CN103302308B - Preparation method of nano tungsten powder - Google Patents
Preparation method of nano tungsten powder Download PDFInfo
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- CN103302308B CN103302308B CN201310236444.0A CN201310236444A CN103302308B CN 103302308 B CN103302308 B CN 103302308B CN 201310236444 A CN201310236444 A CN 201310236444A CN 103302308 B CN103302308 B CN 103302308B
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Abstract
A preparation method of nano tungsten powder comprises the following steps: (1) dissolving ammonium metatungstate, chromium nitrate and a water-soluble carbon source substance into in heated deionized water, electrically stirring to sufficiently mix raw materials, and after uniformly mixing the raw materials, performing spray drying to obtain precursor powder, wherein the weight percentage of the water-soluble carbon source substance is 10-30%, the weight percentage of the chromium nitrate is 0.5-2% and the temperature of the deionized water is 70 DEG C; and (2) putting the precursor powder obtained in the step (1) into a tubular atmosphere furnace, performing auxiliary hydrogen reduction, and before discharging the powder out of a furnace, passivating the powder with an inert gas, wherein the temperature is 710-850 DEG C, the heating rate is 10-15 DEG C/ min and the reaction time is 2-5h. The particle size of the prepared tungsten carbide is 40-70nm; after the prepared tungsten carbide is crushed, agglomeration-free nano tungsten powder can be obtained; the environment is polluted; and the development of a nanocrystalline WC-Co hard alloy can be effectively promoted.
Description
Technical field
The invention belongs to Hardmetal materials and preparation field.
Background technology
Nanocrystalline WC-Co (tungsten-cobalt carbide) carbide alloy is the developing direction becoming carbide alloy because expecting the characteristic having high rigidity and high strength (namely having high-wearing feature and high tenacity concurrently) concurrently.A difficult problem of restriction nanocrystalline WC-Co (tungsten-cobalt carbide) carbide alloy development is the difficulty in nano-tungsten powder preparation.
In fact difficulty in nano-tungsten powder preparation is exactly the difficulty on controlled oxidization tungsten " volatilization-deposition ".At present, tungsten powder preparation method mainly contains tungsten oxide hydrogen reduction and tungsten oxide carbon reduces two kinds, and in reduction process, tungsten powder can be grown up by the volatilization-sedimentation mechanism of tungsten oxide, and these two kinds of methods all can not prepare nano-tungsten powder.Tungsten oxide hydrogen reduction is prepared in the process of tungsten powder has a large amount of water vapours to produce, and the volatilization of water vapour meeting accelerated oxidation tungsten, finally can not get nano-tungsten powder.The reduction of tungsten oxide carbon is prepared in the process of tungsten powder, although the impact of water vapour can be eliminated, required for carbon reduction high temperature also can the volatilization of accelerated oxidation tungsten, so also can not get nano-tungsten powder.Therefore, the key preparing nano-tungsten powder suppresses the volatilization of tungsten oxide.
Summary of the invention
The object of the invention is for the deficiency in existing preparation technology, a kind of preparation method of novel nano tungsten powder is provided.
For solving the problem, technical scheme of the present invention is: prepare at hydrogen reduction method in the process of tungsten powder and add a small amount of carbon and tungsten oxide volatilization inhibitor, the impact utilizing carbon and steam reaction to reduce water vapour to volatilize on tungsten oxide, and the inhibitory action that inhibitor volatilizees to tungsten oxide, finally significantly can reduce the granularity of tungsten powder.
The preparation process that the present invention adopts is as follows.
(1) prepare burden: adopt the method for aqueous solution batching to prepare precursor powder.By a certain amount of ammonium metatungstate, chromic nitrate and water-soluble carbon source material: glucose or sucrose or water soluble phenol resin (carbon source), be dissolved in the deionized water of heating, electric stirring makes raw material fully mix.Wherein the percentage by weight of water-soluble carbon source material is 10 ~ 30%, and chromic nitrate is 0.5 ~ 2%, temperature >=70 DEG C of deionized water, to ensure that batch mixing is even.Raw material mixes the precursor powder that the spray-dired method of rear employing prepares reduction.
(2) reduce: precursor powder obtained in step (1) is put into tube-type atmosphere furnace and carry out carbon and assist hydrogen reduction, reduction temperature is 710 ~ 850
oc, heating rate 10 ~ 15
oc/min, the time is 2 ~ 5h.After reduction terminates, before powder is come out of the stove, carry out Passivation Treatment with inert gas.
The Tungsten Powder Size adopting above-mentioned carbon to assist hydrogen reduction method to prepare is 40 ~ 70nm, and reunite and not serious, the nano-tungsten powder of soilless sticking can be obtained after fragmentation.Tail gas after reduction is water-gas, can directly burn when tail gas is less, when tail gas amount is larger, can collects and use as fuel, can't to environment.Therefore carbon is adopted to assist hydrogen reduction method can effectively advance nanocrystalline WC-Co hard alloy to develop to prepare tungsten powder.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrum of the nano-tungsten powder that embodiment 1 is prepared.
Fig. 2 is the TEM photo of the nano-tungsten powder that embodiment 1 is prepared.
Detailed description of the invention
The present invention will be described further by following examples, but protection scope of the present invention is not limited thereto.
Embodiment 1.
Take ammonium metatungstate 180g, DEXTROSE ANHYDROUS 20g, chromic nitrate 1.5g, be dissolved in the deionized water of 80 DEG C, after raw material fully mixes, adopt spray-dired way to prepare presoma needed for reduction.Precursor powder is put into tube-type atmosphere furnace, passes into hydrogen and reduce, reduction temperature is 780 DEG C, heating rate 10
oc/min, the time is 2h.After reduction terminates, before powder is come out of the stove, change logical argon gas 30min carry out Passivation Treatment.Gained powder is nano grade tungsten powder, and its X ray diffracting spectrum and transmission electron microscope photo are shown in attached Fig. 1 and 2 respectively, and the particle diameter of nano-tungsten powder is 44nm.
Embodiment 2.
Take ammonium metatungstate 180g, DEXTROSE ANHYDROUS 20g, chromic nitrate 1.5g, be dissolved in the deionized water of 80 DEG C, after raw material fully mixes, adopt spray-dired way to prepare presoma needed for reduction.Precursor powder is put into tube-type atmosphere furnace, passes into hydrogen and reduce, reduction temperature is 800 DEG C, heating rate 15
oc/min, the time is 3h.After reduction terminates, before powder is come out of the stove, change logical argon gas 30min carry out Passivation Treatment.The particle diameter of the nano-tungsten powder of gained is 57nm.
Embodiment 3.
Take ammonium metatungstate 170g, DEXTROSE ANHYDROUS 30g, chromic nitrate 2.5g, be dissolved in the deionized water of 80 DEG C, after raw material fully mixes, adopt spray-dired way to prepare presoma needed for reduction.Precursor powder is put into tube-type atmosphere furnace, passes into hydrogen and reduce, reduction temperature is 780 DEG C, heating rate 10
oc/min, the time is 2h.After reduction terminates, before powder is come out of the stove, change logical argon gas 30min carry out Passivation Treatment.The particle diameter of the nano-tungsten powder of gained is 50nm.
Embodiment 4.
Take ammonium metatungstate 170g, DEXTROSE ANHYDROUS 30g, chromic nitrate 2.5g, be dissolved in the deionized water of 80 DEG C, after raw material fully mixes, adopt spray-dired way to prepare presoma needed for reduction.Precursor powder is put into tube-type atmosphere furnace, passes into hydrogen and reduce, reduction temperature is 800 DEG C, and the time is 3h.After reduction terminates, before powder is come out of the stove, change logical argon gas 30min carry out Passivation Treatment.The particle diameter of the nano-tungsten powder of gained is 68nm.
Claims (1)
1. a preparation method for nano-tungsten powder, is characterized in that as follows:
(1) prepare burden: by a certain amount of ammonium metatungstate, chromic nitrate and water-soluble carbon source material: glucose or sucrose or water soluble phenol resin, be dissolved in the deionized water of heating, electric stirring makes raw material fully mix, wherein the percentage by weight of water-soluble carbon source material is 10 ~ 30%, chromic nitrate is 0.5 ~ 2%, temperature >=70 DEG C of deionized water; After raw material mixes, spraying dry, obtains precursor powder;
(2) reduce: the precursor powder in step (1) is put into tube-type atmosphere furnace and carry out carbon and assist hydrogen reduction, reduction temperature is 710 ~ 850
oc, heating rate 10 ~ 15
oc/min, the time is 2 ~ 5h, after reduction terminates, before powder is come out of the stove, carries out Passivation Treatment with inert gas.
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| CN106944629B (en) * | 2016-10-06 | 2019-04-05 | 江西理工大学 | A kind of preparation method of monodisperse superfine/nano-tungsten powder |
| CN110052622B (en) * | 2019-05-31 | 2021-01-05 | 北京科技大学 | Method for preparing high-purity nano tungsten powder by tungsten crystal nucleus assisted tungsten dioxide hydrogen reduction |
| CN110496969B (en) * | 2019-09-23 | 2022-05-03 | 江西理工大学 | Nano tungsten powder and preparation method thereof |
| CN113441728A (en) * | 2021-06-28 | 2021-09-28 | 北京理工大学 | Preparation method of high-uniformity ultrafine/nano tungsten powder |
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| DE4414135C2 (en) * | 1993-04-22 | 1998-05-28 | Kobe Steel Ltd | Production of ultrafine composite powder for sintered hard metals |
| US5885372A (en) * | 1996-10-02 | 1999-03-23 | Nanodyne Incorporated | Multi-step process to incorporate grain growth inhibitors in WC-Co composite |
| CN1091665C (en) * | 1999-08-13 | 2002-10-02 | 武汉工业大学 | Industrilized process for preparing nm-class non-eta-phase compound powder of tungsten carbide and cobalt |
| CN1182932C (en) * | 2003-04-09 | 2005-01-05 | 北京工业大学 | Nano-rare earth tungsten powder and its preparation method |
| CN1297486C (en) * | 2005-04-01 | 2007-01-31 | 北京科技大学 | Method for preparing tungsten trioxide blue tungsten and tungsten powder in Nano grade |
| CN101181690B (en) * | 2007-12-14 | 2010-05-19 | 中山大学 | Microwave induction catalytic preparation method of nano tungsten carbide |
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