CN103708560A - Preparation method of nano tungsten trioxide powder - Google Patents
Preparation method of nano tungsten trioxide powder Download PDFInfo
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- CN103708560A CN103708560A CN201310742106.4A CN201310742106A CN103708560A CN 103708560 A CN103708560 A CN 103708560A CN 201310742106 A CN201310742106 A CN 201310742106A CN 103708560 A CN103708560 A CN 103708560A
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Abstract
The invention relates to a preparation method of nano tungsten trioxide powder, and belongs to the field of powder metallurgy technology. The method comprises the following steps: heating a saturated ammonium tungstate solution till 65-70 DEG C, then adding ammonium chloride, tartaric acid, ethylenediamine tetra-n-propionic acid and diethanol amine respectively in sequence, keeping stirring during the adding process till being dissolved completely and continuously stirring for 1-2h; then adding nitric acid under the condition of keeping stirring to form tungstic acid gel; then putting the gel in a heating furnace for drying at 140-150 DEG C, then warming up till 340-380 DEG C for calcination, and finally ball-milling and smashing to obtain the nano tungsten trioxide powder with the average particle size of 23-28 nm. The method disclosed by the invention is mild and stable for reaction process and easy to control, prepared nano tungsten trioxide is thin and uniform in particles and high in powder purity. Moreover, the process is simple and easy to control, so that the industrial production investment is few, the production technology is simple and convenient, the production cost is low, and industrial large-scale production is convenient to realize.
Description
Technical field
The technology that the present invention relates to prepare nano tungsten trioxide powder, belongs to powder metallurgical technology.
Background technology
For WC-Co Wimet, refinement WC grain is to improve the effective way of Cemented Carbide Hardness and intensity, and particularly nano WC-Co Cemented Carbide Properties is superior, is widely used.Produce nano hard alloy gordian technique it-be to prepare nanometer WC powder or WC-Co composite powder.Its preparation method has multiple, and the method for studying at present more deeply has:
(1) mechanical alloying
Mechanical alloying is each elemental metalpowder in alloy prepared by needs, and as W-Ni-Fe, each element powders such as W-Cu carries out high-energy ball milling in stirring, planet or rotor high energy ball mill, adopts protection of inert gas in mechanical milling process, to prevent Powder Oxidation.In alloying process, body of powder is repeatedly mixed under the effect of ball, collision, temperature rising, cold welding and tear, each element powders mixes the degree very uniformly that reaches, between each element powders, mutual diffusion occurs, can make immiscible W, the lower powdered alloy of the alloying elements such as Cu or solubleness is as W, Ni, there is mutual diffusion in Fe etc., forms the W-Cu with certain solubility or larger solubleness, W-Ni-Fe supersaturated solid solution and Ni amorphous phase.Adopt mixing of mechanical alloying powder degree high, reach the mixing of atom level level, can prepare the nano composite powder below 20nm.Its main drawback is in process, easily to introduce impurity, and powder is easy to agglomerating one-tenth piece, and wall sticking phenomenon is serious.Employing as ball-milling medium, can be prepared the powder that purity is higher with the tungsten ball of material.
Mechanical alloying method is similar on high-energy ball milling method surface, but has difference in essence.Mechanical alloying is exactly by the element powders of wanting alloying mechanically mixing according to a certain ratio, long time running in the equipment such as high energy ball mill, rotary machine can be passed to powder, powder is under the collision repeatedly of ball-milling medium simultaneously, withstand shocks, shear, rub and compress the effect of many kinds of force, experience extruding repeatedly, cold welding and crushing process, become the ultrafine particle that disperse distributes, under solid-state, realize alloying.There is investigator just to utilize mechanical alloying method to synthesize nanometer WC powder.They are placed in ball mill by Graphite Powder 99 and tungsten powder in the atomic ratio ratio of 1: 1, under argon shield, ball milling is 110 hours, the WC powder that to have synthesized grain fineness number be 7.2nm.
(2) spraying conversion process
Rutgers University and Nanodyne company, the University of Science & Technology, Beijing of the U.S. are all studied this method, and its primary process is to utilize water-soluble precursor thermochemistry synthesis of nano WC-Co, and its step is as follows:
1) preparation and the mixing precursor compound aqueous solution, fixedly the composition of starting soln, is used metatungstic acid ammonia [(NH conventionally
4)
6(H
2w
12o
40)
4h
2o] and CoCl
2, Co (NO
3)
2or Co (CH
3cOO)
2do the precursor compound aqueous solution;
2) by starting soln through spraying dry amorphous precursor powder;
3) through the reaction of fluidized-bed gas carburization, precursor powder is converted into the nanometer WC-Co powder that is less than 50nm.
Spraying conversion process has the following advantages:
1) by solution, mix the WC that can realize molecular level, the even mixing of Co, is easy to add different additives;
2) with traditional raw material and equipment, just can produce;
3) be suitable for on-line Control and can realize automatic control;
4) production system is dead front type, has reduced waste and the pollution to environment of the production means;
5) the WC-Co powder that is less than 50nm can be made, and the size range of 20～40nm can be reached.
(3) original position carburizing reduction method
The key of the method is that wolframic acid and cobalt salt are dissolved in organic solution, moves to after drying atmosphere furnace interior in the temperature range of 800～900 ℃, by 90%Ar-10%H
2the carbonization of mixed gas direct-reduction become WC-Co powder, the grain fineness number that makes powder is 50～80nm.The innovation of the method is to utilize polymkeric substance as original position carbon, directly by H
2one step is reduced into the single-phase WC-Co powder of nanometer by presoma, without carbonization process.Original position carburizing reduction method can reduce diffusion length, is a kind of very attractive large scale production method.In technological process, sintering temperature, atmosphere and the formation of nano WC-Co is all had to impact as a small amount of Cobaltous diacetate additive of catalyzer.The weak point of the method is still can find undecomposed polymkeric substance or uncombined carbon in the finished product, and then product performance are affected.
(4) plasma method
Plasma chemistry gaseous phase deposition is prepared a kind of method that carbide is extensive employing.By plasma generation thermal source, temperature can be up to 4000～5000 ℃, raw material at this temperature, decompose and react, synthetic generation.At present, the mode that produces thermal source mainly contains: direct-current plasma, high-frequency thermal plasma, direct current and the high frequency heat generation plasma body that combines.The raw material of preparing nano-carbide employing is generally W, WC, or WO
3, utilize CH
4as carbon source, mainly generate WC or W
2c.The research that Guishan Mountain wise man also waits shows: work as CH
4the mol ratio of/WC is greater than at 15 o'clock, obtains WC
1-xcontent is 90wt%～95wt%, WC
1-xpowder specific-surface area detection is 34m
2/ g, is equivalent to 10nm.Transmission electron microscope observing WC
1-xparticle size is 5～20nm, favorable dispersity.Due to CH
4cost is high, according to C-H state diagram, CH
4at high temperature decompose.At 2000～4000K, primary product is C
2h
2, with temperature, increasing carbon atom concn increases.Therefore there is people to propose to use C
2h
2replace expensive CH
4.The shortcoming of the method is to be difficult for maintaining the continual and steady of plasma jet, if plasma jet can not continually and steadily, can not guarantee that the evaporation of raw material and sufficient reacting carry out.
(5) reduction/carborization once
This technique is developed by U.S. Rutgers university.By gas phase mixture H
2/ CO (mol ratio is 2: 1 or 1: 1) surpasses ammonium tungstate or the Tungsten oxide 99.999 precursor powder of 700 ℃ by Heating temperature, then a step reduction and carbonization makes nanometer tungsten carbide (<10nm).The committed step of this technique is to control heating rate well, thereby makes its enough slow balance that guarantees reduction and carbonization dynamic process.Desirable reaction process is that O atom in precursor powder is by H
2after reduction, immediately by CO carbonization.For most of precursor powders, approximately 2 ℃ of heating rate/min is more satisfactory.This method has been simplified process.
Also available chemical precipitation method is prepared tungsten-cobalt/cobalt oxide ultrafine powder.Take this powder as raw material, at H
2under carbonaceous gas condition, adopting the continuous reduction and carbonization technique of low temperature to prepare mean particle size is that 0.1 μ m left and right, principal phase content are that WC-23%Co and uncombined carbon are less than 0.1% WC-Co composite powder.
(6) sol-gel method
Its ultimate principle is that the metallic compound of facile hydrolysis is reacted with water or other material in certain solvent, through hydrolysis and polycondensation process gelation gradually, in aftertreatments such as drying, calcining and reduction, obtains required material.Its primitive reaction has hydrolysis and polyreaction, can prepare at low temperatures purity is high, size distribution is even, chemically reactive is high single, multicomponent mixture (molecular level mixing).The people such as Srikanth, Raghunathan has prepared multiple nanocrystalline tungsten-based alloy composite powder with sol-gel processing, as W-Mo, and W-Cu, WC-Co powder.Take and produce pure tungsten as example, first by Na
2wO
42H
2o crystal joins in the hydrochloric acid of 0.1mol/L further acidifying and is heated between 298～330K, controls chemosynthesis condition as pH value etc., just can obtain gelatinous wolframic acid presoma, after being dried, reduces and can obtain tungsten powder.Prepare multiple element nanocrystalline tungsten base composite powder method similarly, it is that various metals salts solution is mixed.The manocrystalline powders structure of preparing by the method is single, and chemical control is accurate, operates comparatively simply, and cost is also cheaper, but because technological process is more complicated, has larger difficulty when batch production.
(7) coprecipitation method
Co-precipitation (Coprecipitation) method obtains presoma by the coprecipitation reaction of ammonium metawolframate or sodium wolframate and cobaltous hydroxide or Cobaltous diacetate, then presoma is inserted to H
2in there are reduction reactions in 600～700 ℃, then at the CO/CO of 700 ℃
2in mixed gas, direct carbonization obtains nano WC-Co composite powder end, last, inserts N
2in be cooled to room temperature.Its key is how rationally to control CO/CO
2ratio, the presoma that makes micron-scale is all broken into nano level WC-Co particle through reduction and carburizing reagent.
These methods, some is large with traditional technology difference, improvement of manufacturing line investment is large; Have plenty of and be difficult to stably produce in batches nanometer powder.Comprehensively it seems there is not yet the method for simply and effectively producing nanometer anhydrous wolframic acid powder in batches, thereby can utilize traditional CEMENTED CARBIDE PRODUCTION line to produce nano hard alloy.
Summary of the invention
The present invention proposes a kind of preparation method of nanometer anhydrous wolframic acid powder, for overcoming the deficiency of above method, prepares nanometer anhydrous wolframic acid powder for the preparation of nano-tungsten powder and tungsten carbide powder, also can be for sensor field.
Nanometer anhydrous wolframic acid powder preparation method of the present invention, comprises the steps: saturated ammonium tungstate solution to be heated to 65-70 ℃, then adds ammonium chloride, and add-on is 8-13g/L, stirs 0.5-1h; Then add respectively in order tartrate, ethylenediamine tetrapropionic acid(EDTP) and diethanolamine, add-on is respectively 11-14g/L, 23-32g/L and 6-9g/L, stirs and to make it to dissolve completely and to continue stirring 1-2h; Continue to stir and add nitric acid 320-380ml/L, form wolframic acid gel; Gel is placed in to process furnace and at 140-150 ℃, is dried, temperature rise rate 1-2 ℃/min, insulation 1-2h, then 2-3 ℃/min is warming up to 340-380 ℃ of insulation 2-3h calcining, and last ball mill pulverizing obtains nano tungsten trioxide.
Advantage of the present invention is that additive tartrate, ethylenediamine tetrapropionic acid(EDTP) and diethanolamine are all organism, decomposes volatilization noresidue after calcining; The volatilization eliminating in calcination process equally of the composition of nitric acid and ammonia chloride, therefore the nano tungsten trioxide powder purity of preparation is high.
By adding tartrate, ethylenediamine tetrapropionic acid(EDTP) and these organism of diethanolamine, make reaction process stable gently, be easy to control, the tungstic oxide particle of preparation is tiny evenly, and particle size is less than 50nm, mean particle size 23-28nm.
In addition, because flow process is simple, be easy to control, make suitability for industrialized production less investment, production technique is simple, convenient, and product cost is low, is convenient to realize industrialized mass production.
Embodiment
The present invention be take ammonium tungstate solution as main raw material, utilizes sol-gel method to prepare nanometer anhydrous wolframic acid powder.
First method of the present invention is heated to 65-70 ℃ by saturated ammonium tungstate solution, then adds ammonium chloride, and add-on is 8-13g/L, stirs 0.5-1h; Then add respectively in order tartrate, ethylenediamine tetrapropionic acid(EDTP) and diethanolamine, add-on is respectively 11-14g/L, 23-32g/L and 6-9g/L, stirs and to make it to dissolve completely and to continue stirring 1-2h; Continue to stir and add nitric acid 320-380ml/L, form wolframic acid gel.Add-on is wherein all by the criterion calculation of every liter of ammonium tungstate solution.
Then gel is placed in to process furnace and is dried at 140-150 ℃, temperature rise rate 1-2 ℃/min, insulation 1-2h, then 2-3 ℃/min is warming up to 340-380 ℃ of insulation 2-3h calcining, and last ball mill pulverizing obtains nano tungsten trioxide.The tungstic oxide particle of preparation is tiny even, and particle size is less than 50nm, and mean particle size is 23-28nm.
Ammonium chloride in the present invention plays the effect of buffer reagent, the forming core of wolframic acid is had to promoter action simultaneously.Tartrate, ethylenediamine tetrapropionic acid(EDTP) play the effect of complexing agent, and diethanolamine plays auxiliary complex-former effect, and these three kinds of reagent comprehensively improve complex reaction effect, thus after adding nitric acid, under the promotion of ammonium chloride, can stable and uniform ground wolframic acid gel.The average particle size of wolframic acid gel is 19-24nm.
Gel drying and calcining obtain nanometer anhydrous wolframic acid powder, are first slowly warmed up to 140-150 ℃, are mainly drying and dehydratings, are warming up to subsequently 340-380 ℃ of calcining, wolframic acid is decomposed and be transformed into tungstic oxide.Here need to control temperature rise rate, heat up too fast cause bubbling and volatilization large, process is wayward.After calcining, have agglomeration, need Ball milling to process, finally obtain nanometer anhydrous wolframic acid powder, particle size is less than 50nm, and mean particle size is 23-28nm.
Nano tungsten trioxide powder purity prepared by the inventive method is high, and the nano-tungsten powder purity obtaining after reduction reaches more than 99.95%, and granularity can be controlled at 60-70nm left and right.Tungsten-carbide powder granularity after carbonization can be controlled at 95-110nm.
Embodiment 1
Saturated ammonium tungstate solution is heated to 65 ℃, then adds ammonium chloride, add-on is 8g/L, stirs 0.5h; Then add respectively in order tartrate, ethylenediamine tetrapropionic acid(EDTP) and diethanolamine, add-on is respectively 11g/L, 32g/L and 6g/L, stirs and to make it to dissolve completely and to continue stirring 1h; Continue to stir and add nitric acid 320ml/L, form wolframic acid gel; Gel is placed in to process furnace and at 140 ℃, is dried, 1 ℃/min of temperature rise rate, insulation 1h, then 2 ℃/min is warming up to 340 ℃ of insulation 3h calcining, and last ball mill pulverizing obtains nano tungsten trioxide.
Embodiment 2
Saturated ammonium tungstate solution is heated to 70 ℃, then adds ammonium chloride, add-on is 13g/L, stirs 1h; Then add respectively in order tartrate, ethylenediamine tetrapropionic acid(EDTP) and diethanolamine, add-on is respectively 14g/L, 23g/L and 9g/L, stirs and to make it to dissolve completely and to continue stirring 2h; Continue to stir and add nitric acid 380ml/L, form wolframic acid gel; Gel is placed in to process furnace and at 150 ℃, is dried, 2 ℃/min of temperature rise rate, insulation 2h, then 3 ℃/min is warming up to 380 ℃ of insulation 2h calcining, and last ball mill pulverizing obtains nano tungsten trioxide.
Embodiment 3
Saturated ammonium tungstate solution is heated to 68 ℃, then adds ammonium chloride, add-on is 12g/L, stirs 1h; Then add respectively in order tartrate, ethylenediamine tetrapropionic acid(EDTP) and diethanolamine, add-on is respectively 13g/L, 25g/L and 8g/L, stirs and to make it to dissolve completely and to continue stirring 2h; Continue to stir and add nitric acid 370ml/L, form wolframic acid gel; Gel is placed in to process furnace and at 150 ℃, is dried, 2 ℃/min of temperature rise rate, insulation 2h, then 3 ℃/min is warming up to 370 ℃ of insulation 2h calcining, and last ball mill pulverizing obtains nano tungsten trioxide.
Embodiment 4
Saturated ammonium tungstate solution is heated to 67 ℃, then adds ammonium chloride, add-on is 11g/L, stirs 0.75h; Then add respectively in order tartrate, ethylenediamine tetrapropionic acid(EDTP) and diethanolamine, add-on is respectively 12g/L, 27g/L and 7g/L, stirs and to make it to dissolve completely and to continue stirring 1.5h; Continue to stir and add nitric acid 350ml/L, form wolframic acid gel; Gel is placed in to process furnace and at 145 ℃, is dried, 1.5 ℃/min of temperature rise rate, insulation 1.5h, then 2.5 ℃/min is warming up to 360 ℃ of insulation 2.5h calcining, and last ball mill pulverizing obtains nano tungsten trioxide.
Embodiment 5
Saturated ammonium tungstate solution is heated to 66 ℃, then adds ammonium chloride, add-on is 9g/L, stirs 0.5h; Then add respectively in order tartrate, ethylenediamine tetrapropionic acid(EDTP) and diethanolamine, add-on is respectively 11g/L, 30g/L and 7g/L, stirs and to make it to dissolve completely and to continue stirring 2h; Continue to stir and add nitric acid 330ml/L, form wolframic acid gel; Gel is placed in to process furnace and at 140 ℃, is dried, 2 ℃/min of temperature rise rate, insulation 1h, then 2 ℃/min is warming up to 350 ℃ of insulation 3h calcining, and last ball mill pulverizing obtains nano tungsten trioxide.
Embodiment 6
Saturated ammonium tungstate solution is heated to 69 ℃, then adds ammonium chloride, add-on is 8-13g/L, stirs 0.5-1h; Then add respectively in order tartrate, ethylenediamine tetrapropionic acid(EDTP) and diethanolamine, add-on is respectively 11-14g/L, 23-32g/L and 6-9g/L, stirs and to make it to dissolve completely and to continue stirring 1-2h; Continue to stir and add nitric acid 320-380ml/L, form wolframic acid gel; Gel is placed in to process furnace and at 140-150 ℃, is dried, temperature rise rate 1-2 ℃/min, insulation 1-2h, then 2-3 ℃/min is warming up to 340-380 ℃ of insulation 2-3h calcining, and last ball mill pulverizing obtains nano tungsten trioxide.
Claims (1)
1. a preparation method for nano tungsten trioxide powder, is characterized in that comprising the steps:
Saturated ammonium tungstate solution is heated to 65-70 ℃, then adds ammonium chloride, add-on is 8-13g/L, stirs 0.5-1h; Then add respectively in order tartrate, ethylenediamine tetrapropionic acid(EDTP) and diethanolamine, add-on is respectively 11-14g/L, 23-32g/L and 6-9g/L, stirs and to make it to dissolve completely and to continue stirring 1-2h; Continue to stir and add nitric acid 320-380ml/L, form wolframic acid gel; Gel is placed in to process furnace and at 140-150 ℃, is dried, temperature rise rate 1-2 ℃/min, insulation 1-2h, then 2-3 ℃/min is warming up to 340-380 ℃ of insulation 2-3h calcining, and last ball mill pulverizing obtains nano tungsten trioxide powder.
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|---|---|---|---|---|
| CN104370764A (en) * | 2014-10-20 | 2015-02-25 | 华中科技大学 | Diethylenetriamine derivatives, and preparation method and application thereof |
| CN105129857A (en) * | 2015-10-12 | 2015-12-09 | 上海第二工业大学 | Flower-shaped tungsten oxide nanometer material and preparing method thereof |
| CN105742615A (en) * | 2016-04-20 | 2016-07-06 | 北京科技大学 | Method for preparing hexagonal structure WO3.0.33H2O/C powder |
| CN106745275A (en) * | 2017-01-24 | 2017-05-31 | 南昌大学 | A kind of preparation method of hydration tungstic trioxide nano-slice |
| CN108251685A (en) * | 2018-01-22 | 2018-07-06 | 北京科技大学 | A kind of tungsten dispersed and strengthened copper-based composite material and preparation method thereof |
| CN109351359A (en) * | 2018-10-18 | 2019-02-19 | 吉林师范大学 | It is a kind of using carbon nanotube as the preparation method of the more metal carbides of Material synthesis |
| CN112941558A (en) * | 2020-12-30 | 2021-06-11 | 河南科技大学 | Preparation method of composite material catalytic electrode |
| CN116354399A (en) * | 2023-06-02 | 2023-06-30 | 崇义章源钨业股份有限公司 | Method for preparing loose nano tungsten oxide |
| CN116573673A (en) * | 2023-06-08 | 2023-08-11 | 翁百成 | Preparation method of nano tungsten trioxide |
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| CN104370764A (en) * | 2014-10-20 | 2015-02-25 | 华中科技大学 | Diethylenetriamine derivatives, and preparation method and application thereof |
| CN105129857A (en) * | 2015-10-12 | 2015-12-09 | 上海第二工业大学 | Flower-shaped tungsten oxide nanometer material and preparing method thereof |
| CN105742615A (en) * | 2016-04-20 | 2016-07-06 | 北京科技大学 | Method for preparing hexagonal structure WO3.0.33H2O/C powder |
| CN106745275A (en) * | 2017-01-24 | 2017-05-31 | 南昌大学 | A kind of preparation method of hydration tungstic trioxide nano-slice |
| CN106745275B (en) * | 2017-01-24 | 2018-06-22 | 南昌大学 | A kind of preparation method of hydration tungstic trioxide nano-slice |
| CN108251685B (en) * | 2018-01-22 | 2020-04-07 | 北京科技大学 | Tungsten dispersion strengthening copper-based composite material and preparation method thereof |
| CN108251685A (en) * | 2018-01-22 | 2018-07-06 | 北京科技大学 | A kind of tungsten dispersed and strengthened copper-based composite material and preparation method thereof |
| CN109351359A (en) * | 2018-10-18 | 2019-02-19 | 吉林师范大学 | It is a kind of using carbon nanotube as the preparation method of the more metal carbides of Material synthesis |
| CN112941558A (en) * | 2020-12-30 | 2021-06-11 | 河南科技大学 | Preparation method of composite material catalytic electrode |
| CN112941558B (en) * | 2020-12-30 | 2023-08-22 | 河南科技大学 | Preparation method of composite material catalytic electrode |
| CN116354399A (en) * | 2023-06-02 | 2023-06-30 | 崇义章源钨业股份有限公司 | Method for preparing loose nano tungsten oxide |
| CN116354399B (en) * | 2023-06-02 | 2023-08-04 | 崇义章源钨业股份有限公司 | Method for preparing loose nano tungsten oxide |
| CN116573673A (en) * | 2023-06-08 | 2023-08-11 | 翁百成 | Preparation method of nano tungsten trioxide |
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