CN103056376B - Method for preparing spherical nanostructure tungsten/cobalt carbide compound powder - Google Patents
Method for preparing spherical nanostructure tungsten/cobalt carbide compound powder Download PDFInfo
- Publication number
- CN103056376B CN103056376B CN201310000618.3A CN201310000618A CN103056376B CN 103056376 B CN103056376 B CN 103056376B CN 201310000618 A CN201310000618 A CN 201310000618A CN 103056376 B CN103056376 B CN 103056376B
- Authority
- CN
- China
- Prior art keywords
- cobalt
- tungsten
- powder
- carbide
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
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 preparing spherical nanostructure tungsten/cobalt carbide compound powder, particularly relate to a kind of method utilizing cemented carbide crystal in industry to prepare spherical nanostructure tungsten/cobalt carbide compound powder.
Background technology
The WC-Co hard alloy of nanostructured ultra-fine grain has the excellent serviceability of high rigidity, high strength, mainly can be used to make surface-mounted integrated circuit microbit, dot-matrix printer, printing syringe needle, overall aperture knife tool, carpenter with cutter, accurate tool and mould, cutting of hardworking material cutter etc.The crystal grain of WC base cemented carbide is more tiny, and defect is fewer, and wherein Binder Phase such as Co phase average free path diminishes, and material bending strength and hardness values 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 with the diminishing of wherein hard phase composition WC average grain diameter, the narrowing and effectively strengthened of size distribution.
Waste hand alloy material mainly produces in process of production, as produce during powder production desktop material, fabric, the useless briquetting in forming process, sintering waste product, aft-loaded airfoil waste product etc.; Another kind ofly to produce in product use procedure, e.g., useless drill bit, useless blade, useless pricker sheet etc.The latter's quantity is many, and intractability is large.
Key component due to carbide alloy is tungsten carbide, metallic cobalt and rare metal additive etc., economic worth is high, the effective way reducing production cost is not only in the regeneration of waste hand alloy material, and is of great significance resources conservation, environmental friendliness tool.
The Efficient utilization method of the waste hand alloy material produced in product use procedure, conventional method comprises mechanical crushing method, zinc melts method, electrochemical process, nitre method and redox carbonizatin method etc.
Mechanical crushing method is the comparatively simple recovery method of one, it does not change the chemical composition of waste hand alloy material, also without the need to being separated the constituent element such as tungsten, cobalt, as long as carry out Mechanical Crushing and ball milling to after the process of waste hand alloy material surface cleaning, carbide alloy mixture can be obtained.Before fragmentation, reply carbide alloy carries out high-temperature process, makes it short texture, expanded porous, then by Mechanical Crushing, significantly can improve the crushing effect of carbide alloy particularly bulk, high binding agent hard alloy scraps.
The molten method of zinc reclaims hard alloy scraps and forms primarily of " zinc is molten " and " dezincify " two procedures.Hard alloy scraps through classifying and clean up and spelter load in sintered molten crucible according to the ratio of 1:1 ~ 2 in the lump, vacuumize, feeding temperature-raising to 900 ~ 1000 DEG C, after held for some time, carry out vacuum and propose zinc process, after 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 utilizes electrolysis principle, in a cell carbide alloy is made anode, different according to the electrode potential of material, by controlling electrolytic process parameter, in different electrolyte, make WC or Co enter solution in the form of an ion respectively, or be precipitated out with the form of the earth of positive pole.By reclaiming the cobalt in dielectric and the tungsten carbide in solid phase, carry out the recycling of carbide alloy.
Nitre method nitre makes oxidant, at high temperature makes the tungsten in hard alloy scraps be oxidized and react to generate sodium tungstate, and sodium tungstate frit obtains sodium tungstate solution through levigate leaching, then through purification removing impurity, just can obtain various tungsten product (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 at high temperature oxidized by hard alloy scraps, and volume of material is increased, and spalling becomes loose breakable object, obtains WO through pulverizing
3with CoWO
4composite oxides, obtain the composite powder of tungsten and cobalt, after joining carbon, obtain WC/Co composite powder, be directly used in production carbide alloy about 1200 DEG C carbonizations after composite oxides reduction.
The preparation of the ultrafine nanometer tungsten carbide/cobalt composite powder of current ultra-fine grain tungsten carbide/cobalt carbide alloy manufacture mainly contains following method:
(1) solution phase chemical reduction: principle is be dissolved in liquid by appropriate soluble metallic salt raw material, is mixed with the metal salt solution of special component and solution is carried out atomization process; Be superfine nano metal carbide powders with reducing agent by the reducing metal ions of ionic state again.
(2) carbon-thermal reduction method: principle is the mixed solution 1. first needing to make primitive reaction raw material and various additive; 2. again this mixed solution is carried out spraying dry pretreatment to produce precursor powder; 3. the last carbon-thermal reduction that utilized by produced precursor powder is to prepare tungsten carbide/cobalt composite powder.As US Patent No. 5352269(1994) just use spraying dry and fluidization carbothermal method to prepare tungsten carbide/cobalt composite powder.
Above method all also exists certain deficiency and defect:
1. be by passing into enough CH in carbonisation
4or CO/CO
2carry out Gas-solid surface reaction introduce carbon atom Deng carbon potential atmosphere gas, so long distance gas diffusion process will inevitably expend the more time 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. obtained nanometer tungsten carbide/Co composite powder is easy to oxidized because of ingress of air, thus reduces properties of product.
3. use fluid bed to carry out reduction and carbonization reaction, the gas consumption that participation can be made to react and energy consumption increase all greatly, and the reaction time is long, and reaction efficiency is lower, adds production cost equally.
By patent document retrieval and inquisition, obtain following prior art:
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; disclose a kind of fluidized preparation method of WC-Co composite powder; it mainly comprises the following steps: take tungsten-cobalt composite oxide powder as raw material; material powder is dropped in fluid bed, pass into hydrogen and inert gas at 600 ~ 900 DEG C and make it reduction, 1 ~ 3 hour reaction time; After reduction process terminates, drop into solid-state carbon source, at the temperature of 700 ~ 1300 DEG C, carry out continuous carbonization, 30 ~ 150 minutes reaction time; Finally pass into carbonaceous gas, hydrogen and inert gas and carry out tune carbon, reaction temperature 600 ~ 1000 DEG C, 10 ~ 60 minutes reaction time, obtain WC-Co (WC-Co) composite powder.The WC-Co composite powder uniform composition that obtains, stable performance, impurity content is low, can meet higher industrial production requirement, can be widely used in the multiple suitability for industrialized production preparing ultra-fine cemented carbide.
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 to prepare oxide powder: (1) by 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, then 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 spraying dry or spraying dry add calcination.Oxide powder is put into the reacting furnace under ambiance, by controlling reduction and carbonization temperature and reaction time, washing carbon temperature and the reaction time obtains nanometer WC-Co composite powder.Simple and direct safe, the easy control of present invention process, not do not pollute, cost of investment is low, be suitable for industrial-scale production.
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; disclose a kind of preparation method of composite hard alloy powder of tungsten carbide and titanium cobalt carbide; the weight item scope of composite powder is in WC55-75%, TiC15-35%, Co surplus; it is characterized in that: first that the soluble-salt of tungstenic, cobalt, titanium is soluble in water in proportion, stir; Above-mentioned solution mist is changed into droplet, and drop size is less than 1 μm, uses heated air drying granulation, intake air temperature 200-300 DEG C simultaneously, air outlet temperature 100-200 DEG C; By the powder collected at 600-800 DEG C of roasting 1-5 hour, then carry out carbonization and namely obtain WC-TiC-Co cemented carbide powder.The present invention can the existing technique of economization greatly, and prepared powdered ingredients and even tissue, 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 adopted is different from the invention, therefore the present invention is creative relative to the patent document retrieved above.
Summary of the invention
The key technical problem that will solve required for the present invention is to provide one can carry out regeneration and technical process is simple, the novel processing step of Nanometre grade tungsten carbide/Co composite powder that properties of product are excellent by high efficiente callback cemented carbide crystal material.
In order to overcome the above problems, the technical solution used in the present invention: a kind of method preparing spherical nanostructure tungsten/cobalt carbide compound powder, is characterized in that comprising following processing step:
Step 1: initiation material is the useless residual tungsten carbide/cobalt material in production process or after using, the initiation material cleaned up on surface is exposed in oxygen-containing atmosphere, adopt the temperature being greater than 850 DEG C to carry out high temperature sintering, initial useless residual raw material can be oxidized fully; Further break process is carried out to the useless residual tungsten carbide/cobalt after oxidation, obtains tungsten-cobalt composite oxide powder through oxidation, fragmentation;
Step 2: select mass fraction to be the tungsten-cobalt composite oxide powder that the step 1 of 93-96% obtains, the water-soluble carburizing nodulizer of 3-6% and 0.1-2% Water Soluble Compound grain growth inhibitor are in 3-5 water doubly to be dissolved in quality, are mixed with mixed aqueous solution;
Step 3: the intermediate product mixed aqueous solution of step 2 being obtained after fast spraying drying distributed components;
Step 4: the intermediate product obtained after step 3, needs the reduction synthesis through 900-1000 DEG C of temperature and tune carbon, prepares the tungsten carbide/cobalt composite powder material with nanostructured.
Under better status of implementation, it is broken that the loose spongy precursor powder obtained after oxidation that described step 1 obtains also needs to carry out grinding, and carry out 60 order sieve classifications by the requirement of precursor powder particle size; Wait until next step by the precursor powder of sieve aperture as reaction raw materials to use, do not continue to pulverize until reach desired particle size requirement by the precursor powder of sieve aperture.
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 one in polyethylene glycol (PEG), polyvinyl alcohol (PVA), starch, sugar or two or more high-molecular organic adhesive mixes mutually.Water-soluble carburizing nodulizer plays reduction and carburization in the reduction, carbonisation of powder, and another effect increases solution viscosity, improves Surface Tension of Liquid Drops, is convenient to manufacture spherical powder.
Adopt the beneficial effect that the present invention obtains:
1, in sum, technique of the present invention can also be used with process cemented carbide crystal material again in high efficiente callback, its technical process and equipment simple, prepared powder property is excellent, is a kind of not only environmental protection but also the preparation method of economic novel nano ultrafine tungsten carbide/Co composite powder.
2, described water-soluble carburizing nodulizer comprises one in polyethylene glycol (PEG), polyvinyl alcohol (PVA), starch, sugar or two or more high-molecular organic adhesive mixes mutually.Described water-soluble carburizing nodulizer plays reduction and carburization in the reduction, carbonisation of powder, and another effect increases solution viscosity, improves Surface Tension of Liquid Drops, is convenient to manufacture spherical powder.Described water-soluble carburizing nodulizer can reduce processing cost and effective protection of the environment, meets the construction of resource-efficient and environment friendly society.
3, can excessive grain be effectively stoped to be grown up owing to adding grain growth inhibitor in step 2 in reaction raw materials, thus control grain refinement, the grain graininess of goods and distribution thereof, therefore the kind of crystallizing inhibitor select, addition manner and the raising of interpolation time to properties of product most important.In technical scheme proposed by the invention, abandon the interpolation using method of traditional solid-state crystallizing inhibitor, and creationary employing water miscible compound crystallizing inhibitor (comprise water-soluble vanadic salts/chromic salts, as ammonium dichromate, ammonium metavanadate, VC/Cr
3c
2or V
2o
5/ Cr
3o
5deng), make grain growth inhibitor can evenly be diffused between each crystal grain, be present between crystal boundary or be dissolved in Binder Phase, thus more effectively can stop grain growth, making crystal grain obtain further refinement.
Accompanying drawing explanation
Fig. 1 is the technical process figure of nanostructured WC/Co composite powder preparation method.
Detailed description of the invention
Below in conjunction with drawings and Examples the invention will be further elaborated explanation.
See Fig. 1, this novel preparation process utilizing cemented carbide crystal material to carry out production nanostructured tungsten carbide/cobalt composite powder as raw material is mainly made up of oxidation fragmentation, reduction, these three basic working procedure of carbonization.
First waste hand alloy material containing tungsten cobalt element needs under oxidizing atmosphere (air, oxygen or both mixtures) to carry out calcination heating, and that the hard ware material of bulk is obtained is fully oxidized; And feed product volume after peroxidization can increase 2 ~ 4 times, and become loose, the spongy material of porous, be easy to carry out follow-up break process; The color of material also can change to breen by light blue along with the change of wherein contained cobalt amount gradually.Sample starts surface oxidation occurs higher than when 850 DEG C at calcination temperature, and the thickness of oxide layer carries out the prolongation of time and progressive additive, until complete oxidation along with calcination and oxidation reaction.Product is primarily of WO
3and CoWO
4formed.
In the process that calcination and oxidation reaction are carried out, the factor affecting 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. determine that another important factor in order of complete oxidation time is weight and the surface area size thereof of material products; Surface area is larger, and the oxidization time required for complete oxidation is shorter, and oxidation reaction is carried out more thorough.
Under better status of implementation, the Sponge Porosity material after complete oxidation needs the reducing process carrying out just carrying out after the previous works such as sieve classification crossed by Mechanical Crushing, grinding and powder next step.
See Fig. 1, can obtained containing the metal powder mixture of tungsten and cobalt in add water-soluble carburizing nodulizer (as polyethylene glycol (PEG), polyvinyl alcohol (PVA), starch, sugar etc.) and correspondence composite grain to grow up inhibitor (ammonium dichromate, ammonium metavanadate, VC/Cr
3c
2or its oxide) co-formulation becomes mixed aqueous solution and after spray-dried granulation, gained ultrafine precursor powder (about 1400 DEG C) at the temperature lower than normal carburizing temperature carries out reduction and carbonization process, 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 manufacture Surface Engineering material again can be further used for.
This technique can make grain refinement, the comprehensive reutilization of cemented carbide crystal material is become a reality, and technical process is simple, easy to operate, low for equipment requirements, the recovery utilization rate of raw material, up to more than 95%, has good economic benefit and social benefit.
Example 1:
Step 1: initiation material is the useless residual tungsten carbide/cobalt material in production process or after using, initiation material is exposed in oxygen-containing atmosphere, adopt the temperature of 850 DEG C to carry out high temperature sintering, the useless residual raw material that initiation material surface has been cleaned up can be oxidized fully; Further break process is carried out to the useless residual tungsten carbide/cobalt after oxidation, obtains tungsten-cobalt composite oxide precursor powder through oxidation, fragmentation;
Step 2: select the precursor powder that the step 1 of 95kg obtains, it is in the water of 300kg that 3kg starch and the water-soluble chromic salts of 2kg are dissolved in quality, is mixed with mixed aqueous solution;
Step 3: the mixed aqueous solution of step 2 must be obtained superfine composite salt powder after fast spraying drying;
Step 4: the dusty material obtained after step 3, needs the reduction synthesis through 900 DEG C of temperature and tune carbon, prepares 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 tungsten carbide/cobalt composite powder is spherical in shape, tungsten carbide crystal grain degree≤75nm.
Example 2:
Step 1: initiation material is the useless residual tungsten carbide/cobalt material in production process or after using, initiation material is exposed in oxygen-containing atmosphere, adopt the temperature of 880 DEG C to carry out high temperature sintering, the useless residual raw material that initiation material surface has been cleaned up can be oxidized fully; Further break process is carried out to the useless residual tungsten carbide/cobalt after oxidation, obtains tungsten-cobalt composite oxide precursor powder through oxidation, fragmentation;
Step 2: select mass fraction to be the precursor powder that the step 1 of 93kg obtains, it is in the water of 400kg that 6kg sugar and the water-soluble vanadic salts of 1kg are dissolved in quality, is mixed with mixed aqueous solution;
Step 3: the mixed aqueous solution of step 2 must be obtained superfine composite salt powder after fast spraying drying;
Step 4: the dusty material obtained after step 3, needs the reduction synthesis through 1000 DEG C of temperature and tune carbon, prepares 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 tungsten carbide/cobalt composite powder is spherical in shape, tungsten carbide crystal grain degree≤70nm.
Example 3:
Step 1: initiation material is the useless residual tungsten carbide/cobalt material in production process or after using, initiation material is exposed in oxygen-containing atmosphere, adopt the temperature of 900 DEG C to carry out high temperature sintering, the useless residual raw material that initiation material surface has been cleaned up can be oxidized fully; Further break process is carried out to the useless residual tungsten carbide/cobalt after oxidation, obtains tungsten-cobalt composite oxide precursor powder through oxidation, fragmentation;
Step 2: select the precursor powder that the step 1 of 93.9kg obtains, it is in the water of 300kg that 6kg polyethylene glycol (PEG) and the water-soluble chromic salts of 0.1kg are dissolved in quality, is mixed with mixed aqueous solution;
Step 3: the mixed aqueous solution of step 2 must be obtained superfine composite salt powder after fast spraying drying;
Step 4: the dusty material obtained after step 3, needs the reduction synthesis through 950 DEG C of temperature and tune carbon, prepares 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 tungsten carbide/cobalt composite powder is spherical in shape, tungsten carbide crystal grain degree≤68nm.
Example 4:
Step 1: initiation material is the useless residual tungsten carbide/cobalt material in production process or after using, initiation material is exposed in oxygen-containing atmosphere, adopt the temperature of 950 DEG C to carry out high temperature sintering, the useless residual raw material that initiation material surface has been cleaned up can be oxidized fully; Further break process is carried out to the useless residual tungsten carbide/cobalt after oxidation, obtains tungsten-cobalt composite oxide precursor powder through oxidation, fragmentation;
In order to better reaction effect can be obtained, accelerate the reaction time, improve the recovery utilization rate of useless residual tungsten carbide/cobalt raw material.It is broken that the loose spongy precursor powder obtained after oxidation that described step 1 obtains also needs to carry out grinding, and carry out 60 order sieve classifications by the requirement of precursor powder particle size; Wait until next step by the precursor powder of sieve aperture as reaction raw materials to use, do not continue to pulverize until reach desired particle size requirement by the precursor powder of sieve aperture.
Step 2: select the precursor powder that the step 1 of 94kg obtains, it is in the water of 500kg that 5kg polyvinyl alcohol (PVA) and the water-soluble vanadic salts of 1kg are dissolved in quality, is mixed with mixed aqueous solution;
Step 3: the mixed aqueous solution of step 2 must be obtained superfine composite salt powder after fast spraying drying;
Step 4: the dusty material obtained after step 3, needs the reduction synthesis through 980 DEG C of temperature and tune carbon, prepares 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 tungsten carbide/cobalt composite powder is spherical in shape, tungsten carbide crystal grain degree≤65nm.
Example 5:
Step 1: initiation material is the useless residual tungsten carbide/cobalt material in production process or after using, initiation material is exposed in oxygen-containing atmosphere, adopt the temperature of 850 DEG C to carry out high temperature sintering, the useless residual raw material that initiation material surface has been cleaned up can be oxidized fully; Further break process is carried out to the useless residual tungsten carbide/cobalt after oxidation, obtains tungsten-cobalt composite oxide precursor powder through oxidation, fragmentation;
Step 2: select the precursor powder that the step 1 of 95kg obtains, it is in the water of 300kg that 3kg polyethylene glycol (PEG) is dissolved in quality 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 fast spraying drying;
Step 4: the dusty material obtained after step 3, needs the reduction synthesis through 900 DEG C of temperature and tune carbon, prepares 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 tungsten carbide/cobalt composite powder is spherical in shape, tungsten carbide crystal grain degree≤60nm.
Above a kind of method preparing nanometer tungsten carbide/cobalt composite powder body material provided by the present invention is described in detail, set forth principle of the present invention and embodiment herein, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; Meanwhile, 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. prepare a method for spherical nanostructure tungsten/cobalt carbide compound powder, it is characterized in that comprising following processing step:
Step 1: initiation material is the useless residual tungsten carbide/cobalt material in production process or after using, and is exposed in oxygen-containing atmosphere by initiation material clean for surface clean, adopts the temperature being greater than 850 DEG C to carry out high temperature sintering, useless residual raw material can be oxidized fully; Further break process is carried out to the useless residual tungsten carbide/cobalt after oxidation, obtains tungsten-cobalt composite oxide powder through oxidation, fragmentation;
Step 2: select mass fraction to be the tungsten-cobalt composite oxide powder that the step 1 of 93-96% obtains, the water-soluble carburizing nodulizer of 3-6% and 0.1-2% Water Soluble Compound grain growth inhibitor are in 3-5 water doubly to be dissolved in quality, are mixed with mixed aqueous solution;
Step 3: the intermediate product mixed aqueous solution of step 2 being obtained after fast spraying drying distributed components;
Step 4: the intermediate product obtained after step 3, needs the reduction synthesis through 900-1000 DEG C of temperature and tune carbon, prepares the tungsten carbide/cobalt composite powder material with nanostructured.
2. a kind of method preparing spherical nanostructure tungsten/cobalt carbide compound powder according to claim 1, it is characterized in that: it is broken that the loose spongy precursor powder obtained after oxidation that described step 1 obtains also needs to carry out grinding, and carry out 60 order sieve classifications by the requirement of precursor powder particle size; Wait until next step by the precursor powder of sieve aperture as reaction raw materials to use, do not continue to pulverize until reach desired particle size requirement by the precursor powder of sieve aperture.
3. a kind of method preparing spherical nanostructure tungsten/cobalt carbide compound 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 preparing spherical nanostructure tungsten/cobalt carbide compound powder according to claim 1; It is characterized in that described water-soluble carburizing nodulizer comprises one in polyethylene glycol (PEG), polyvinyl alcohol (PVA), starch or two or more high-molecular organic adhesive mixes mutually.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310000618.3A CN103056376B (en) | 2013-01-04 | 2013-01-04 | Method for preparing spherical nanostructure tungsten/cobalt carbide compound powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310000618.3A CN103056376B (en) | 2013-01-04 | 2013-01-04 | Method for preparing spherical nanostructure tungsten/cobalt carbide compound powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103056376A CN103056376A (en) | 2013-04-24 |
| CN103056376B true CN103056376B (en) | 2015-04-08 |
Family
ID=48099426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310000618.3A Active CN103056376B (en) | 2013-01-04 | 2013-01-04 | Method for preparing spherical nanostructure tungsten/cobalt carbide compound powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103056376B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106563802B (en) * | 2015-10-08 | 2020-02-07 | 荆门市格林美新材料有限公司 | Preparation method of granular coated cobalt powder |
| CN105648383B (en) * | 2016-01-12 | 2018-07-27 | 江西理工大学 | A kind of preparation method at WC-Co composite powder end used for hot spraying |
| 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 |
| 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 |
| CN111826539B (en) * | 2020-06-09 | 2021-11-26 | 厦门金鹭特种合金有限公司 | Control method for adjusting hard alloy bonding phase composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1254628A (en) * | 1999-08-13 | 2000-05-31 | 武汉工业大学 | Industrilized process for preparing nm-class non-eta-phase compound powder of tungsten carbide and cobalt |
| CN1331352A (en) * | 2000-06-19 | 2002-01-16 | 韩国机械研究院 | Method of mfg. tungsten carbide/cobalt series hard metal by utilizing grain growth inhibitor |
| CN1563461A (en) * | 2004-03-26 | 2005-01-12 | 武汉理工大学 | Method for preparing composite powder of nano tungsten carbide-coblt through direct reducition and carbonization |
| CN101767204A (en) * | 2010-02-03 | 2010-07-07 | 株洲硬质合金集团有限公司 | Fluidized preparation method for WC-Co composite powder |
-
2013
- 2013-01-04 CN CN201310000618.3A patent/CN103056376B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1254628A (en) * | 1999-08-13 | 2000-05-31 | 武汉工业大学 | Industrilized process for preparing nm-class non-eta-phase compound powder of tungsten carbide and cobalt |
| CN1331352A (en) * | 2000-06-19 | 2002-01-16 | 韩国机械研究院 | Method of mfg. tungsten carbide/cobalt series hard metal by utilizing grain growth inhibitor |
| CN1563461A (en) * | 2004-03-26 | 2005-01-12 | 武汉理工大学 | Method for preparing composite powder of nano tungsten carbide-coblt through direct reducition and carbonization |
| CN101767204A (en) * | 2010-02-03 | 2010-07-07 | 株洲硬质合金集团有限公司 | Fluidized preparation method for WC-Co composite powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103056376A (en) | 2013-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103056376B (en) | Method for preparing spherical nanostructure tungsten/cobalt carbide compound powder | |
| EP2368843B1 (en) | Method for producing composite lithium iron phosphate material | |
| CN103909274B (en) | A kind of method preparing cobalt cladding nanometer WC crystal composite powder and ultra-fine cemented carbide | |
| CN103658637B (en) | A kind of method of electrolytic preparation dendroid fine copper powder | |
| CN105161314B (en) | Nano-nickel oxide/nickel/graphene composite material and its preparation method and application | |
| CN109128141B (en) | Preparation method of nano WC-Co composite powder | |
| CN103035899A (en) | Method for performing carbon coating modification on nano-powder by adopting water-soluble polymer | |
| CN106252651B (en) | A kind of porous composite negative pole material of lithium ion battery and preparation method thereof | |
| CN110997198B (en) | Silver particles and method for producing same | |
| CN108080647B (en) | Nano/superfine WC-Co composite powder and preparation method thereof | |
| CN103305784A (en) | Preparation method of spherical spinel powder for thermal spraying | |
| CN106976917A (en) | Sheet cobalt black two-dimensional layer carbonization titanium composite material and its two-step preparation | |
| CN107460503A (en) | The method that micro-nano copper powder is reclaimed from waste printed circuit board | |
| CN107470646B (en) | Preparation method of superfine tungsten powder composite powder | |
| CN104451758A (en) | Method for preparing titanium carbide by performing molten salt electrolysis on high titanium slags | |
| CN110026220B (en) | Transition metal carbide/graphitized carbon-like composite powder and preparation method thereof | |
| CN103951416B (en) | A kind of composite Nano ZnO voltage-sensitive ceramic raw powder's production technology | |
| CN108356287B (en) | A method of catalysis gel prepares tungsten dispersed and strengthened copper-based composite material | |
| EP2232616A1 (en) | Powder for electrolyte in fuel cells | |
| CN108441668B (en) | Silver-tungsten electric contact material and preparation method thereof | |
| CN111039676A (en) | Method for preparing zirconium carbide, hafnium or vanadium powder in situ by utilizing molten salt disproportionation reaction | |
| CN106944628A (en) | A kind of scrap hard alloy, which is reclaimed, prepares ultrafine WC Co composite powder methods | |
| CN111363947A (en) | Silver tungsten carbide graphite composite material added with nickel alloy and preparation method thereof | |
| CN103449435A (en) | Method for producing micro-nanoscale carbide ceramics by carbon coating | |
| CN115283670A (en) | Ti (C, N) -Mo-Fe composite powder and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 410000 in Hunan Dingli Technology Co., Ltd., east of Lantian North Road, north of liangtang East Road, west of Shuangtang Road, Xingsha industrial base, Changsha Economic and Technological Development Zone, Changsha City, Hunan Province Patentee after: ADVANCED CORPORATION FOR MATERIALS & EQUIPMENTS Co.,Ltd. Address before: Changsha County City, Hunan province 410000 Changsha Muyun Town Industrial Park Patentee before: ADVANCED CORPORATION FOR MATERIALS & EQUIPMENTS Co.,Ltd. |
|
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 410199 No. 1271, liangtang East Road, Xingsha industrial base (Changlong Street), Changsha area, China (Hunan) pilot Free Trade Zone, Changsha, Hunan Province Patentee after: ADVANCED CORPORATION FOR MATERIALS & EQUIPMENTS Co.,Ltd. Address before: 410000 in Hunan Dingli Technology Co., Ltd., east of Lantian North Road, north of liangtang East Road, west of Shuangtang Road, Xingsha industrial base, Changsha Economic and Technological Development Zone, Changsha City, Hunan Province Patentee before: ADVANCED CORPORATION FOR MATERIALS & EQUIPMENTS Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 410199 No. 1271, liangtang East Road, Xingsha industrial base (Changlong Street), Changsha area, China (Hunan) pilot Free Trade Zone, Changsha, Hunan Province Patentee after: Hunan Dingli Technology Co.,Ltd. Address before: 410199 No. 1271, liangtang East Road, Xingsha industrial base (Changlong Street), Changsha area, China (Hunan) pilot Free Trade Zone, Changsha, Hunan Province Patentee before: ADVANCED CORPORATION FOR MATERIALS & EQUIPMENTS Co.,Ltd. |