CN108892141A - A kind of high-purity, ultrafine tungsten carbide preparation method - Google Patents

A kind of high-purity, ultrafine tungsten carbide preparation method Download PDF

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Publication number
CN108892141A
CN108892141A CN201811037172.0A CN201811037172A CN108892141A CN 108892141 A CN108892141 A CN 108892141A CN 201811037172 A CN201811037172 A CN 201811037172A CN 108892141 A CN108892141 A CN 108892141A
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China
Prior art keywords
carbon
tungsten carbide
purity
ball milling
temperature
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CN201811037172.0A
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Chinese (zh)
Inventor
张国华
王凯飞
焦树强
周国治
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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Priority to CN201811037172.0A priority Critical patent/CN108892141A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/949—Tungsten or molybdenum carbides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention discloses a kind of high-purity, ultrafine tungsten carbide preparation methods, belong to chemical metallurgy technical field.Use yellow tungsten and carbon black for raw material, ingredient, ball milling are carried out according to certain proportion, carbon thermal reduction is carried out at 1000~1300 DEG C, reduzate is after C content is analyzed, match carbon by WC theory C content is secondary, secondary carburizing preparation WC is carried out in 1100~1500 DEG C of temperature ranges.Compared to other WC techniques, raw material sources of the present invention are wider, and preparation process is simple, considerably reduce production cost；Superfine tungsten carbide powder is prepared using two-step method, so that product has all obtained better control in granularity and carbon content, the carbon electrode that dissociates in final product WC is low.Therefore simple production process of the present invention, production cost is low, to equipment without particular/special requirement, it is easy to accomplish technology.

Description

A kind of high-purity, ultrafine tungsten carbide preparation method
Technical field
The invention belongs to chemical metallurgy technical fields, disclose a kind of high-purity, ultrafine tungsten carbide preparation method, relate to A kind of method that two-step method reduction and carbonization prepares tungsten carbide.
Background technique
Diamondite is to be invented by the Shroter of Germany in nineteen twenty-three earliest, and tungsten carbide base carbide alloy has spy Different corrosion resistance, high rigidity, excellent fracture toughness and compression strength, there is the title of modern industry tooth.In order to further mention The mechanical property of high WC hard alloy, optimal approach are to refine its grain size, and the crystal grain of alloy is thinner, and defect is smaller, This hard alloy not only has high hardness and wearability, but also has high intensity and toughness.It is widely used in making integrated electricity Road plate microbit, dot-matrix printer printing syringe needle, accurate tool and mould, difficult-to-machine material cutter, wood cutter, medical dental drill Deng.
Currently, industrial tungsten-carbide powder is all made of after tungsten powder is mixed with carbon black and forms through high temperature cabonization, production cost by The influence of the factors such as higher temperature, remains high always, and the technique is produced into the source of raw material tungsten powder, carbonisation This height, the tungsten-carbide powder granularity of preparation is larger, carbon content is higher.For this purpose, enterprise, the research institution etc. of many countries all carry out Numerous studies, Japan Patent (publication number 2005-335997, publication date 08.12.2005) is by small WO3Or WO2.9Powder End is mixed with carbon black powders, in N2It is heated to 1050-1200 DEG C in atmosphere, obtains W, W2The intermediate that C and WC coexist, then in H2 It is heated to 900~1300 DEG C in atmosphere, tungsten-carbide powder is obtained, after the method is by once matching the carbonization twice under carbon and high temperature It obtains in product tungsten-carbide powder, total carbon nonstoichiometry carbon amounts is more, and free carbon is higher.Zhuzhou hard alloy group Company (102649671 A of CN) use on this basis carbon black and purple tungsten preparation carbon black mass percent for 13.4~ Precursor powder is once carbonized by 14.5% precursor powder, carries out secondary carbonization after a carbonized product allotment carbon amounts Obtain superfine tungsten carbide powder.In the method, since mixed carbon comtent is higher in presoma, the theoretical product being once carbonized close to WC, Carbonized product need to only be incorporated minimal amount of carbon black and carry out secondary carbonization, therefore the mixing of carbon black and a carbonized product is relatively tired Difficulty becomes the critical issue of preparation high quality tungsten carbide.The higher cost of purple tungsten simultaneously so that the production cost of the technique compared with It is high.
Summary of the invention
In view of the above problems, the present invention provides a kind of sides for preparing ultrafine tungsten carbide using carbon black and yellow tungsten as raw material Method, to be solved is to prepare ultrafine tungsten carbide using low cost, efficient method.
In order to achieve the above objectives, technical solution provided by the invention is：
A method of ultrafine tungsten carbide being prepared, the method is using carbon black and yellow tungsten as raw material, using ball milling mixing It is roasted in two steps in furnace afterwards, obtains ultrafine tungsten carbide product after cooling.
Specific preparation process is as follows：
(1) by yellow tungsten and carbon black in molar ratio 1:2.7~1:3.5 (carbon black mass percent is 12.26%~15.34%) Mixing ball milling 5~20 hours, carries out a carbothermic reduction reaction, when soaking time is 1~4 under an argon atmosphere；
(2) by a carbon thermal reduction product obtained in step (1) after C content is analyzed, by the theoretical C content of WC (6.13%) progress is secondary matches carbon, ball milling 5-20 hours, carries out secondary carburization reaction in a hydrogen atmosphere, soaking time is 4~8 Hour.
Further, step (1) carbon thermal reduction temperature is 1000~1300 DEG C, and the recovery time is 1~4 small When, step
Suddenly secondary carburization reaction temperature described in (2) is 1100~1500 DEG C, and soaking time is 4-8 hours.
Further, ball milling described in step (1~2) is dry grinding or wet-milling 5-20 hours, in mixed raw material when wet-milling Middle addition
Alcoholic solution, and dried material after ball milling.
Further, in the method, the furnace mode that enters of powder material is to heat up with furnace or to after target temperature in step (1) Directly put
Enter in furnace；After reaction, the sample type of cooling is under an argon atmosphere with furnace to a reduzate in step (1) It is cooling or
It directly takes out under high temperature and is cooled to room temperature in argon atmosphere；In step (2) after carburization reaction, sample is cooling Mode is
It furnace cooling or is rapidly cooled to room temperature in a hydrogen atmosphere in a hydrogen atmosphere.
Further, the range of the partial size of product tungsten carbide is 50~200nm after reaction.
Further, the obtained product of step (2) is subjected to ball milling, sieving, available granularity is more uniform to be surpassed Thin carbonization
Tungsten powder.
It is had the advantages that compared with existing well-known technique using technical solution provided by the invention：
(1) for the present invention using yellow tungsten and carbon black respectively as tungsten source and carbon source, other opposite tungsten sources have that source is wide, valence The features such as lattice are low, and preparation method is simple, low energy consumption, can significantly reduce the production cost of traditional tungsten carbide；
(2) present invention using two-stage method prepare ultra-fine, high-purity tungsten-carbide powder, it can be achieved that in final product carbon content essence Quasi- control, makes the phosphorus content of product closer to the theoretical carbon content of tungsten carbide.
(3) mixed carbon comtent control is 12.26%~15.337% when the present invention is once carbonized, so that product after primary carbonization Main phase is W, W2C and a small amount of WC is incorporated carbon black again and carries out secondary carburization reaction after accurate carbon determination.Compared to prior art, The secondary amount with carbon is more, is easy to mix with a carbonized product.
Specific embodiment
To further appreciate that the contents of the present invention, the present invention will be further described with reference to the examples below.
Embodiment one：
(1) yellow tungsten powder and carbon black are precisely weighed, the forerunner that the mass percent of carbon content is 12.26% is obtained after mixing Body powder, it is dry after ball milling 5h, uniformly mixed powder material is made.
(2) under argon atmosphere, the powder material obtained in (1) is entered into furnace to temperature, it is small that 1 is kept the temperature at 1100 DEG C When.
(3) heat preservation terminates, and is cooled to room temperature after taking-up in argon atmosphere, obtains a carbonized product, and detection total carbon contains Amount is 0.43%, precisely matches carbon, drying after ball milling 10h by WC theory carbon content (6.13%).
(4) by step (3) it is secondary with powder after carbon in H2Secondary carbonization is carried out under atmosphere, secondary carburizing temperature is 1200 DEG C, carbonization time 6h.After reaction, sample is cooled to room temperature in hydrogen atmosphere, obtains secondary carbonized product, partial size Range is 80-120nm.
Embodiment two：
(1) yellow tungsten powder and carbon black are precisely weighed, the forerunner that the mass percent of carbon content is 13.05% is obtained after mixing Body powder, it is dry after ball milling 10h, uniformly mixed powder material is made.
(2) under argon atmosphere, the powder material obtained in (1) is entered into furnace to temperature, it is small that 4 are kept the temperature at 1000 DEG C When.
(3) heat preservation terminates, and is cooled to room temperature after taking-up in argon atmosphere, obtains a carbonized product, and detection total carbon contains Amount is 2.76%, precisely matches carbon, drying after ball milling 5h by WC theory carbon content.
(4) by step (3) it is secondary with powder after carbon in H2Secondary carbonization is carried out under atmosphere, secondary carburizing temperature is 1300 DEG C, carbonization time 6h.After reaction, sample is cooled to room temperature in hydrogen atmosphere, obtains secondary carbonized product, partial size Range is 110-140nm.
Embodiment three：
(1) yellow tungsten powder and carbon black are precisely weighed, the forerunner that the mass percent of carbon content is 14.59% is obtained after mixing Body powder, it is dry after ball milling 20h, uniformly mixed powder material is made.
(2) under argon atmosphere, the powder material obtained in (1) is entered into furnace to temperature, it is small that 1 is kept the temperature at 1100 DEG C When.
(3) heat preservation terminates, and is cooled to room temperature after taking-up in argon atmosphere, obtains a carbonized product, and detection total carbon contains Amount is 3.65%, precisely matches carbon, drying after ball milling 10h by WC theory carbon content.
(4) by step (3) it is secondary with powder after carbon in H2Secondary carbonization is carried out under atmosphere, secondary carburizing temperature is 1200 DEG C, carbonization time 6h.After reaction, sample is cooled to room temperature in hydrogen atmosphere, obtains secondary carbonized product, partial size Range is 130-160nm.
Example IV：
(1) yellow tungsten powder and carbon black are precisely weighed, the forerunner that the mass percent of carbon content is 15.34% is obtained after mixing Body powder, it is dry after ball milling 5h, uniformly mixed powder material is made.
(2) under argon atmosphere, the powder material obtained in (1) is entered into furnace to temperature, it is small that 1 is kept the temperature at 1300 DEG C When.
(3) heat preservation terminates, and is cooled to room temperature after taking-up in argon atmosphere, obtains a carbonized product, and detection total carbon contains Amount is 4.41%, precisely matches carbon, drying after ball milling 20h by WC theory carbon content.
(4) by step (3) it is secondary with powder after carbon in H2Secondary carbonization is carried out under atmosphere, secondary carburizing temperature is 1500 DEG C, carbonization time 4h.After reaction, sample is cooled to room temperature in hydrogen atmosphere, obtains secondary carbonized product, partial size Range is 140~170nm.

Claims (6)

1. a kind of high-purity, ultrafine tungsten carbide production method, it is characterised in that include the following steps:
(1) by yellow tungsten and carbon black in molar ratio 1:2.7~1:3.5 mixing, it is dry after ball milling 5~20 hours, under an argon atmosphere A carbothermic reduction reaction is carried out, soaking time is 1~4 hour, obtains a carbonized product；
(2) by a carbon thermal reduction product obtained in step (1) after C content is analyzed, by the theoretical C content (6.13%) of WC Carry out it is secondary with carbon, it is dry after ball milling 5~20 hours, carry out secondary carburization reaction in a hydrogen atmosphere, soaking time is that 4-8 is small When.
2. high-purity, ultrafine tungsten carbide production method according to claim 1, which is characterized in that step (1) is described primary Carbon thermal reduction temperature is 1000~1300 DEG C, and the recovery time is 1~4 hour, and secondary carburization reaction temperature described in step (2) is 1100~1500 DEG C, soaking time is 4-8 hours.
3. high-purity, ultrafine tungsten carbide production method according to claim 1, which is characterized in that step (1~2) is described Ball milling be dry grinding or wet-milling 5-20 hour, when wet-milling, adds alcoholic solution in mixed raw material, and dry after ball milling Dry material.
4. high-purity, ultrafine tungsten carbide production method according to claim 1, which is characterized in that powder is former in step (1) The furnace mode that enters of material is to heat up with furnace or to being directly placed into furnace after target temperature；A reduzate reaction knot in step (1) Shu Hou, the sample type of cooling are to directly take out to be cooled to room in argon atmosphere under furnace cooling under an argon atmosphere or high temperature Temperature；In step (2) after carburization reaction, the sample type of cooling is fast for furnace cooling in a hydrogen atmosphere or in a hydrogen atmosphere Speed is cooled to room temperature.
5. high-purity, ultrafine tungsten carbide production method according to claim 1, which is characterized in that product is carbonized after reaction The range of the partial size of tungsten is 50~200nm.
6. high-purity, ultrafine tungsten carbide production method according to claim 1, which is characterized in that further by step (2) Obtained product carry out ball milling, sieving, the more uniform superfine tungsten carbide powder of granularity can be obtained.
CN201811037172.0A 2018-09-06 2018-09-06 A kind of high-purity, ultrafine tungsten carbide preparation method Pending CN108892141A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109867286A (en) * 2019-04-15 2019-06-11 北京科技大学 A kind of preparation method of ultrafine tungsten carbide
CN110240163A (en) * 2019-07-30 2019-09-17 株洲硬质合金集团有限公司 A kind of method that coarse tungsten powder prepares fine grain WC powder in use
CN111392727A (en) * 2020-03-25 2020-07-10 九江金鹭硬质合金有限公司 Tungsten carbide powder for die material and preparation method thereof
CN113086984A (en) * 2021-05-27 2021-07-09 西安斯瑞先进铜合金科技有限公司 Preparation method of chromium carbide powder
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
CN115285995A (en) * 2022-07-15 2022-11-04 赣州华茂钨材料有限公司 Tungsten carbide powder production process

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CN104803385A (en) * 2015-04-13 2015-07-29 南昌大学 Method for preparing ultrafine tungsten carbide powder from arsenic-containing ammonium metatungstate
CN106185944A (en) * 2016-07-01 2016-12-07 南昌大学 A kind of method preparing superfine tungsten carbide containing arsenic and the ammonium paratungstate of phosphorus or ammonium metatungstate
CN107265458A (en) * 2017-07-01 2017-10-20 赣州海盛钨钼集团有限公司 Tungsten powder grading system for extra-coarse grained carbide alloy method
CN107867690A (en) * 2017-11-30 2018-04-03 株洲三鑫硬质合金生产有限公司 A kind of high temperature base WC powder and its preparation method and application

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WO2002020403A1 (en) * 2000-09-06 2002-03-14 H.C. Starck Gmbh Ultracoarse, monorystalline tungsten carbide and method for producing the same, and hard metal produced therefrom
US20050036934A1 (en) * 2003-08-12 2005-02-17 Rickard Sandberg Method of making submicron cemented carbide
CN101618873A (en) * 2009-07-29 2010-01-06 自贡市华刚硬质合金新材料有限公司 Production method of macrocrystalline WC powder
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109867286A (en) * 2019-04-15 2019-06-11 北京科技大学 A kind of preparation method of ultrafine tungsten carbide
CN110240163A (en) * 2019-07-30 2019-09-17 株洲硬质合金集团有限公司 A kind of method that coarse tungsten powder prepares fine grain WC powder in use
CN110240163B (en) * 2019-07-30 2022-09-06 株洲硬质合金集团有限公司 Method for preparing fine-grain WC powder by using medium-coarse-grain tungsten powder
CN111392727A (en) * 2020-03-25 2020-07-10 九江金鹭硬质合金有限公司 Tungsten carbide powder for die material and preparation method 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
CN113086984A (en) * 2021-05-27 2021-07-09 西安斯瑞先进铜合金科技有限公司 Preparation method of chromium carbide powder
CN115285995A (en) * 2022-07-15 2022-11-04 赣州华茂钨材料有限公司 Tungsten carbide powder production process
CN115285995B (en) * 2022-07-15 2023-11-17 赣州华茂钨材料有限公司 Tungsten carbide powder production process

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Application publication date: 20181127