CN108772569A - A kind of hydrothermal preparing process of superfine nano tungsten powder - Google Patents
A kind of hydrothermal preparing process of superfine nano tungsten powder Download PDFInfo
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- CN108772569A CN108772569A CN201810657397.XA CN201810657397A CN108772569A CN 108772569 A CN108772569 A CN 108772569A CN 201810657397 A CN201810657397 A CN 201810657397A CN 108772569 A CN108772569 A CN 108772569A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- 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
Abstract
The present invention proposes a kind of hydrothermal preparing process of superfine nano tungsten powder.The one or more and ammonium metatungstate difference of dispersant cetyl trimethylammonium bromide CTAB, neopelex SDBS or lauryl sodium sulfate SDS is soluble in water, it is mixed after clarification, with nitric acid or salt acid for adjusting pH, with being ultrasonically treated fully dispersed, dissolving obtained solution；It places it in and carries out hydro-thermal reaction in reaction kettle；Suspension obtained by the reaction is filtered, washed after reaction, is dried；Finally two steps are carried out with hydrogen to restore to obtain superfine nano tungsten powder.Hydrothermal preparation method with addition dispersant is pollution-free, at low cost, and powder object obtained is mutually pure, reunion is small, crystal grain is small, and average grain size reaches 10~30nm and crystallite size distributed pole is narrow.The method, which prepares superfine nano tungsten powder, has significant advantage.
Description
Technical field
The present invention proposes a kind of technology of the hydrothermal preparing process of the superfine nano tungsten powder of addition dispersant, belongs to powder
Preparation engineering technical field.
Background technology
Nano material has superior mechanical property than common polycrystalline material, it is considered to be 21 century application prospect is very
Wide new material.Nano-tungsten powder is the material for preparing ultra-fine (nanometer) tungsten hard alloy etc..It is high quality X-ray tube tungsten target
The raw material of micron-sized tungsten foil, on the other hand, the ultrafine tungsten powder that the production of ultrafine gain size must use are reached with thickness
Make raw material.Ultrafine gain size has high rigidity, wearability, red hardness and higher obdurability concurrently, can solve certain spies
The processing problem of different material, be widely used in manufacturing metal cutting tool, the miniature drill of printed wiring board, dot-matrix printer needle
First-class precision instrument, precision die, wear part etc..In addition to this, nano-tungsten powder is in electronics industry, fine chemistry industry, surface skill
Also there is prodigious demand in the fields such as art, aerospace industry.
Superfine nano powder is generally referred to as diameter in 100nm powder below, has high sintering activity.To nanometer
For tungsten powder, the smaller crystal boundary of crystal grain is more, and impurity element distribution is more uniform, and ductile-brittle transition temperature can also reduce；Crystal grain is smaller in height
Recovery and recrystallization when warm is hindered, and recrystallization temperature is higher, and black brittleness is lower；Crystal grain is smaller, intensity hardness, plasticity
Toughness can improve.But nano-tungsten powder is more tiny, prepares more difficult.
The preparation method of superfine nano tungsten powder has traditional high-energy ball milling method, gas evaporation method, self propagating high temperature also at present
The methods of former method, tungstates method, spray drying process, each method has certain limitation.And Hydrothermal preparation method rarely has and relates to
And also have no the pertinent literature that 10nm or so superfine nano tungsten powders are prepared with hydro-thermal method.Under thermal and hydric environment, metal salt solution can analyse
Go out metal oxide, obtain the smaller metal oxide of crystal grain, the tungsten grain that when follow-up hydrogen reducing obtains can smaller.Hydro-thermal method
Impurity is not introduced, crystal grain is also smaller, but the rear metal oxide being precipitated can deposit the gold being formerly precipitated in water-heat process
Belong on oxide grain, causes growing up and reuniting for crystal grain.The present invention proposes a kind of addition dispersant and prepares superfine nano tungsten
The technology of the hydrothermal preparing process of powder.
Invention content
In view of the deficiencies of the prior art, the present invention proposes a kind of hydro-thermal system that dispersant is added and prepares superfine nano tungsten powder
Standby technology, realizes the mixing of high-purity, uniformity.The average grain size for the composite powder that the technology enables to most carefully may be used
Reach 10nm or so, and particle size distribution is extremely narrow.Basic principle prepared by hydro-thermal is that ammonium metatungstate fully dissolves, in high temperature
Hydrolysis generates oxide under high pressure.
Dispersant cetyl trimethylammonium bromide CTAB, neopelex SDBS, dodecyl sulphate is added
Sodium SDS can form adsorption layer on surface when tungsten oxide is precipitated, form one layer of film being made of dispersant, make solid particle table
The charge in face increases, and due to mutually exclusive with identical charge each other, raising forms the intergranular reaction of steric hindrance
Power to inhibit particle agglomeration in process of setting, and reduces growing up for crystal grain.With the Hydrothermal preparation method of addition dispersant without dirt
It contaminates, is at low cost, powder object obtained is mutually pure, reunion is small, crystal grain is small, and average grain size reaches 10~30nm and crystallite size point
Cloth is extremely narrow.
Specific technical solution is as follows：
A kind of hydrothermal preparing process of superfine nano tungsten powder, which is characterized in that include the following steps：
(1) dispersant and ammonium metatungstate are dissolved in deionized water respectively, are mixed after clarifying, it is 1~3 to adjust pH
Afterwards, it is that 100~200W is ultrasonically treated 0.33~1.5h with ultrasonic power, obtains mixed solution；
(2) and then in a kettle hydro-thermal reaction is carried out, suspension is filtered, washed after reaction, is dried；
(3) it is finally restored to obtain ultrafine yttria doping tungsten composite powder with pure two step of hydrogen.
In the step (1) dispersant be cetyl trimethylammonium bromide CTAB, neopelex SDBS or
Lauryl sodium sulfate SDS's is one or more；The quality of dispersant is the 2~10% of ammonium metatungstate quality.
Ammonium metatungstate is a concentration of in mixed solution in the step (1)：0.03~0.1g/mL；With nitric acid or hydrochloric acid
It is 1~3 to adjust pH.
Reaction kettle loading is 70~90% in the step (2)；170~190 DEG C of hydrothermal temperature, soaking time 24
~36h；It is filtered 2~4 times with deionized water or distilled water.
The temperature and time of two steps reduction is respectively in the step (3)：550~650 DEG C, 1~2h；700~800 DEG C,
1.5~2.5h.Advantages of the present invention：
1, compared with traditional Mechanical Alloying, hydrothermal preparing process can be on the basis of ensureing purity, to crystalline substance
Size, the shape of grain realize accurate regulation and control, and whole process is pollution-free.
2, by the way that the hydrothermal preparing process of different dispersants is added, so that crystal grain has been obtained apparent refinement, most can carefully obtain
The superfine nano tungsten powder of 10nm or so.
3, compared with other techniques, the small decades of times of powder grain and size distribution made from the hydro-thermal method because of addition dispersant
Extremely narrow, so in subsequent calcination and reduction process, temperature declines 100~200 DEG C, and required calcining and recovery time also shorten relatively
0.5~2h reduces the waste of resource.
4, the present invention can not only realize the preparation of superfine nano tungsten powder, while be also very suitable for a large amount of powder system of single batch
It is standby.
Description of the drawings
Fig. 1：The SEM pictures of superfine nano tungsten powder prepared by embodiment 1；
Fig. 2：The XRD diagram piece of superfine nano tungsten powder prepared by embodiment 1；
Fig. 3：The SEM pictures of superfine nano tungsten powder prepared by embodiment 2；
Fig. 4：The SEM pictures of superfine nano tungsten powder prepared by embodiment 4；
Fig. 5：The SEM pictures of superfine nano tungsten powder prepared by embodiment 5.
Specific implementation mode
The feature of the present invention is further described below by example, but the invention is not limited in following examples.
Embodiment 1
(1) 0.3g dispersant cetyl trimethylammonium bromide CTAB and 3g ammonium metatungstates AMT is dissolved in 30mL respectively
In ionized water, mixed after clarifying, be used in combination deionized water added to 100ml (a concentration of 0.03g/mL of AMT,
The quality of CTAB is the 10% of ammonium metatungstate quality), it is 1 with nitre acid for adjusting pH, then (sonification power is with supersound process
100W, ultrasonic time 1h) fully dissolve obtained solution after dispersion.
(2) solution is placed in reaction kettle, loading 80%, hydro-thermal reaction is carried out at 180 DEG C, heat preservation is for 24 hours.
(3) obtained suspension is filtered after reacting and is washed with deionized 2 times, is then dried in vacuo at 60 DEG C
8h。
(4) it powder is calcined into 0.5h in 500 DEG C of air draughts removes residual dispersant and obtain tungsten oxide powder.
(5) tungsten oxide powder two step reduction (600 DEG C of heat preservations 1.5h, 800 DEG C of heat preservation 1.5h) are carried out in hydrogen gas stream to obtain
To superfine nano tungsten powder.Finally the precursor powder is cooled to room temperature in hydrogen atmosphere, obtains even grain size, is averaged
Crystallite dimension is the superfine nano tungsten powder of 22.5nm, and surface topography is as shown in Figure 1, object is mutually as shown in Figure 2.With addition dispersant
Powder object made from hydro-thermal method is mutually pure, and without granularity bimodal distribution phenomenon, crystal grain is minimum and particle-size distribution is extremely narrow, and the method has
Significant advantage.
Embodiment 2
(1) 0.5g dispersant cetyl trimethylammonium bromide CTAB and 10g ammonium metatungstates AMT is dissolved in 30mL respectively
It in ionized water, is mixed after clarifying, deionized water is used in combination to be added to 100ml (a concentration of 0.1g/mL, CTAB of AMT
Quality be the 5% of ammonium metatungstate quality), be 2 with nitre acid for adjusting pH, then be ultrasonically treated (sonification power 200W, it is super
Sound time 0.33h) fully dissolve obtained solution after dispersion.
(2) solution is placed in reaction kettle, loading 70%, hydro-thermal reaction is carried out at 170 DEG C, keep the temperature 36h.
(3) obtained suspension is filtered after reacting and is washed with deionized 3 times, is then dried in vacuo at 60 DEG C
8h。
(4) it powder is calcined into 0.5h in 500 DEG C of air draughts removes residual dispersant and obtain tungsten oxide powder.
(5) tungsten oxide powder two step reduction (550 DEG C of heat preservations 2h, 700 DEG C of heat preservation 2h) are carried out in hydrogen gas stream to be surpassed
Thin nano-tungsten powder.Finally the precursor powder is cooled to room temperature in hydrogen atmosphere, obtains even grain size, average crystal grain
Size is the superfine nano tungsten powder of 12.5nm, and surface topography is as shown in Figure 3.Powder object made from hydro-thermal method with addition dispersant
Xiang Chun, without granularity bimodal distribution phenomenon, crystal grain is minimum and particle-size distribution is extremely narrow, and the method has significant advantage.
Embodiment 3
(1) 0.1g neopelex SDBS and 5g ammonium metatungstates AMT is dissolved in respectively in 30mL deionized waters, is waited for
It is mixed after clarification, being used in combination deionized water to be added to 100ml, (quality of a concentration of 0.05g/mL of AMT, CTAB are inclined
The 2% of ammonium tungstate quality), with nitre acid for adjusting pH be 3, then with supersound process (sonification power 150W, ultrasonic time
1.5h) obtained solution fully after dissolving dispersion.
(2) solution is placed in reaction kettle, loading 90%, hydro-thermal reaction is carried out at 190 DEG C, heat preservation is for 24 hours.
(3) obtained suspension is filtered after reacting and is washed with deionized 4 times, is then dried in vacuo at 60 DEG C
12h。
(4) it powder is calcined into 0.5h in 500 DEG C of air draughts removes residual dispersant and obtain tungsten oxide powder.
(5) tungsten oxide powder two step reduction (650 DEG C of heat preservations 1h, 750 DEG C of heat preservation 1.5h) are carried out in hydrogen gas stream to obtain
Superfine nano tungsten powder.Finally the precursor powder is cooled to room temperature in hydrogen atmosphere, obtains even grain size, average crystalline substance
Particle size is the superfine nano tungsten powder of 29.5nm.Powder object is mutually pure made from hydro-thermal method with addition dispersant, double without granularity
Peak Distribution Phenomena, crystal grain is minimum and particle-size distribution is extremely narrow, and the method has significant advantage.
Embodiment 4
(1) 0.3g dispersant lauryl sodium sulfate SDS and 3g ammonium metatungstates AMT is dissolved in 30mL deionized waters respectively
In, it is mixed after clarifying, deionized water is used in combination to be added to 100ml (a concentration of 0.03g/mL of AMT, the matter of CTAB
Amount is the 10% of ammonium metatungstate quality), be 1 with salt acid for adjusting pH, then be ultrasonically treated (sonification power 100W, it is ultrasonic
Time 1h) fully dissolve obtained solution after dispersion.
(2) solution is placed in reaction kettle, loading 80%, hydro-thermal reaction is carried out at 180 DEG C, keep the temperature 30h.
(3) obtained suspension is filtered after reacting and is washed with distilled water 3 times, 8h is then dried in vacuo at 60 DEG C.
(4) it powder is calcined into 0.5h in 500 DEG C of air draughts removes residual dispersant and obtain tungsten oxide powder.
(5) tungsten oxide powder two step reduction (600 DEG C of heat preservations 1.5h, 700 DEG C of heat preservation 2.5h) are carried out in hydrogen gas stream to obtain
To superfine nano tungsten powder.Finally the precursor powder is cooled to room temperature in hydrogen atmosphere, obtains even grain size, is averaged
Crystallite dimension is the superfine nano tungsten powder of 19.5nm, and surface topography is as shown in Figure 4.Powder made from hydro-thermal method with addition dispersant
Last object is mutually pure, and without granularity bimodal distribution phenomenon, crystal grain is minimum and particle-size distribution is extremely narrow, and the method has significant advantage.
Embodiment 5
(1) by 0.15g dispersant cetyl trimethylammonium bromide CTAB and 0.15g dispersant lauryl sodium sulfate
SDS is dissolved in together in 30mL deionized waters, then 3g ammonium metatungstates AMT is dissolved in another 30mL deionized waters, by two after clarifying
Part solution mixes, and being used in combination deionized water to be added to 100ml, (a concentration of 0.03g/mL of AMT, the quality of dispersant are
The 10% of ammonium metatungstate quality), with nitre acid for adjusting pH be 1, then with supersound process (sonification power 100W, ultrasonic time
1h) obtained solution fully after dissolving dispersion.
(2) solution is placed in reaction kettle, loading 80%, hydro-thermal reaction is carried out at 170 DEG C, heat preservation is for 24 hours.
(3) obtained suspension is filtered after reacting and is washed with deionized 3 times, is then dried in vacuo at 60 DEG C
8h。
(4) it powder is calcined into 0.5h in 500 DEG C of air draughts removes residual dispersant and obtain tungsten oxide powder.
(5) tungsten oxide powder two step reduction (600 DEG C of heat preservations 1.5h, 800 DEG C of heat preservation 1.5h) are carried out in hydrogen gas stream to obtain
To superfine nano tungsten powder.Finally the precursor powder is cooled to room temperature in hydrogen atmosphere, obtains even grain size, is averaged
Crystallite dimension is the superfine nano tungsten powder of 18.9nm, and surface topography is as shown in Figure 5.Powder made from hydro-thermal method with addition dispersant
Last object is mutually pure, and without granularity bimodal distribution phenomenon, crystal grain is minimum and particle-size distribution is extremely narrow, and the method has significant advantage.
Claims (5)
1. a kind of hydrothermal preparing process of superfine nano tungsten powder, which is characterized in that include the following steps：
(1) dispersant and ammonium metatungstate are dissolved in deionized water respectively, are mixed after clarifying, after tune pH is 1~3,
It is that 100~200W is ultrasonically treated 0.33~1.5h with ultrasonic power, obtains mixed solution；
(2) and then in a kettle hydro-thermal reaction is carried out, suspension is filtered, washed after reaction, is dried；
(3) it is finally restored to obtain ultrafine yttria doping tungsten composite powder with pure two step of hydrogen.
2. according to the method described in claim 1, it is characterized in that dispersant is cetyl trimethylammonium bromide in step (1)
CTAB, neopelex SDBS, lauryl sodium sulfate SDS it is one or more；The quality of dispersant is metatungstic acid
The 2~10% of ammonium quality.
3. according to the method described in claim 1, it is characterized in that concentration of the ammonium metatungstate in mixed solution in step (1)
For：0.03~0.1g/mL；It is 1~3 with nitric acid or hydrochloric acid tune pH.
4. according to the method described in claim 1, it is characterized in that reaction kettle loading is 70~90% in step (2)；Hydro-thermal
170~190 DEG C of reaction temperature, 24~36h of soaking time；It is filtered 2~4 times with deionized water or distilled water.
5. according to the method described in claim 1, it is characterized in that the temperature and time that two steps restore in step (3) is respectively：
550~650 DEG C, 1~2h；700~800 DEG C, 1.5~2.5h.
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| CN112338197A (en) * | 2020-10-19 | 2021-02-09 | 赣州有色冶金研究所 | Method for preparing superfine spherical tungsten powder based on hydrothermal method |
| CN112760677A (en) * | 2020-12-28 | 2021-05-07 | 中国科学技术大学 | Iridium-tungsten alloy nano material, preparation method thereof and application of iridium-tungsten alloy nano material as acidic oxygen evolution reaction electrocatalyst |
| CN115740475A (en) * | 2022-11-11 | 2023-03-07 | 中国恩菲工程技术有限公司 | Nano molybdenum powder and preparation method thereof |
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