CN1044798C - Dimension controllable method for prepn. of Nanometre grade tungsten carbide - Google Patents
Dimension controllable method for prepn. of Nanometre grade tungsten carbide Download PDFInfo
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- CN1044798C CN1044798C CN95112712A CN95112712A CN1044798C CN 1044798 C CN1044798 C CN 1044798C CN 95112712 A CN95112712 A CN 95112712A CN 95112712 A CN95112712 A CN 95112712A CN 1044798 C CN1044798 C CN 1044798C
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- tungsten carbide
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- wolfram varbide
- grade tungsten
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Abstract
The present invention relates to a preparation method of nano-grade tungsten carbide. In the method, gas-solid phase reaction is adopted to prepare the nano-grade tungsten carbide, namely that active tungstic acid is prepared to be put in the carbon monoxide (CO) atmosphere for reaction, and the nano-grade tungsten carbide is obtained. The grain size of the nano-grade tungsten carbide prepared by the present invention can be controlled by the calcination temperature and calcination time, and the nano-grade tungsten carbide has the advantages of simple preparation method, low cost, easy acquisition of raw materials, strong practicability and easy popularization and application.
Description
The present invention relates to the preparation method of Nanometre grade tungsten carbide.
Learn that according to literature search the method for preparing wolfram varbide has two classes.One class is with WCL
6, H
2, C, CH
4At high temperature calcine for raw material and to form; Another kind of is the organometallics of using tungsten, and reaction makes wolfram varbide in special device.First kind method, owing to will under 1500 ℃ high temperature, react, severe reaction conditions, the wolfram varbide size of preparation is in micron dimension.The second class preparation method is because the raw material that is adopted is the organometallics of tungsten, and this compounds is synthetic very difficult, prepares used reaction unit complex structure in addition, and the particle diameter of the tungsten-carbide powder of preparing is in sub-micrometer scale, and cost is very high.
The object of the invention provides the method for a sharp preparation size controllable nano level wolfram varbide.
The inventive method is to adopt gas-solid phase reaction to prepare the wolfram varbide of nanometer scale, at first prepares active tungstic acid, reacts in the atmosphere of carbon monoxide (CO) then, obtains nano level wolfram varbide.Concrete preparation method:
The sodium tungstate solution of preparation 8%～15%, add 0.5%～2% the tensio-active agent be equivalent to sodium wolframate weight, drop to 2～10 droplets/second speed in the nitric acid of 1M, the pH value of solution is remained between 0.5～2, with sedimentation and filtration, use deionized water wash then after dropwising, use washing with alcohol again, with the anhydrous diethyl ether washing, the precipitation after the washing is placed baking oven 1～4 hour at last, promptly obtain the active tungstic acid of white.Oven temperature is controlled between 60～120 ℃, active tungstic acid is placed in the quartzy porous boat, be placed in the reduction furnace, feed pure carbon monoxide gas,, promptly obtain nano level wolfram varbide 450 ℃～900 ℃ temperature lower calcinations 2～5 hours.The particle diameter of wolfram varbide is by calcining temperature and time decision.
The present invention adopts gas-solid phase reaction to prepare the wolfram varbide of nanometer scale, at first prepares active tungstic acid.Active tungstic acid is a kind of white powder, and its chemical property is much more active than common yellow wolframic acid, it can with a lot of compound react withs.The purpose of preparation active tungstic acid is in order to reduce the temperature of back single step reaction, speed of response to be accelerated.In the process of preparation active tungstic acid, the inventive method has added low quantity of surfactant, these tensio-active agents can so that the size ratio of the active tungstic acid for preparing not add the granularity of active tungstic acid of tensio-active agent preparation littler, more even.These tensio-active agents can vapor away in the back single step reaction is heated process in decomposition, can not bring impurity to product.
Advantage of the present invention and characteristic are:
1. because the preparation method prepares active tungstic acid earlier, and active tungstic acid reacts in carbon monoxide atmosphere then, and calcining temperature is low, the median size of the wolfram varbide of generation is in nanometer scale;
2. because calcining temperature of the present invention and calcination time can be controlled the particle diameter that generates wolfram varbide, thereby to the size of wolfram varbide is controlled;
3. prepare wolfram varbide with the inventive method, cost is low, and starting material easily obtain.
Wolfram varbide is a kind of important carbide, can be used to do Hardmetal materials, makes the tool surface coating, the sedan limousine top coat.Nanometre grade tungsten carbide can also add into coating as pigment except such use, make coating have property.In a word, wolfram varbide has broad application prospects.
Embodiment 1:
Weighing 100 gram sodium wolframates are dissolved into the solution of 600ml with it, add 1 gram tensio-active agent cetylamine, add to the HNO of 900ml 1M with 2 droplets/second speed
3In the solution, this moment, pH value was 0.3, vigorous stirring when dripping cetylamine dropwises the back and continues to stir 15 minutes, with sedimentation and filtration, with the 2000ml deionized water wash once, use ethanol and the washing of 150ml anhydrous diethyl ether of 600ml 95% then respectively, after liquid is drained, throw out is put into 80 ℃ of bakings of baking oven 2 hours, promptly obtain the active tungstic acid of white, its particle diameter is about 20nm.The active tungstic acid that makes is placed quartzy porous bateau, place in the reduction furnace and calcined 2 hours, calcining temperature is 450 ℃, obtains black powder.Black powder is made X-ray, and confirmation is a wolfram varbide, does Electronic Speculum and sees that median size is 20nm; See accompanying drawing 1.Embodiment 2:
Weighing 200 restrains sodium wolframates, is dissolved into the solution of 1200ml, adds tensio-active agent Sodium dodecylbenzene sulfonate 2 grams, drops to the HNO of the 2M of 1500ml
3In the solution, this moment, the PH of solution was 1, vigorous stirring during dropping dropwises the back and continues to stir 20 minutes, filters, use the 4000ml water washing then once, respectively with 1000ml dehydrated alcohol and the washing of 500ml anhydrous diethyl ether, the precipitation after the washing is put into baking oven again, baking is 4 hours in the time of 100 ℃, can obtain the active tungstic acid of white, its median size is 25mm.Active tungstic acid is packed in the cellular quartz boat, place reduction furnace to calcine, 800 ℃ of calcining temperatures, obtain black powder at 3.5 hours time.Black powder is X-ray, confirms sufficient wolfram varbide, can see that through Electronic Speculum the wolfram varbide median size of generation is 55nm, see accompanying drawing 2.
Description of drawings:
The wolfram varbide electromicroscopic photograph that accompanying drawing 1 is made for embodiment 1;
The wolfram varbide electromicroscopic photograph that accompanying drawing 2 is made for embodiment 2.
Claims (1)
1. the preparation method of a controllable nanon size level wolfram varbide, it is characterized in that, the sodium tungstate solution of preparation 8%-15%, add the 0.5%-2% be equivalent to wolframic acid weight cetylamine or, dodecane stem benzene sulfonic acid sodium salt, drop to 2～10 droplets/second speed in the nitric acid of 1M, the pH value of solution is remained between 0.5～2, with sedimentation and filtration, use deionized water wash then after dropwising, use washing with alcohol again, with the anhydrous diethyl ether washing, the precipitation after the washing is placed baking oven 1～4 hour at last, promptly obtain the active tungstic acid of white, active tungstic acid is placed in the quartzy porous boat, be placed in the reduction furnace, oven temperature is controlled between 60～120 ℃, feed pure carbon monoxide gas, at 450 ℃～900 ℃ temperature combustion 2-5 hours, promptly obtain nano level wolfram varbide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112712A CN1044798C (en) | 1995-09-29 | 1995-09-29 | Dimension controllable method for prepn. of Nanometre grade tungsten carbide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112712A CN1044798C (en) | 1995-09-29 | 1995-09-29 | Dimension controllable method for prepn. of Nanometre grade tungsten carbide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1122768A CN1122768A (en) | 1996-05-22 |
| CN1044798C true CN1044798C (en) | 1999-08-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95112712A Expired - Fee Related CN1044798C (en) | 1995-09-29 | 1995-09-29 | Dimension controllable method for prepn. of Nanometre grade tungsten carbide |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062842C (en) * | 1998-09-22 | 2001-03-07 | 中国科学院山西煤炭化学研究所 | Process for preparing ultrafine metal carbide powder |
| CN102557029A (en) * | 2012-01-04 | 2012-07-11 | 南昌大学 | Synthetic method of fibrous nano-tungsten carbide |
| CN104030288B (en) * | 2014-06-12 | 2015-11-04 | 东北大学 | Produce the method for wolfram varbide |
| CN106430209B (en) * | 2016-09-19 | 2019-02-12 | 中冶东方工程技术有限公司 | The preparation method and product of meso-porous nano tungsten carbide |
| CN107737943B (en) * | 2017-11-03 | 2019-08-02 | 重庆大学 | A kind of method that Reduction of methanol prepares tungsten carbide or/and tungsten powder |
| CN113929099A (en) * | 2021-10-27 | 2022-01-14 | 赣州海盛钨钼集团有限公司 | Preparation method of superfine tungsten carbide powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3902917A (en) * | 1970-06-04 | 1975-09-02 | Bosch Gmbh Robert | Process for the production of tungsten carbide catalyst adapted for use in fuel cells |
| US4172808A (en) * | 1977-03-24 | 1979-10-30 | Licentia Patent-Verwaltungs-G.M.B.H. | Process for the production of a tungsten carbide catalyst by carburization of tungsten oxides |
-
1995
- 1995-09-29 CN CN95112712A patent/CN1044798C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3902917A (en) * | 1970-06-04 | 1975-09-02 | Bosch Gmbh Robert | Process for the production of tungsten carbide catalyst adapted for use in fuel cells |
| US4172808A (en) * | 1977-03-24 | 1979-10-30 | Licentia Patent-Verwaltungs-G.M.B.H. | Process for the production of a tungsten carbide catalyst by carburization of tungsten oxides |
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| CN1122768A (en) | 1996-05-22 |
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