carpenter's usefulness cutter, accurate tool and mould, cutting of hardworking material cutter etc.The crystal grain of WC base cemented carbide is more tiny, and defective is fewer, and wherein Binder Phase such as Co phase average free path diminish, and material bending strength and hardness numerical value all can be higher; And when other condition homogeneous phases simultaneously, the properties of WC base cemented carbide---hardness, elastic modelling quantity, wearability and compression strength etc. all can narrowing down and effectively strengthened with the diminishing of hard phase composition WC average grain diameter wherein, size distribution.
Waste hand alloy material mainly produces in process of production, the desktop material that produces during such as powder production, fabric, the useless briquetting in the forming process, sintering waste product, rear processing waste product etc.; Another kind ofly in the product use procedure, produce, as, useless drill bit, useless blade, useless pricker sheet etc.Latter's quantity is many, and intractability is large.
Because the key component of carbide alloy is tungsten carbide, metallic cobalt and rare metal additive etc., economic worth is high, the effective way that reduces production costs is not only in the regeneration of waste hand alloy material, and resources conservation, environmental friendliness tool are of great significance.
The waste hand alloy material that produces in the product use procedure efficiently utilize method, comprise mechanical crushing method, the molten method of zinc, electrochemical process, nitre method and redox carbonizatin method etc. in the conventional method.
Mechanical crushing method is a kind of comparatively simple recovery method, it does not change the chemical composition of waste hand alloy material, also need not the constituent elements such as tungsten, cobalt are separated, as long as to carrying out Mechanical Crushing and ball milling after the processing of waste hand alloy material cleaning surfaces, can obtain carbide alloy mixture.Before the fragmentation, the reply carbide alloy carries out high-temperature process, makes it short texture, expansion porous, by Mechanical Crushing, can significantly improve the particularly crushing effect of bulk, high binding agent hard alloy scraps of carbide alloy again.
The molten method of zinc reclaims hard alloy scraps and mainly is comprised of " zinc is molten " and " dezincify " two procedures.Hard alloy scraps through classifying and cleaning up and spelter are packed in the lump according to the ratio of 1:1～2 in the sintered molten crucible, vacuumize, feeding temperature-raising to 900～1000 ℃, behind the insulation certain hour, carry out vacuum and propose the zinc processing, after the cooling spongiform cobalt powder and tungsten carbide agglomerate are drawn off, through ball milling, fragmentation, adjustment alloying component, again make carbide alloy.
Electrochemistry recycling carbide alloy is to utilize electrolysis principle, in electrolytic cell, carbide alloy is made anode, electrode potential according to material is different, by the control electrolytic process parameter, in different electrolyte, make WC or Co enter solution with ionic species respectively, or be precipitated out with the form of the earth of positive pole.By the cobalt in the recovery dielectric and the tungsten carbide in the solid phase, carry out the recycling of carbide alloy.
The nitre method is made oxidant with nitre, at high temperature makes tungsten oxidation and reaction in the hard alloy scraps generate sodium tungstate, and the sodium tungstate frit obtains sodium tungstate solution through levigate leaching, removes impurity through purification again, just can make various tungsten products (such as APT, WO
3, WC, W powder etc.); Leached mud is then for extracting the raw material of cobalt etc.
Redox carbonizatin method essence is with at high temperature oxidation of hard alloy scraps, and volume of material is increased, and spalling becomes loose breakable object, obtains WO through pulverizing
3With CoWO
4Obtain the composite powder of tungsten and cobalt behind the composite oxides, composite oxides reduction, join carbon after, get the WC/Co composite powder 1200 ℃ of left and right sides carbonizations, be directly used in the production carbide alloy.
The at present preparation of the ultrafine nanometer tungsten carbide/cobalt composite powder of ultra-fine grain tungsten carbide/cobalt carbide alloy manufacturing usefulness mainly contains following method:
(1) liquid phase chemical reduction method: principle is for to be dissolved in an amount of soluble metallic salt raw material in the liquid, is mixed with the metal salt solution of special component and with the solution processing that atomizes; With reducing agent the metal ion of ionic state is reduced to the superfine nano metal carbide powders again.
(2) carbon thermal response method: 1. principle at first needing to make the mixed solution of primitive reaction raw material and various additives; 2. again this mixed solution is carried out the spray-drying preliminary treatment and produce precursor powder; 3. at last utilize the carbon thermal response to prepare the tungsten carbide/cobalt composite powder precursor powder of producing.Such as US Patent No. 5352269(1994) just use spray-drying and fluidization carbon thermal reduction method to prepare the tungsten carbide/cobalt composite powder.
Above method all exists certain deficiency and defective:
1. be by passing into the CH of capacity in the carbonisation
4Or CO/CO
2Carry out Gas-solid surface Deng carbon potential atmosphere gas and react to introduce carbon atom, such length will inevitably expend the more time apart from gas diffusion process and need to pass into more carbon potential atmosphere gas, the reaction speed that will slow down like this and greatly increase production cost.
2. prepared nanometer tungsten carbide/Co composite powder be easy to because of ingress of air oxidized, thereby reduce properties of product.
3. use fluid bed to carry out the reduction and carbonization reaction, gas consumption and the energy consumption of participating in reaction are all increased greatly, and the reaction time is long, reaction efficiency is lower, has increased equally production cost.
By the patent document retrieval and inquisition, obtain following prior art:
The patentee is Zhuzhou Hard Alloy Group Co Ltd, patent name is the fluidized preparation method of WC-Co composite powder, number of patent application is 201010104957.2, a kind of fluidized preparation method of WC-Co composite powder is disclosed, it mainly may further comprise the steps: take tungsten-cobalt composite oxide powder as raw material, material powder is dropped in the fluid bed, pass into hydrogen and inert gas at 600～900 ℃ and make it reduction, 1～3 hour reaction time; After reduction process finishes, drop into solid-state carbon source, under 700～1300 ℃ temperature, carry out continuous carbonization, 30～150 minutes reaction time; Pass at last carbonaceous gas, hydrogen and inert gas and transfer carbon, 600～1000 ℃ of reaction temperatures in 10～60 minutes reaction time, obtain WC-Co (WC-Co) composite powder.The WC-Co composite powder homogeneous chemical composition that obtains, stable performance, impurity content is low, can satisfy the higher industrial production requirement, can be widely used in the suitability for industrialized production of multiple preparation ultra-fine cemented carbide.
The patentee is Wuhan University of Technology, and patent name is the direct-reduction carbonization manufacture method of tungsten-cobalt carbide nano composite powder, and number of patent application is 200410012902.3, discloses a kind of direct-reduction carbonization manufacture method of tungsten-cobalt carbide nano composite powder.Adopt one of three kinds of modes preparation oxide powder: (1) with tungsten cobalt raw material, crystallizing inhibitor, carbon dust in proportion mixing and ball milling make the mixed-powder of oxide and carbon dust; (2) tungsten cobalt raw material, crystallizing inhibitor are made oxide powder with combination process, again itself and carbon dust mixing and ball milling are made the mixed-powder of oxide and carbon dust; (3) tungsten cobalt raw material, crystallizing inhibitor and solubility carbon source are mixed in proportion, make the oxide powder of carbon containing with combination process.Above-mentioned combination process refers to that spray pyrolysis or spray-drying or spray-drying add calcination.Oxide powder is put into reacting furnace under the ambiance, by control reduction and carbonization temperature and the reaction time, wash the carbon temperature and the reaction time makes the nano WC-Co composite powder end.Simple safe technological process of the present invention, easily control, do not pollute, cost of investment is low, be suitable for industrial-scale production.
The patentee is Metal Inst., Chinese Academy of Sciences, patent name is a kind of preparation method of composite hard alloy powder of tungsten carbide and titanium cobalt carbide, number of patent application is 00110137.4, a kind of preparation method of composite hard alloy powder of tungsten carbide and titanium cobalt carbide is disclosed, the weight item scope of composite powder is in WC55-75%, TiC15-35%, Co surplus, it is characterized in that: at first that the soluble-salt of tungstenic, cobalt, titanium is soluble in water in proportion, stir; Mentioned solution is atomized into droplet, and drop size is used the heated air drying granulation simultaneously less than 1 μ m, and intake air temperature 200-300 ℃, air outlet temperature 100-200 ℃; The powder collected at 600-800 ℃ of roasting 1-5 hour, is carried out carbonization again and namely gets the WC-TiC-Co cemented carbide powder.The present invention is the existing technique of economization greatly, and prepared powder composition and even tissue, and granularity can reach nano-scale.
According to the inquiry of above patent document, above patent document the technical problem to be solved and technical scheme that adopts is different from the invention, so the present invention is creative with respect to the above patent document that retrieves.
Summary of the invention
The key technical problem that will solve required for the present invention provides that a kind of can high efficiente callback useless residual Hardmetal materials carries out regeneration and technical process is simple, the novel preparation method of Nanometre grade tungsten carbide/Co composite powder that properties of product are good.
In order to overcome the above problems the technical solution used in the present invention: a kind of method for preparing spherical nanostructure tungsten carbide/cobalt composite powder is characterized in that comprising following processing step:
Step 1: initiation material is in the production process or the useless residual tungsten carbide/cobalt material after using, the initiation material that the surface has been cleaned up is exposed in the oxygen-containing atmosphere, employing is carried out high temperature sintering greater than 850 ℃ temperature, makes initial useless residual raw material can obtain sufficient oxidation; Useless residual tungsten carbide/cobalt after the oxidation is further carried out break process, obtain tungsten-cobalt composite oxide powder through oxidation, fragmentation;
Step 2: selecting mass fraction is the tungsten-cobalt composite oxide powder that the step 1 of 93-96% obtains, and the water-soluble carburizing nodulizer of 3-6% and 0.1-2% Water Soluble Compound grain growth inhibitor are mixed with mixed aqueous solution to be dissolved in quality in 3-5 water doubly;
Step 3: the intermediate product that the mixed aqueous solution of step 2 is obtained distributed components after the fast spraying drying;
Step 4: the intermediate product that obtains after the process step 3, need synthetic through the reduction of 900-1000 ℃ of temperature and accent carbon, prepare the tungsten carbide/cobalt composite powder material with nanostructured.
Under better status of implementation, the loose spongy precursor powder that obtains after oxidation that described step 1 obtains also needs to grind fragmentation, and carries out 60 mesh sieves by the requirement of precursor powder particle size and divide classification; Wait until next step by the precursor powder of sieve aperture as reaction raw materials and use, the precursor powder by sieve aperture does not continue to pulverize until reach the desired particle size requirement.
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, 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.
The beneficial effect that adopts the present invention to obtain:
1, in sum, technique of the present invention can also be used with the useless residual Hardmetal materials of processing again in high efficiente callback, its technical process and equipment are simple, prepared powder property is good, is the preparation method of a kind of not only environmental protection but also economic novel nano ultrafine tungsten carbide/Co composite powder.
2, 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.
3, can effectively stop excessive grain to be grown up owing in step 2, 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.
Description of drawings
Fig. 1 is nanostructured WC/Co composite powder preparation method's technical process figure.
The specific embodiment
Below in conjunction with drawings and Examples the invention will be further elaborated explanation.
Referring to Fig. 1, the useless residual Hardmetal materials of this utilization comes the novel preparation process of production nanostructured tungsten carbide/cobalt composite powder mainly to be comprised of oxidation fragmentation, reduction, this three basic operation of carbonization as raw material.
The waste hand alloy material that contains the tungsten cobalt element at first need to be under oxidizing atmosphere (air, oxygen or both mixtures) carry out the calcination heating and make the hard ware material of bulk can access abundant oxidation; And feed product volume after peroxidization can increase 2～4 times, and becomes spongy material loose, porous, is easy to carry out follow-up break process; The color of material also can along with the variation of contained cobalt amount wherein gradually by the light blue breen that changes to.Sample begins to occur surface oxidation when calcination temperature is higher than 850 ℃, and the thickness of oxide layer is along with calcination and oxidation reaction are carried out the prolongation of time and progressive additive, until complete oxidation.Product is mainly by WO
3And CoWO
4Form.
In the process that calcination and oxidation reaction are carried out, the factor that affects the material complete oxidation time mainly contains: 1. the content of oxygen in oxide isolation can affect the reaction speed of oxidation reaction process widely; 2. another important factor in order that determines the complete oxidation time is weight and the surface area size thereof of material products; Surface area is larger, and the needed oxidization time of complete oxidation is shorter, and oxidation reaction is carried out more thoroughly.
Under better status of implementation, the Sponge Porosity material behind the complete oxidation need to carry out Mechanical Crushing, grinding and powder and cross the reducing process that just can carry out next step after the previous works such as sieve classification.
Referring to Fig. 1, can in the metal powder mixture that contains tungsten and cobalt that makes, add water-soluble carburizing nodulizer (such as polyethylene glycol (PEG), polyvinyl alcohol (PVA), starch, sugar etc.) and corresponding compound grain growth inhibitor (ammonium dichromate, ammonium metavanadate, VC/Cr
3C
2Or its oxide) jointly be mixed with mixed aqueous solution and spray-dried granulation after, gained ultrafine precursor powder carries out reduction and carbonization and processes being lower than under the temperature of normal carburizing temperature (about 1400 ℃), form loose frangible WC/Co compound, the superfine nano WC/Co composite powder of function admirable can be prepared, and the preparation that ultrafine gain size and high-performance are made surperficial engineering material again can be further used for.
This technique can make grain refinement, the comprehensive reutilization of useless residual Hardmetal materials is become a reality, and technical process is simple, easy to operate, low for equipment requirements, the recovery utilization rate of raw material has good economic benefit and social benefit up to more than 95%.
Example 1:
Step 1: initiation material is in the production process or the useless residual tungsten carbide/cobalt material after using, initiation material is exposed in the oxygen-containing atmosphere, adopt 850 ℃ temperature to carry out high temperature sintering, the useless residual raw material that the initiation material surface has been cleaned up can obtain sufficient oxidation; Useless residual tungsten carbide/cobalt after the oxidation is further carried out break process, obtain tungsten-cobalt composite oxide precursor powder through oxidation, fragmentation;
Step 2: the precursor powder of selecting the step 1 of 95kg to obtain, the water-soluble chromic salts of 3kg starch and 2kg is dissolved in the water that quality is 300kg, is mixed with mixed aqueous solution;
Step 3: the mixed aqueous solution of step 2 must be obtained superfine composite salt powder after the fast spraying drying;
Step 4: through the dusty material that obtains after the step 3, need to synthesize and accent carbon through the reduction of 900 ℃ of temperature, prepare the tungsten carbide/cobalt composite powder material with nanostructured.
By example 1, the recovery utilization rate of useless residual tungsten carbide/cobalt raw material is up to more than 95%, and the tungsten carbide/cobalt composite powder is spherical in shape, tungsten carbide crystal grain degree≤75nm.
Example 2:
Step 1: initiation material is in the production process or the useless residual tungsten carbide/cobalt material after using, initiation material is exposed in the oxygen-containing atmosphere, adopt 880 ℃ temperature to carry out high temperature sintering, the useless residual raw material that the initiation material surface has been cleaned up can obtain sufficient oxidation; Useless residual tungsten carbide/cobalt after the oxidation is further carried out break process, obtain tungsten-cobalt composite oxide precursor powder through oxidation, fragmentation;
Step 2: selecting mass fraction is the precursor powder that the step 1 of 93kg obtains, and the water-soluble vanadic salts of 6kg sugar and 1kg is dissolved in the water that quality is 400kg, is mixed with mixed aqueous solution;
Step 3: the mixed aqueous solution of step 2 must be obtained superfine composite salt powder after the fast spraying drying;
Step 4: through the dusty material that obtains after the step 3, need to synthesize and accent carbon through the reduction of 1000 ℃ of temperature, prepare the tungsten carbide/cobalt composite powder material with nanostructured.
By example 2, the recovery utilization rate of useless residual tungsten carbide/cobalt raw material is up to more than 95%, and the tungsten carbide/cobalt composite powder is spherical in shape, tungsten carbide crystal grain degree≤70nm.
Example 3:
Step 1: initiation material is in the production process or the useless residual tungsten carbide/cobalt material after using, initiation material is exposed in the oxygen-containing atmosphere, adopt 900 ℃ temperature to carry out high temperature sintering, the useless residual raw material that the initiation material surface has been cleaned up can obtain sufficient oxidation; Useless residual tungsten carbide/cobalt after the oxidation is further carried out break process, obtain tungsten-cobalt composite oxide precursor powder through oxidation, fragmentation;
Step 2: the precursor powder of selecting the step 1 of 93.9kg to obtain, 6kg polyethylene glycol (PEG) and the water-soluble chromic salts of 0.1kg are dissolved in the water that quality is 300kg, are mixed with mixed aqueous solution;
Step 3: the mixed aqueous solution of step 2 must be obtained superfine composite salt powder after the fast spraying drying;
Step 4: through the dusty material that obtains after the step 3, need to synthesize and accent carbon through the reduction of 950 ℃ of temperature, prepare the tungsten carbide/cobalt composite powder material with nanostructured.
By example 3, the recovery utilization rate of useless residual tungsten carbide/cobalt raw material is up to more than 95%, and the tungsten carbide/cobalt composite powder is spherical in shape, tungsten carbide crystal grain degree≤68nm.
Example 4:
Step 1: initiation material is in the production process or the useless residual tungsten carbide/cobalt material after using, initiation material is exposed in the oxygen-containing atmosphere, adopt 950 ℃ temperature to carry out high temperature sintering, the useless residual raw material that the initiation material surface has been cleaned up can obtain sufficient oxidation; Useless residual tungsten carbide/cobalt after the oxidation is further carried out break process, obtain tungsten-cobalt composite oxide precursor powder through oxidation, fragmentation;
In order to obtain better reaction effect, accelerate the reaction time, improve the recovery utilization rate of useless residual tungsten carbide/cobalt raw material.The loose spongy precursor powder that obtains after oxidation that described step 1 obtains also needs to grind fragmentation, and carries out 60 mesh sieves by the requirement of precursor powder particle size and divide classification; Wait until next step by the precursor powder of sieve aperture as reaction raw materials and use, the precursor powder by sieve aperture does not continue to pulverize until reach the desired particle size requirement.
Step 2: the precursor powder of selecting the step 1 of 94kg to obtain, 5kg polyvinyl alcohol (PVA) and the water-soluble vanadic salts of 1kg are dissolved in the water that quality is 500kg, are mixed with mixed aqueous solution;
Step 3: the mixed aqueous solution of step 2 must be obtained superfine composite salt powder after the fast spraying drying;
Step 4: through the dusty material that obtains after the step 3, need to synthesize and accent carbon through the reduction of 980 ℃ of temperature, prepare the tungsten carbide/cobalt composite powder material with nanostructured.
By example 4, the recovery utilization rate of useless residual tungsten carbide/cobalt raw material is up to more than 96%, and the tungsten carbide/cobalt composite powder is spherical in shape, tungsten carbide crystal grain degree≤65nm.
Example 5:
Step 1: initiation material is in the production process or the useless residual tungsten carbide/cobalt material after using, initiation material is exposed in the oxygen-containing atmosphere, adopt 850 ℃ temperature to carry out high temperature sintering, the useless residual raw material that the initiation material surface has been cleaned up can obtain sufficient oxidation; Useless residual tungsten carbide/cobalt after the oxidation is further carried out break process, obtain tungsten-cobalt composite oxide precursor powder through oxidation, fragmentation;
Step 2: the precursor powder of selecting the step 1 of 95kg to obtain, 3kg polyethylene glycol (PEG) is dissolved in the water that quality is 300kg with starch mixture and the water-soluble chromic salts of 2kg, is mixed with mixed aqueous solution;
Step 3: the mixed aqueous solution of step 2 must be obtained superfine composite salt powder after the fast spraying drying;
Step 4: through the dusty material that obtains after the step 3, need to synthesize and accent carbon through the reduction of 900 ℃ of temperature, prepare the tungsten carbide/cobalt composite powder material with nanostructured.
By example 5, the recovery utilization rate of useless residual tungsten carbide/cobalt raw material is up to more than 95%, and the tungsten carbide/cobalt composite powder is spherical in shape, tungsten carbide crystal grain degree≤60nm.
More than a kind of method for preparing nanometer tungsten carbide/cobalt composite powder body material 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 (4)
1. method for preparing spherical nanostructure tungsten carbide/cobalt composite powder is characterized in that comprising following processing step:
Step 1: initiation material is in the production process or the useless residual tungsten carbide/cobalt material after using, and the initiation material that surface clean is clean is exposed in the oxygen-containing atmosphere, adopts and carries out high temperature sintering greater than 850 ℃ temperature, makes useless residual raw material can obtain sufficient oxidation; Useless residual tungsten carbide/cobalt after the oxidation is further carried out break process, obtain tungsten-cobalt composite oxide powder through oxidation, fragmentation;
Step 2: selecting mass fraction is the tungsten-cobalt composite oxide powder that the step 1 of 93-96% obtains, and the water-soluble carburizing nodulizer of 3-6% and 0.1-2% Water Soluble Compound grain growth inhibitor are mixed with mixed aqueous solution to be dissolved in quality in 3-5 water doubly;
Step 3: the intermediate product that the mixed aqueous solution of step 2 is obtained distributed components after the fast spraying drying;
Step 4: the intermediate product that obtains after the process step 3, need synthetic through the reduction of 900-1000 ℃ of temperature and accent carbon, prepare the tungsten carbide/cobalt composite powder material with nanostructured.
2. a kind of method for preparing spherical nanostructure tungsten carbide/cobalt composite powder according to claim 1, it is characterized in that: the loose spongy precursor powder that obtains after oxidation that described step 1 obtains also needs to grind fragmentation, and carries out 60 mesh sieves by the requirement of precursor powder particle size and divide classification; Wait until next step by the precursor powder of sieve aperture as reaction raw materials and use, the precursor powder by sieve aperture does not continue to pulverize until reach the desired particle size requirement.
3. a kind of method for preparing spherical nanostructure tungsten carbide/cobalt 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.
4. a kind of method for preparing spherical nanostructure 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.
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| CN105648383A (en) * | 2016-01-12 | 2016-06-08 | 江西理工大学 | Preparing method for WC-Co composite powder for thermal spraying |
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| CN109485046A (en) * | 2018-11-30 | 2019-03-19 | 株洲硬质合金集团有限公司 | A kind of tungsten carbide powder and preparation method thereof |
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| CN103909274A (en) * | 2014-04-25 | 2014-07-09 | 湖南顶立科技有限公司 | Method for preparing cobalt coated nanometer WC crystal composite powder and ultra-thin grain hard alloy |
| CN103909274B (en) * | 2014-04-25 | 2016-06-15 | 湖南顶立科技有限公司 | A kind of method preparing cobalt cladding nanometer WC crystal composite powder and ultra-fine cemented carbide |
| CN106563802A (en) * | 2015-10-08 | 2017-04-19 | 荆门市格林美新材料有限公司 | Granular coating cobalt powder preparation method |
| CN105648383A (en) * | 2016-01-12 | 2016-06-08 | 江西理工大学 | Preparing method for WC-Co composite powder for thermal spraying |
| CN109485046A (en) * | 2018-11-30 | 2019-03-19 | 株洲硬质合金集团有限公司 | A kind of tungsten carbide powder and preparation method thereof |
| CN109485046B (en) * | 2018-11-30 | 2022-06-03 | 株洲硬质合金集团有限公司 | Tungsten carbide powder and preparation method thereof |
| CN109266939A (en) * | 2018-12-05 | 2019-01-25 | 株洲江钨博大硬面材料有限公司 | A kind of high-densit WC-WB-Co spherical powder hard material and preparation method thereof |
| CN109266939B (en) * | 2018-12-05 | 2020-07-24 | 株洲江钨博大硬面材料有限公司 | Preparation method of high-density WC-WB-Co spherical powder hard-face material |
| CN111826539A (en) * | 2020-06-09 | 2020-10-27 | 厦门金鹭特种合金有限公司 | Control method for adjusting hard alloy bonding phase composition |
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