CN108543952A - A kind of method of precursor process synthesis WC base nano composite powders - Google Patents
A kind of method of precursor process synthesis WC base nano composite powders Download PDFInfo
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- CN108543952A CN108543952A CN201810242863.8A CN201810242863A CN108543952A CN 108543952 A CN108543952 A CN 108543952A CN 201810242863 A CN201810242863 A CN 201810242863A CN 108543952 A CN108543952 A CN 108543952A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
A kind of method of precursor process synthesis WC base nano composite powders, feature include the following steps：Step 1：It is that 32.0% ~ 45.0% water-soluble tungstates, 10.0% ~ 15.0% water soluble cobaltous salt, 0.3% ~ 0.5% water-soluble vanadium/chromium salt-mixture and 40.0% ~ 56.0% Water Soluble Organic Carbon are dissolved in deionized water by mass percent.Step 2：Solution in step 1 is stirred evenly with glass bar, after heated, dry, obtains the presoma composite powder containing tungsten source, cobalt source, chromium source, vanadium source and carbon source.Step 3：The presoma composite powder that step 2 obtains is placed in high temperature reaction stove, is sintered under vacuum or argon gas atmosphere protective condition, the WC base composite powders with nano-scale are finally prepared.The present invention can be greatly lowered manufacturing cost, shorten manufacturing cycle, have the characteristics that simple for process, product is uniform, be suitble to industrialized production.
Description
Technical field
The present invention relates to a kind of methods that precursor process synthesizes WC base nano composite powders, and it is compound to belong to nanometer metal ceramic
Preparation Technique of Powders field.
Background technology
WC-Co composite powder end and its alloy be modern industry, national defence and the particularly important functional material of New technical use and
Tool is widely used in the numerous areas such as aerospace, ship, automobile, electrical, electronics, chemical industry.Experiment shows hard alloy crystalline substance
Grain is thinner, and comprehensive performance is better, and when grain size is less than 0.5 μm, hardness and strength all increase substantially, it is seen that nano WC-Co is multiple
It is the key that produce high-performance superfine hard alloy to close powder.In addition, surface spraying hard material also carries spraying composite powder
Go out higher standard, does not require nothing more than powder size fine uniform, and the requirement to powder shape, mobility, hardness etc. is also got over
Come harsher.
The study found that in the case where cobalt phase content is constant, when WC grain drops to 1 μm or less, the hardness of hard alloy
It is then improved simultaneously with intensity, and the amplitude of this raising further decreases and more obvious with grain size.It is this to have height concurrently
The hard alloy of hardness and high intensity shows extremely excellent performance in the cutting process, to break hard alloy
The raising of hardness necessarily leads to the traditional concept of strength reduction.
In recent years, the preparation of ultra-fine/nanometer WC-Co composite powder and the research and development of granularity control technology, it has also become world's tungsten
One of hot spot of field of powder metallurgy.From the point of view of achievement in research both domestic and external, the preparation method of composite powder mainly has mechanical conjunction
Aurification, oxidation-reduction method, sol-gel method, coprecipitation and spraying conversion method（SCP）Deng.
Mechanical alloying is exactly to be intended to the element powders of alloying mechanical mixture according to a certain ratio, is set in high energy ball mill etc.
Standby middle long time running, can pass to powder, while powder bears to rush under the collision repeatedly of ball-milling medium by rotary machine
Hit, shear, rub and compress the effect of many kinds of force, experience repeatedly extrudes, cold welding and crushing process, becomes the ultra-fine of Dispersed precipitate
Particle realizes alloying in the solid state.Wu Xijun such as Zhejiang University et al. is by WO3+ Mg+C mixed powders are placed in ball grinder,
N2High-energy ball milling prepares the W that average grain size is 6nm in atmosphere2C powders；Hippology ring seminar of Shanghai University utilizes machinery
Alloying process directly prepares the WC-Co powder that crystallite dimension is 11.3nm by W, C, Co powder, but this method is difficult to scale
Change, stablize prepare ultra-fine or nano WC-Co powder body material.
Conversion method of spraying is that soluble tungsten salt and cobalt salt are dissolved in water to form composite solution, spray-dried preparing
A point uniform precursor powder is studied, then handles to obtain nanoscale WC-Co through reduction and carbonization in high-temperature fluidizedization bed compound
Powder.As the primary unicorn of Wuhan University of Technology Wu using tungsten-cobalt liquid phase it is compound-the continuous reduction and carbonization technology of spray drying-fluidization, will
Ammonium metatungstate and nitric hydrate cobalt are mixed with molecular level level, spray-dried to prepare CoWO4/WO3Composite oxides forerunner
Powder is subsequently placed in fluidization reacting furnace, in H2/CH4/CO2/N2Atmosphere is obtained through continuous reduction, carbonization, tune carbon process
Nano-grained composite powder.But this process route is complicated, and particle agglomeration is apparent.
Carbothermic method is using tungsten or tungsten compound as raw material, and carbon black is reducing agent and carbonized stock, makes reduction and carbonization
Two processes are carried out continuously.This is the current widely used method for preparing WC and WC-Co composite powders.Such as Beijing University of Technology
Army et al. is paid using tungsten-cobalt oxide and carbon black as raw material, average grain diameter is prepared about using vacuum in situ reduction and carbonization reaction method
The WC-Co composite powder end of 330nm, using this composite powder as raw material, by adding VC and Cr3C2Grain growth inhibitor simultaneously changes
It is matched, and is then passed through low pressure sintering and is prepared WC-Co hard alloy, as a result, it has been found that as the amount 0.2%VC+0.4% of composite inhibitor
Cr3C2When, obtain the hard alloy that intensity value is 3490MPa.
Invention content
The purpose of the present invention is to provide a kind of synthetic methods of Novel WC-based nano composite powder, to better meet
Application of the WC bases composite powder in ultra-fine/fields such as nano hard alloy manufacture and material surface strengthening spraying.The present invention uses
Be precursor process, equipment is simple needed for this method, and reaction raw materials are cheap, and production process is easy, the period is short, low energy consumption,
Production cost can be greatly lowered, ensure that the WC bases composite powder of synthesis meets work in granularity, dispersibility, grain shape etc.
Industry demand.
The present invention relates to a kind of methods that precursor process synthesizes WC base nano composite powders, it is characterised in that including following work
Skill step：
Step 1：By mass percent be 32.0% ~ 45.0% water-soluble tungstates, 10.0% ~ 15.0% water soluble cobaltous salt,
0.3% ~ 0.5% water-soluble vanadium/chromium salt-mixture and 40.0% ~ 56.0% Water Soluble Organic Carbon are dissolved in deionized water；
Step 2：Solution in step 1 is stirred evenly with glass bar, is heated in drying box, is dry（200 DEG C, 2h）Afterwards, it obtains
To the presoma composite powder containing tungsten source, cobalt source, chromium source, vanadium source and carbon source；
Step 3：The presoma composite powder that step 2 obtains is placed in high temperature reaction stove, in vacuum or argon gas atmosphere ceiling
It is sintered under part, by changing reaction temperature（900~1200℃）And soaking time（1~2.5h）, prepare with nanometer ruler
Very little WC base composite powders.
The water solubility tungstates is any one in ammonium paratungstate or ammonium metatungstate.
The water soluble cobaltous salt is cobalt nitrate.
Water solubility vanadium/chromium the salt-mixture is the mixture of ammonium metavanadate and ammonium dichromate.
The Water Soluble Organic Carbon source is any one in glucose, sucrose, starch.
The high temperature reaction stove is any one in tube furnace or micro-wave oven.
The WC bases composite powder is tungsten carbide-vanadium carbide-chromium carbide-Co composite powder.
The present invention compares the existing method for preparing WC base nano composite powders, has the advantages that：
（1）Reduce manufacturing cost：Using water-soluble tungsten salt, cobalt salt, chromic salts, vanadic salts and organic carbon as raw material, and using oxygen
Compound, high-purity gas are that raw material and reducing agent are compared, and reduce energy consumption and production cost.
（2）It reduces reaction temperature, shorten the reaction time：With water-soluble tungsten salt, cobalt salt, chromic salts, vanadic salts and organic
Carbon prepares precursor solution as raw material.It can ensure that carbon realizes the equal of atomic level with tungsten, vanadium, chromium and cobalt/cobalt oxide in this way
Even mixing shortens the diffusion stroke of atom in carbonisation, greatly reduces reaction temperature, shortens the reaction time.
（3）It is simple for process：Prepare precursor mixed solution after drying, you can carbon thermal reduction is carried out, and is once completed,
Generation technique is simplified, it is easy to operate, it is suitble to industrialized production.
（4）Product is uniform, purity is high：Using presoma carbonizatin method, be conducive to the abundant reaction between reactant, easily obtain
The WC base composite powders of uniform nano-scale are formed, other impurities are not introduced in reaction process, purity is high.
Specific implementation mode
Embodiment 1：
By mass percent be 32.0% ammonium paratungstate, 11.7% cobalt nitrate, 56.0% glucose sugar and water-soluble vanadium/chromium mix
Close salt（0.1% ammonium metavanadate and 0.2% ammonium dichromate）It is dissolved in deionized water, is configured to mixed solution.By mixed solution
It is stirred evenly with glass bar, is heated in drying box, is dry（200 DEG C, 2h）Afterwards, it obtains containing tungsten source, cobalt source, chromium source, vanadium source
And the presoma composite powder of carbon source.Finally, presoma composite powder is subjected to microwave sintering under argon gas atmosphere protective condition,
In differential responses temperature（900~1200℃）And soaking time（1~2.5h）Under, average grain diameter is made and is less than 100nm, size distribution
Uniform WC base composite powders.
Embodiment 2：
By mass percent be 35.0% ammonium metatungstate, 12.5% cobalt nitrate, 52.0% sucrose and water-soluble vanadium/chromium mix
Salt（0.2% ammonium metavanadate and 0.3% ammonium dichromate）It is dissolved in deionized water, is configured to mixed solution.Mixed solution is used
Glass bar stirs evenly, and is heated in drying box, is dry（200 DEG C, 2h）Afterwards, obtain containing tungsten source, cobalt source, chromium source, vanadium source and
The presoma composite powder of carbon source.Finally, presoma composite powder is subjected to microwave sintering under vacuum, in differential responses
Temperature（900~1200℃）And soaking time（1~2.5h）Under, average grain diameter is made less than 100nm, the WC bases of even particle size distribution
Composite powder.
Embodiment 3：
By mass percent be 45.0% ammonium paratungstate, 10.0% cobalt nitrate, 44.6% starch and water-soluble vanadium/chromium mix
Salt（0.2% ammonium metavanadate and 0.2% ammonium dichromate）It is dissolved in deionized water, is configured to mixed solution.Mixed solution is used
Glass bar stirs evenly, and is heated in drying box, is dry（200 DEG C, 2h）Afterwards, obtain containing tungsten source, cobalt source, chromium source, vanadium source and
The presoma composite powder of carbon source.Finally, presoma composite powder is placed in tube furnace, under argon gas atmosphere protective condition into
Row sintering, in differential responses temperature（900~1200℃）And soaking time（1~2.5h）Under, be made average grain diameter be less than 200nm,
The WC base composite powders of even particle size distribution.
Embodiment 4：
By mass percent be 40.0% ammonium metatungstate, 15.0% cobalt nitrate, 44.5% glucose and water-soluble vanadium/chromium mix
Close salt（0.3% ammonium metavanadate and 0.2% ammonium dichromate）It is dissolved in deionized water, is configured to mixed solution.By mixed solution
It is stirred evenly with glass bar, is heated in drying box, is dry（200 DEG C, 2h）Afterwards, it obtains containing tungsten source, cobalt source, chromium source, vanadium source
And the presoma composite powder of carbon source.Finally, presoma composite powder is subjected to microwave sintering under argon gas atmosphere protective condition,
In differential responses temperature（900~1200℃）And soaking time（1~2.5h）Under, average grain diameter is made and is less than 100nm, size distribution
Uniform WC base composite powders.
Claims (7)
1. a kind of method of precursor process synthesis WC base nano composite powders, it is characterised in that：The synthetic method includes following
Step：
Step 1：By mass percent be 32.0% ~ 45.0% water-soluble tungstates, 10.0% ~ 15.0% water soluble cobaltous salt,
0.3% ~ 0.5% water-soluble vanadium/chromium salt-mixture and 40.0% ~ 56.0% Water Soluble Organic Carbon are dissolved in deionized water；
Step 2：Solution in step 1 is stirred evenly with glass bar, is heated in drying box, is dry（200 DEG C, 2h）Afterwards, it obtains
To the presoma composite powder containing tungsten source, cobalt source, chromium source, vanadium source and carbon source；
Step 3：The presoma composite powder that step 2 obtains is placed in high temperature reaction stove, in vacuum or argon gas atmosphere ceiling
It is sintered under part, by changing reaction temperature（900~1200℃）And soaking time（1~2.5h）, prepare with nanometer ruler
Very little WC base composite powders.
2. water-soluble tungstates is any one in ammonium paratungstate or ammonium metatungstate according to claim 1.
3. water soluble cobaltous salt is cobalt nitrate according to claim 1.
4. water-soluble vanadium/chromium salt-mixture is the mixture of ammonium metavanadate and ammonium dichromate according to claim 1.
5. Water Soluble Organic Carbon source is any one in glucose, sucrose, starch according to claim 1.
6. high temperature reaction stove is any one in tube furnace or micro-wave oven according to claim 1.
7. WC bases composite powder is tungsten carbide-vanadium carbide-chromium carbide-Co composite powder according to claim 1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109500386A (en) * | 2018-12-17 | 2019-03-22 | 石家庄铁道大学 | Heterogeneous core-shell structure composite powder and preparation method thereof |
| 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 |
| CN111069618A (en) * | 2020-01-02 | 2020-04-28 | 崇义章源钨业股份有限公司 | WC-Co composite powder and preparation method and application thereof |
| CN113184853A (en) * | 2021-05-26 | 2021-07-30 | 崇义章源钨业股份有限公司 | Superfine tungsten carbide powder and 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428344A (en) * | 2008-12-17 | 2009-05-13 | 四川大学 | Nano-scale wolfram carbine composite powder and method of manufacturing the same |
| US20110111945A1 (en) * | 2009-11-10 | 2011-05-12 | Kennametal Inc. | Inert high hardness material for tool lens production in imaging applications |
| CN102310199A (en) * | 2011-10-10 | 2012-01-11 | 西南大学 | Method for preparing WC-Co nano composite powder by in situ reduction and carbonization |
| CN102839313A (en) * | 2012-08-14 | 2012-12-26 | 四川理工学院 | Nano Cr3C2-WC-Ni composite powder and preparation method thereof |
| CN103056382A (en) * | 2013-01-04 | 2013-04-24 | 湖南顶立科技有限公司 | Method for manufacturing tungsten/ cobalt carbide composite powder with nanostructure |
| CN103614603A (en) * | 2013-12-09 | 2014-03-05 | 株洲硬质合金集团有限公司 | Hard alloy with grain size of less than 200nm and preparation method thereof |
-
2018
- 2018-03-23 CN CN201810242863.8A patent/CN108543952A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428344A (en) * | 2008-12-17 | 2009-05-13 | 四川大学 | Nano-scale wolfram carbine composite powder and method of manufacturing the same |
| US20110111945A1 (en) * | 2009-11-10 | 2011-05-12 | Kennametal Inc. | Inert high hardness material for tool lens production in imaging applications |
| CN102310199A (en) * | 2011-10-10 | 2012-01-11 | 西南大学 | Method for preparing WC-Co nano composite powder by in situ reduction and carbonization |
| CN102839313A (en) * | 2012-08-14 | 2012-12-26 | 四川理工学院 | Nano Cr3C2-WC-Ni composite powder and preparation method thereof |
| CN103056382A (en) * | 2013-01-04 | 2013-04-24 | 湖南顶立科技有限公司 | Method for manufacturing tungsten/ cobalt carbide composite powder with nanostructure |
| CN103614603A (en) * | 2013-12-09 | 2014-03-05 | 株洲硬质合金集团有限公司 | Hard alloy with grain size of less than 200nm and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109500386A (en) * | 2018-12-17 | 2019-03-22 | 石家庄铁道大学 | Heterogeneous core-shell structure composite powder and preparation method thereof |
| 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 |
| CN111069618A (en) * | 2020-01-02 | 2020-04-28 | 崇义章源钨业股份有限公司 | WC-Co composite powder and preparation method and application thereof |
| CN111069618B (en) * | 2020-01-02 | 2022-10-25 | 崇义章源钨业股份有限公司 | WC-Co composite powder and preparation method and application thereof |
| CN113184853A (en) * | 2021-05-26 | 2021-07-30 | 崇义章源钨业股份有限公司 | Superfine tungsten carbide powder and preparation method and application thereof |
| CN113184853B (en) * | 2021-05-26 | 2022-12-27 | 崇义章源钨业股份有限公司 | Superfine tungsten carbide powder and 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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