CN109867286A - A kind of preparation method of ultrafine tungsten carbide - Google Patents
A kind of preparation method of ultrafine tungsten carbide Download PDFInfo
- Publication number
- CN109867286A CN109867286A CN201910299961.XA CN201910299961A CN109867286A CN 109867286 A CN109867286 A CN 109867286A CN 201910299961 A CN201910299961 A CN 201910299961A CN 109867286 A CN109867286 A CN 109867286A
- Authority
- CN
- China
- Prior art keywords
- tungsten carbide
- tungsten
- preparation
- carbon
- ultrafine
- 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.)
- Pending
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention provides a kind of preparation methods of ultrafine tungsten carbide, are related to chemical metallurgy technical field, and preparation process is simple, and production cost is low, and resource is Ke Xunhuanliyong；This method uses yellow tungsten, as carbon source, to roast in two steps as tungsten source, carbon black and methane, obtain the tungsten carbide；Step includes: S1, mix the yellow tungsten and the carbon black by default molar ratio, carries out carbothermic reduction reaction under inert atmosphere conditions, cools down after carbothermic reduction reaction；S2, the product obtained after cooling down in S1, which are placed under the mixed atmosphere of methane and hydrogen, carries out carburization reaction, cooling after carburization reaction, obtains the tungsten carbide.Technical solution provided by the invention is suitable for the preparation process of tungsten carbide.
Description
[technical field]
The present invention relates to chemical metallurgy technical field more particularly to a kind of preparation methods of ultrafine tungsten carbide.
[background technique]
Tungsten carbide powder is the primary raw material for producing hard alloy.It is widely used in high-speed cutting lathe tool, jet is started
Machine component, cermet material, integrated circuit board microbit, dot-matrix printer printing syringe needle, accurate tool and mould, difficult processing material
Expect cutter, wood cutter, medical dental drill etc..
Currently, the method for industrially prepared tungsten-carbide powder is broadly divided into two steps: first, tungsten is restored at high temperature using hydrogen
Oxide prepares high purity tungsten；Second, tungsten carbide is prepared through high temperature cabonization after being mixed with tungsten powder prepared by the first step with carbon black.This
Method in the first step, since hydrogen can generate WO during restoring tungsten oxide under high temperature2(OH)2Ternary gas-phase product,
The granularity of product tungsten powder is caused to be grown up because of chemical vapor transport mechanism.Additionally, it is also well known that solid-solid reaction rate is slower, and
The method need to be incorporated carbon black in second step and tungsten powder is carbonized, thus needs to keep the temperature for a long time at 1400-1600 DEG C, to ensure
Fully reacting.Therefore, the production cost of this method is by higher temperature, longer soaking time in tungsten powder cost, carbonisation
Etc. factors influence, remain high always, and technique preparation tungsten-carbide powder granularity is larger, carbon content is higher.It is open
Number for CN102649671A Chinese patent using carbon black and purple tungsten as carbon source and tungsten source, first by carbon black mass percent
It is once carbonized for 13.4~14.5% precursor powders, product carries out secondary carbonization after deploying carbon amounts with addition of carbon black again
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,
It is secondary to be only incorporated minimal amount of carbon black when matching carbon and carry out secondary carbonization, therefore the mixing of carbon black and a carbonized product is relatively stranded
Difficulty becomes the critical issue of preparation high quality tungsten carbide；And graphite boat is used in two step process, the carbon of final products contains
Amount is difficult to be controlled；The higher cost of purple tungsten simultaneously, so that the production cost of the technique is higher.
Therefore, it is necessary to design a kind of new retardant, to solve the problems, such as or mitigate said one or multiple.
[summary of the invention]
In view of this, preparation process is simple the present invention provides a kind of preparation method of ultrafine tungsten carbide, production cost
Low, resource is Ke Xunhuanliyong.
On the one hand, the present invention provides a kind of preparation method of ultrafine tungsten carbide, which is characterized in that and use yellow tungsten as tungsten source,
Carbon black and methane roast in two steps as carbon source, obtain the tungsten carbide.
The aspect and any possible implementation manners as described above, it is further provided a kind of implementation, the preparation side
The specific steps of method include:
S1, the yellow tungsten and the carbon black are mixed, carries out carbothermic reduction reaction, carbon thermal reduction under inert atmosphere conditions
It cools down after reaction；The carbothermic reduction reaction stage, mixed carbon comtent are 11.46%~15.34%；
S2, the product obtained after cooling down in S1 are placed under the mixed atmosphere of methane and hydrogen and carry out carburization reaction, carburizing
It cools down after reaction, obtains the tungsten carbide.
The aspect and any possible implementation manners as described above, it is further provided a kind of implementation, the carbon heat is also
The reaction temperature of original reaction is 900 DEG C~1400 DEG C, and soaking time is 1~8 hour.
The aspect and any possible implementation manners as described above, it is further provided a kind of implementation, methane accounts in S2
The volume ratio of the mixed atmosphere is 2%~20%.
The aspect and any possible implementation manners as described above, it is further provided a kind of implementation, the carburizing are anti-
The temperature answered is 700 DEG C~1200 DEG C, and soaking time is 1~6 hour.
The aspect and any possible implementation manners as described above, it is further provided a kind of implementation obtains the S2
The tungsten carbide obtained carries out ball milling and sieving again, obtains the tungsten-carbide powder of homogeneous grain diameter.
The aspect and any possible implementation manners as described above, it is further provided a kind of implementation, Huang described in S1
The hybrid mode of tungsten and the carbon black is grinding and/or ball milling mixing.
On the other hand, the present invention provides a kind of tungsten carbide by as above any preparation method preparation, which is characterized in that
The particle size range of the tungsten carbide is 50nm~700nm.
Compared with prior art, the present invention can be obtained including following technical effect: the present invention uses yellow tungsten as tungsten source, carbon
Black and methane prepares tungsten carbide using two one-step baking methods as carbon source, prepared by the technical solution of these technical characteristics composition
Simple production process when tungsten carbide, production cost is low, and whole process green non-pollution, resource can be utilized efficiently, it is easy to accomplish
Technology.
Certainly, it implements any of the products of the present invention it is not absolutely required to while reaching all the above technical effect.
[Detailed description of the invention]
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this field
For those of ordinary skill, without creative efforts, it can also be obtained according to these attached drawings other attached drawings.
Fig. 1 is the flow chart of ultrafine tungsten carbide preparation method provided by one embodiment of the present invention.
[specific embodiment]
For a better understanding of the technical solution of the present invention, being retouched in detail to the embodiment of the present invention with reference to the accompanying drawing
It states.
It will be appreciated that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts it is all its
Its embodiment, shall fall within the protection scope of the present invention.
The term used in embodiments of the present invention is only to be not intended to be limiting merely for for the purpose of describing particular embodiments
The present invention.In the embodiment of the present invention and the "an" of singular used in the attached claims, " described " and "the"
It is also intended to including most forms, unless the context clearly indicates other meaning.
A method of high-purity and controllable granularity tungsten carbide being prepared, the method is using yellow tungsten as tungsten source, carbon black and methane
Gas roasts after uniform mixing in furnace in two steps as carbon source, obtains tungsten carbide product high-purity, that granularity is controllable after cooling.
Specifically preparation step includes:
Step 1, by yellow tungsten and carbon black in molar ratio 1:2.5~1:3.5 (carbon black mass percent is 11.46%~
15.34%) it mixes, carbothermic reduction reaction is carried out under argon atmosphere (can also be other inert atmospheres), soaking time is 1~8
Hour；After carbothermic reduction reaction, sample directly takes out in argon atmosphere under furnace cooling or high temperature under an argon atmosphere
It is cooled to room temperature；
The hybrid mode of carbothermic reduction reaction raw material (i.e. yellow tungsten and carbon black) is grinding or ball milling mixing；Mechanical milling process can divide
For dry grinding or wet-milling 2-20 hours, and dried material after wet ball mill；Powder material after grinding or ball milling enters furnace
Mode is to heat up with furnace or to being directly placed into furnace after target temperature；
Carbon thermal reduction temperature is 900 DEG C~1400 DEG C, and soaking time is 1~8 hour.
Step 2, by carbon thermal reduction product obtained in step 1, seeped under a certain proportion of methane and hydrogen atmosphere
Carbon reaction, soaking time are 1~6 hour；After carburization reaction, sample furnace cooling under the atmosphere of mixed gas after the reaction
Or it is rapidly cooled to room temperature；
In the mixed atmosphere of methane and hydrogen used in carburization reaction, methane proportion is 2%~20% (volume ratio)；
Carburization reaction temperature is 700 DEG C~1200 DEG C, and soaking time is 1~6 hour.
Tungsten carbide is prepared using above-mentioned preparation method, the size tunable of product tungsten carbide after reaction is matched by adjusting
Carbon amounts and reaction temperature adjust the granule size of tungsten carbide, and the particle size range of the tungsten carbide of the preparation method preparation of the application is
50nm~700nm.Ball milling, sieving can be carried out again to obtained product after the completion of tungsten carbide preparation, and it is more uniform to obtain granularity
Tungsten-carbide powder.
Specific embodiment is as follows:
Embodiment one:
(1) by yellow tungsten powder and carbon black, 1:3.5 (carbon black mass percent is 15.337%) is precisely weighed, ball milling in molar ratio
It is dry after 20h, uniformly mixed powder material is made.
(2) under argon atmosphere, the powder material obtained in (1) is heated up with furnace, it is small that 2 is kept the temperature at 1100 DEG C
When.Heat preservation terminates, and furnace cooling to room temperature obtains carbon thermal reduction product.
(3) by the carbon thermal reduction product in step (2) in CH4And H2Carburizing is carried out under mixed atmosphere, wherein methane institute accounting
Example is 10% (volume ratio), and carburizing temperature is 950 DEG C, carbonization time 2h.After reaction, sample is in furnace cooling to room
Temperature, obtains carbonized product, and particle size range is 50~70nm, carbon content 6.13%.
Embodiment two:
(1) by yellow tungsten powder and carbon black, 1:3.1 (carbon black mass percent is 13.83%) is precisely weighed, ball milling in molar ratio
It is dry after 10h, uniformly mixed powder material is made.
(2) under argon atmosphere, the powder material obtained in (1) is heated up with furnace, it is small that 1 is kept the temperature at 1200 DEG C
When.Heat preservation terminates, and furnace cooling to room temperature obtains carbon thermal reduction product.
(3) by the carbon thermal reduction product in step (2) in CH4And H2Carburizing is carried out under mixed atmosphere, wherein methane institute accounting
Example is 10% (volume ratio), and carburizing temperature is 1100 DEG C, carbonization time 3h.After reaction, sample is in furnace cooling to room
Temperature, obtains carbonized product, and particle size range is 130~150nm, carbon content 6.13%.
Embodiment three:
(1) by yellow tungsten powder and carbon black, 1:2.9 (carbon black mass percent is 13.05%) is precisely weighed, ball milling in molar ratio
It is dry after 5h, uniformly mixed powder material is made.
(2) under argon atmosphere, the powder material obtained in (1) is heated up with furnace, it is small that 5 is kept the temperature at 1300 DEG C
When.Heat preservation terminates, and furnace cooling to room temperature obtains carbon thermal reduction product.
(3) by the carbon thermal reduction product in step (2) in CH4And H2Carburizing is carried out under mixed atmosphere, wherein methane institute accounting
Example is 15% (volume ratio), and carburizing temperature is 950 DEG C, carbonization time 2h.After reaction, sample is in furnace cooling to room
Temperature, obtains carbonized product, and particle size range is 450~470nm, carbon content 6.13%.
Example IV:
(1) by yellow tungsten powder and carbon black, 1:2.7 (carbon black mass percent is 12.26%) is precisely weighed, ball milling in molar ratio
It is dry after 2h, uniformly mixed powder material is made.
(2) under argon atmosphere, the powder material obtained in (1) is heated up with furnace, it is small that 8 is kept the temperature at 1400 DEG C
When.Heat preservation terminates, and furnace cooling to room temperature obtains carbon thermal reduction product.
(3) by the carbon thermal reduction product in step (2) in CH4And H2Carburizing is carried out under mixed atmosphere, wherein methane institute accounting
Example is 5% (volume ratio), and carburizing temperature is 1200 DEG C, carbonization time 4h.After reaction, sample is in furnace cooling to room
Temperature, obtains carbonized product, and particle size range is 640~700nm, carbon content 6.14%.
It is had the following beneficial effects: compared with existing well-known technique using technical solution provided by the invention
1, the present invention using yellow tungsten and carbon black respectively as the tungsten source of carbothermic reduction reaction and carbon source, other opposite tungsten sources,
There is the features such as source is wide, price is low, the production cost of traditional tungsten carbide can be significantly reduced；
2, the present invention prepares tungsten-carbide powder using two-step method, and in carburizing process by adjust a certain proportion of methane and
The mixed gas of hydrogen carries out carburizing, it can be achieved that carbon content is precisely controlled in final product；
3, mixed carbon comtent control is 11.46%~15.337% at the carbothermic reduction reaction stage by the present invention, so that carbon heat is also
Oxygen content is extremely low in product after original, avoids in mixed gas carburizing of the second stage using methane and hydrogen, because hydrogen with
Oxygen reacts and generates chemical gaseous phase migration mechanism, and then final products granularity is caused to become larger, unevenly；By reaction temperature and match
The tungsten carbide powder being evenly distributed to the controllable of tungsten carbide size is realized in the adjustment of carbon amounts；
4, the present invention uses the mixed atmosphere of methane and hydrogen in carbon impregnation stage, substantially after the carbon in consumption methane
Hydrogen is generated, therefore only need to be incorporated again methane in tail gas and can be recycled, so that resource is recycled.
Above to a kind of preparation method of ultrafine tungsten carbide provided by the embodiment of the present application, it is described in detail.With
The explanation of upper embodiment is merely used to help understand the present processes and its core concept；Meanwhile for the general of this field
Technical staff, according to the thought of the application, there will be changes in the specific implementation manner and application range, in conclusion
The contents of this specification should not be construed as limiting the present application.
Some vocabulary has such as been used to censure specific components in specification and claims.Those skilled in the art
, it is to be appreciated that hardware manufacturer may call the same component with different nouns.Present specification and claims are not
In such a way that the difference of title is as component is distinguished, but with the difference of component functionally as the criterion of differentiation.Such as
It is an open language in "comprising", " comprising " of the specification and claims in the whole text mentioned in, therefore " packet should be construed to
Containing/including but not limited to "." substantially " refer within the acceptable error range, those skilled in the art can centainly miss
The technical problem is solved in poor range, basically reaches the technical effect.Specification subsequent descriptions be implement the application compared with
Good embodiment, so the description is being not intended to limit the scope of the present application for the purpose of the rule for illustrating the application.
The protection scope of the application is subject to view the appended claims institute defender.
It should also be noted that, the terms "include", "comprise" or its any other variant are intended to nonexcludability
Include, so that commodity or system including a series of elements not only include those elements, but also including not clear
The other element listed, or further include for this commodity or the intrinsic element of system.In the feelings not limited more
Under condition, the element that is limited by sentence "including a ...", it is not excluded that in the commodity or system for including the element also
There are other identical elements.
It should be appreciated that term "and/or" used herein is only a kind of incidence relation for describing affiliated partner, indicate
There may be three kinds of relationships, for example, A and/or B, can indicate: individualism A, exist simultaneously A and B, individualism B these three
Situation.In addition, character "/" herein, typicallys represent the relationship that forward-backward correlation object is a kind of "or".
Above description shows and describes several preferred embodiments of the present application, but as previously described, it should be understood that the application
Be not limited to forms disclosed herein, should not be regarded as an exclusion of other examples, and can be used for various other combinations,
Modification and environment, and the above teachings or related fields of technology or knowledge can be passed through in application contemplated scope described herein
It is modified.And changes and modifications made by those skilled in the art do not depart from spirit and scope, then it all should be in this Shen
It please be in the protection scope of the appended claims.
Claims (8)
1. a kind of preparation method of ultrafine tungsten carbide, which is characterized in that use yellow tungsten as tungsten source, carbon black and methane as carbon source,
It roasts in two steps, obtains the tungsten carbide.
2. the preparation method of ultrafine tungsten carbide according to claim 1, which is characterized in that specific steps include:
S1, the yellow tungsten and the carbon black are mixed, carries out carbothermic reduction reaction, carbothermic reduction reaction under inert atmosphere conditions
After it is cooling；The carbothermic reduction reaction stage, mixed carbon comtent are 11.46%~15.34%；
S2, the product obtained after cooling down in S1 are placed under the mixed atmosphere of methane and hydrogen and carry out carburization reaction, carburization reaction
After it is cooling, obtain the tungsten carbide.
3. the preparation method of ultrafine tungsten carbide according to claim 2, which is characterized in that the carbothermic reduction reaction it is anti-
Answering temperature is 900 DEG C~1400 DEG C, and soaking time is 1~8 hour.
4. the preparation method of ultrafine tungsten carbide according to claim 2, which is characterized in that methane accounts for the gaseous mixture in S2
The volume ratio of atmosphere is 2%~20%.
5. the preparation method of ultrafine tungsten carbide according to claim 2, which is characterized in that the temperature of the carburization reaction is
700 DEG C~1200 DEG C, soaking time is 1~6 hour.
6. the preparation method of ultrafine tungsten carbide according to claim 2, which is characterized in that the tungsten carbide obtained to S2
Ball milling and sieving are carried out again, obtain the tungsten-carbide powder of homogeneous grain diameter.
7. the preparation method of ultrafine tungsten carbide according to claim 2, which is characterized in that Huang tungsten described in S1 and the carbon
Black hybrid mode is grinding and/or ball milling mixing.
8. a kind of tungsten carbide by any preparation method preparation of claim 1-7, which is characterized in that the grain of the tungsten carbide
Diameter range is 50nm~700nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910299961.XA CN109867286A (en) | 2019-04-15 | 2019-04-15 | A kind of preparation method of ultrafine tungsten carbide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910299961.XA CN109867286A (en) | 2019-04-15 | 2019-04-15 | A kind of preparation method of ultrafine tungsten carbide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109867286A true CN109867286A (en) | 2019-06-11 |
Family
ID=66922606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910299961.XA Pending CN109867286A (en) | 2019-04-15 | 2019-04-15 | A kind of preparation method of ultrafine tungsten carbide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109867286A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5372797A (en) * | 1991-11-20 | 1994-12-13 | The Dow Chemical Company | Low temperature method for synthesizing micrograin tungsten carbide |
| WO2001058806A1 (en) * | 2000-02-08 | 2001-08-16 | Micasu Tungsten Llc | Method for producing tungsten carbide |
| US20040265208A1 (en) * | 2003-04-25 | 2004-12-30 | Zongtao Zhang | Method for the production of metal carbides |
| CN1724350A (en) * | 2004-07-20 | 2006-01-25 | 中南大学 | Process for preparing superfine wolfram carbide powder |
| CN1785898A (en) * | 2005-11-03 | 2006-06-14 | 武汉化工学院 | Preparation method of nano-carbon tube-nano tungston carbide composite powder |
| CN101985356A (en) * | 2010-12-10 | 2011-03-16 | 中国科学院上海硅酸盐研究所 | Method for preparing tungsten carbide nano-powder |
| CN102649571A (en) * | 2012-05-07 | 2012-08-29 | 株洲硬质合金集团有限公司 | Production method for superfine tungsten carbide powder |
| CN103626181A (en) * | 2013-12-12 | 2014-03-12 | 株洲硬质合金集团有限公司 | Method for preparing uniform and ultrafine tungsten carbide |
| CN105537606A (en) * | 2015-12-30 | 2016-05-04 | 钢铁研究总院 | Preparation method of ultra-fine tungsten carbide powder |
| CN108892141A (en) * | 2018-09-06 | 2018-11-27 | 北京科技大学 | A kind of high-purity, ultrafine tungsten carbide preparation method |
| 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 |
-
2019
- 2019-04-15 CN CN201910299961.XA patent/CN109867286A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5372797A (en) * | 1991-11-20 | 1994-12-13 | The Dow Chemical Company | Low temperature method for synthesizing micrograin tungsten carbide |
| WO2001058806A1 (en) * | 2000-02-08 | 2001-08-16 | Micasu Tungsten Llc | Method for producing tungsten carbide |
| US20040265208A1 (en) * | 2003-04-25 | 2004-12-30 | Zongtao Zhang | Method for the production of metal carbides |
| CN1569625A (en) * | 2003-04-25 | 2005-01-26 | 美国英佛曼公司 | Method for the production of metal carbides |
| CN1724350A (en) * | 2004-07-20 | 2006-01-25 | 中南大学 | Process for preparing superfine wolfram carbide powder |
| CN1785898A (en) * | 2005-11-03 | 2006-06-14 | 武汉化工学院 | Preparation method of nano-carbon tube-nano tungston carbide composite powder |
| CN101985356A (en) * | 2010-12-10 | 2011-03-16 | 中国科学院上海硅酸盐研究所 | Method for preparing tungsten carbide nano-powder |
| CN102649571A (en) * | 2012-05-07 | 2012-08-29 | 株洲硬质合金集团有限公司 | Production method for superfine tungsten carbide powder |
| CN103626181A (en) * | 2013-12-12 | 2014-03-12 | 株洲硬质合金集团有限公司 | Method for preparing uniform and ultrafine tungsten carbide |
| CN105537606A (en) * | 2015-12-30 | 2016-05-04 | 钢铁研究总院 | Preparation method of ultra-fine tungsten carbide powder |
| CN108892141A (en) * | 2018-09-06 | 2018-11-27 | 北京科技大学 | A kind of high-purity, ultrafine tungsten carbide preparation method |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| S. DECKER等: "Study of the preparation of bulk tungsten carbide catalysts with C2H6/H2 andC2H4/H2 carburizing mixtures", 《CATALYSIS LETTERS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1069604C (en) | Method to produce transition metal carbide from partially reduced transition metal compound | |
| US5567662A (en) | Method of making metallic carbide powders | |
| CN108455614B (en) | Method for preparing nano WC powder at low temperature and in short process | |
| CN109641753B (en) | Tungsten carbide powder and preparation thereof | |
| CN102649571A (en) | Production method for superfine tungsten carbide powder | |
| CN103626181A (en) | Method for preparing uniform and ultrafine tungsten carbide | |
| EP0973690B1 (en) | Method to produce a transition metal carbide from a partially reduced transition metal compound | |
| CN108892141A (en) | A kind of high-purity, ultrafine tungsten carbide preparation method | |
| CN109867286A (en) | A kind of preparation method of ultrafine tungsten carbide | |
| US6852304B2 (en) | Fine tungsten carbide powder and process for producing the same | |
| CN103408015A (en) | Preparation method of ultrafine tungsten carbide powder | |
| CN108557834A (en) | A kind of preparation method of four tungsten boride superhard materials of chromium doping | |
| CN109079151A (en) | A kind of method of high temperature solution phase reduction method tungsten oxide preparation extra-coarse tungsten powder | |
| CN117620190A (en) | Preparation method of high-purity superfine rhenium powder | |
| CN108840681A (en) | A kind of nano boron carbide and preparation method thereof | |
| US4454105A (en) | Production of (Mo,W) C hexagonal carbide | |
| CN108675301B (en) | Method for preparing boron carbide by gas-solid method | |
| US2849275A (en) | Production of refractory metal carbides | |
| CN107243644A (en) | A kind of preparation method of the diamond tool copper-based prealloy powder of ultra-fine quaternary | |
| JP3413625B2 (en) | Method for producing titanium carbonitride powder | |
| US4115526A (en) | Process for the preparation of reactive tungsten and derivatives thereof | |
| CN109019605A (en) | A kind of smelting process of boron carbide material | |
| JP5618364B2 (en) | Method for producing ultrafine and homogeneous titanium carbonitride solid solution powder | |
| JP4382113B2 (en) | Method for producing titanium carbonitride powder | |
| CN107737943B (en) | A kind of method that Reduction of methanol prepares tungsten carbide or/and tungsten powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190611 |