CN106799490B - The method that room temperature aqueous solution prepares three-dimensional bicontinuous structure nanoporous tungsten - Google Patents
The method that room temperature aqueous solution prepares three-dimensional bicontinuous structure nanoporous tungsten Download PDFInfo
- Publication number
- CN106799490B CN106799490B CN201710206247.2A CN201710206247A CN106799490B CN 106799490 B CN106799490 B CN 106799490B CN 201710206247 A CN201710206247 A CN 201710206247A CN 106799490 B CN106799490 B CN 106799490B
- Authority
- CN
- China
- Prior art keywords
- tungsten
- powder
- ball
- aqueous solution
- bicontinuous structure
- 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.)
- Active
Links
Classifications
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- 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
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The method that room temperature aqueous solution prepares three-dimensional bicontinuous structure nanoporous tungsten, belongs to de- alloying and prepares nano porous metal field.It is that 70%-90% weighs tungsten powder and aluminium powder is added stearic acid and carries out high-energy ball milling as process control agent using the molar fraction of aluminium, wherein stearic additive amount is the 0.5-1.5% of ball-milled powder gross mass, abrading-ball is 20-40 with powder quality ratio：1, drum's speed of rotation 300-600r/min, Ball-milling Time 20-30h obtain tungsten aluminium alloy powder；Prepared tungsten aluminium alloy powder is placed in the 0.5-1M acid of deoxygenation or the aqueous solution of alkali and carries out de- alloying 15-25h, after ultra-pure water and ethyl alcohol are cleaned and dried, obtains the nanoporous tungsten with three-dimensional bicontinuous structure.Roughening effect the invention avoids the high temperature of liquid metal to porous structure.
Description
Technical field
The present invention relates to a kind of to prepare the nanoporous with three-dimensional bicontinuous structure feature in room temperature aqueous environment
The method of tungsten belongs to de- alloying and prepares nano porous metal field.
Background technology
Nano porous metal due to having the characteristics that large specific surface area, active site is more and is widely used in energy and deposits
The fields such as storage, catalysis and sensing.De- alloying process is to prepare one of common method of nano porous metal material at present.The party
The principle of method is to be optionally removed alloy in certain corrosive medium using difference in Electrode Potential larger between master alloy constituent element
The more active ingredient of middle chemical property, and remaining inert fraction formed by way of self assembly it is (tough with three-dimensional co-continuous
Band and duct are continuous) nano-porous structure.Receiving for the metals such as gold, platinum, palladium and copper is successfully prepared by the technology
Rice porous structure.Refractory metal has the characteristics that high-melting-point and high intensity, has as the structure member under high-temperature service wide
General application prospect.In order to extend scope and the application of nano porous metal, Recent study person are dedicated to exploitation and prepare hardly possible
The new technology of molten metal nano porous structure.A kind of de- alloying process of new liquid metal, this method have been developed at present
Using molten metal as removing alloy media, using different component in alloy, different intermiscibility realizes de- close in the molten metal
Golden process.But since the technology carries out in high temperature fluent metal, institutional framework roughening inevitably occurs, is unfavorable for obtaining
Nanostructure is obtained, the characteristic size of the porous niobium prepared by the technology is 170-400nm.According to the above present Research it is found that
It obtains characteristic size and is still the technical barrier for being badly in need of solving in the refractory metal porous structure of nanoscale.
In view of the above-mentioned problems, present inventor is by taking refractory metals tungsten as an example, it is water-soluble by mechanical alloying and room temperature
De- alloying process in pendular ring border develops a kind of side preparing the nanoporous tungsten with three-dimensional bicontinuous structure feature
Method, this method is easy to operate, is easy to industrialized production, and prepared POROUS TUNGSTEN particle size can be controlled in 100nm or less.
Invention content
The present invention is proposed for the problem that there is the nanoporous tungsten of three-dimensional bicontinuous structure feature to be faced is prepared at present
Using mechanical alloying and in room temperature aqueous environment, chemistry takes off the solution technology that alloying is combined.
The method that room temperature aqueous solution prepares three-dimensional bicontinuous structure nanoporous tungsten, includes the following steps：
(1) it is that 70%-90% weighs tungsten powder and aluminium powder, and stearic acid is added as process control agent by the molar fraction of aluminium
High-energy ball milling is carried out, wherein stearic additive amount is the 0.5-1.5% of ball-milled powder gross mass, abrading-ball is with powder quality ratio
20-40：1, drum's speed of rotation 300-600r/min, Ball-milling Time 20-30h obtain tungsten aluminium alloy powder；
(2) by prepared tungsten aluminium alloy powder be placed in deoxygenation 0.5-1M acid (acid preferably is selected from sulfuric acid, hydrochloric acid and hydrogen fluorine
Acid) or the aqueous solution of alkali (the preferred sodium hydroxide of alkali) in carry out de- alloying 15-25h, after ultra-pure water and ethyl alcohol are cleaned and dried,
Obtaining has the nanoporous tungsten of three-dimensional bicontinuous structure feature.
Compared with the de- alloy of existing liquid metal prepares the method for nanoporous refractory metal, advantage of the invention exists
In：De- alloy process is carried out in room temperature aqueous solution, the high temperature for avoiding liquid metal acts on the roughening of porous structure, therefore
Particle size can be obtained in the porous tungsten structure of nanoscale, POROUS TUNGSTEN particle size can control in 100nm or less.
Description of the drawings
The phase transition process of different ball milling stage tungsten aluminium alloy powders in Fig. 1 embodiments 1
The microstructure of the tungsten aluminium alloy powder finally obtained in Fig. 2 embodiments 1
The microstructure of the nanoporous tungsten powder obtained in Fig. 3 embodiments 1
The microstructure of the nanoporous tungsten powder obtained in Fig. 4 embodiments 2
The microstructure of the nanoporous tungsten powder obtained in Fig. 5 embodiments 3
The microstructure of (b) powder after (a) and de- alloy before alloy is taken off in Fig. 6 comparative examples 1.
Specific implementation mode
With reference to embodiment, the invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1：
By 1：4 molar ratio weighs 3.1507g tungsten powders, 1.8493g aluminium powders and 0.05g stearic acid and carries out high-energy ball milling, mill
Ball is 20 with powder quality ratio：1, drum's speed of rotation 600r/min, Ball-milling Time 30h obtain single-phase tungsten aluminium alloy powder,
The X-ray diffraction the result is shown in Figure 1 of different ball milling stage powder, microstructure such as Fig. 2 institutes of the tungsten aluminium alloy powder finally obtained
Show.High-purity argon gas is passed through in the beaker equipped with 1M sulfuric acid solutions after 10min, being put into tungsten aluminium alloy powder, to carry out de- alloy anti-
It answers, continues logical argon gas 10min, it is ensured that the oxygen in solution thoroughly removes, and is sealed beaker mouth with sealed membrane.Alloy reaction to be taken off
After carrying out 15h, 3 times are respectively washed with ultra-pure water and ethyl alcohol with suction filtration mode and collect powder sample, that is, obtaining has three-dimensional pair
The nanoporous tungsten powder of continuous structure feature, microstructure are as shown in Figure 3.
Embodiment 2：
Tungsten powder and aluminium powder are weighed for 70% by the molar fraction of aluminium, the stearic acid that mass fraction is 1.5% is added and was used as
Program-controlled preparation carries out high-energy ball milling, and abrading-ball is 40 with powder quality ratio：1, drum's speed of rotation 300r/min, Ball-milling Time are
20h obtains tungsten aluminium alloy powder.High-purity argon gas is passed through in the beaker equipped with 1M hydrochloric acid solutions after 15min, partinium is put into
Powder carries out de- alloy reaction, continues logical argon gas 10min, is sealed beaker mouth with sealed membrane.Alloy reaction to be taken off carries out 25h
Afterwards, 3 times are respectively washed with ultra-pure water and ethyl alcohol with suction filtration mode and collect powder sample, the micro- shape of the nanoporous tungsten of acquisition
Looks are as shown in Figure 4.
Embodiment 3：
Tungsten powder and aluminium powder are weighed for 90% by the molar fraction of aluminium, the stearic acid that mass fraction is 0.5% is added and was used as
Program-controlled preparation carries out high-energy ball milling, and abrading-ball is 30 with powder quality ratio：1, drum's speed of rotation 500r/min, Ball-milling Time are
25h obtains tungsten aluminium alloy powder.High-purity argon gas is passed through in the beaker equipped with 0.5M sodium hydroxide solutions after 10min, tungsten is put into
Al alloy powder carries out de- alloy reaction, continues logical argon gas 10min, is sealed beaker mouth with sealed membrane.Alloy to be taken off react into
After row 20h, 3 times are respectively washed with ultra-pure water and ethyl alcohol with suction filtration mode and collect powder sample, the nanoporous tungsten of acquisition
Microstructure is as shown in Figure 5.
Comparative example 1：
Tungsten powder and aluminium powder are weighed for 50% by the molar fraction of aluminium, the stearic acid that mass fraction is 1% is added and carries out high energy
Ball milling, abrading-ball are 20 with powder quality ratio：1, drum's speed of rotation 600r/min, Ball-milling Time 30h obtain single-phase tungsten aluminium and close
Bronze end.High-purity argon gas is passed through in the beaker equipped with 1M sulfuric acid solutions after 10min, tungsten aluminium alloy powder is put into and carries out de- alloy
Reaction continues logical argon gas 10min, is sealed beaker mouth with sealed membrane.After de- alloy react carry out 20h after, with filter mode with
Ultra-pure water and ethyl alcohol are respectively washed 3 times and collect powder sample.Sample topography before and after de- alloy there is no substantially changeing,
Nano-porous structure cannot be obtained, as shown in Figure 6.
Comparative example 2：
Tungsten powder and aluminium powder are weighed for 50% by the molar fraction of aluminium, the stearic acid that mass fraction is 1% is added and carries out high energy
Ball milling, abrading-ball are 30 with powder quality ratio：1, drum's speed of rotation 500r/min, Ball-milling Time 20h obtain single-phase tungsten aluminium and close
Bronze end.High-purity argon gas is passed through in the beaker equipped with 1M sodium hydroxide solutions after 10min, tungsten aluminium alloy powder is put into and is taken off
Alloy reacts, and continues logical argon gas 10min, is sealed beaker mouth with sealed membrane.After de- alloy reacts progress 25h, with suction filtration side
Formula is respectively washed 3 times with ultra-pure water and ethyl alcohol and collects powder sample.Sample topography before and after de- alloy is apparent there is no occurring
Change, nano-porous structure cannot be obtained.
Claims (4)
1. a kind of method that room temperature aqueous solution prepares three-dimensional bicontinuous structure nanoporous tungsten, which is characterized in that including walking as follows
Suddenly：
(1) it is that 70%-90% weighs tungsten powder and aluminium powder, and stearic acid is added and is carried out as process control agent by the molar fraction of aluminium
High-energy ball milling, wherein stearic additive amount is the 0.5-1.5% of ball-milled powder gross mass, abrading-ball is 20- with powder quality ratio
40：1, drum's speed of rotation 300-600r/min, Ball-milling Time 20-30h obtain tungsten aluminium alloy powder；
(2) prepared tungsten aluminium alloy powder is placed in the 0.5-1M acid of deoxygenation or the aqueous solution of alkali and carries out de- alloying 15-
25h obtains the nanoporous tungsten with three-dimensional bicontinuous structure feature after ultra-pure water and ethyl alcohol are cleaned and dried.
2. the method that a kind of room temperature aqueous solution described in accordance with the claim 1 prepares three-dimensional bicontinuous structure nanoporous tungsten,
It is characterized in that, acid is selected from sulfuric acid, hydrochloric acid and hydrofluoric acid.
3. the method that a kind of room temperature aqueous solution described in accordance with the claim 1 prepares three-dimensional bicontinuous structure nanoporous tungsten,
It is characterized in that, alkali is sodium hydroxide.
4. a kind of three-dimensional bicontinuous structure nanoporous tungsten being prepared according to claim 1-3 any one of them methods,
It is characterized in that, POROUS TUNGSTEN particle size is in 100nm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710206247.2A CN106799490B (en) | 2017-03-31 | 2017-03-31 | The method that room temperature aqueous solution prepares three-dimensional bicontinuous structure nanoporous tungsten |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710206247.2A CN106799490B (en) | 2017-03-31 | 2017-03-31 | The method that room temperature aqueous solution prepares three-dimensional bicontinuous structure nanoporous tungsten |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106799490A CN106799490A (en) | 2017-06-06 |
| CN106799490B true CN106799490B (en) | 2018-11-13 |
Family
ID=58981643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710206247.2A Active CN106799490B (en) | 2017-03-31 | 2017-03-31 | The method that room temperature aqueous solution prepares three-dimensional bicontinuous structure nanoporous tungsten |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106799490B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107433328B (en) * | 2017-09-21 | 2019-04-09 | 上海交通大学 | A kind of flake copper powder and preparation method thereof carrying nanometer copper crystal |
| CN107790733B (en) * | 2017-11-10 | 2020-02-07 | 上海交通大学 | Nano copper powder and preparation method thereof |
| CN107983963B (en) * | 2017-11-30 | 2020-04-03 | 北京工业大学 | Low-temperature preparation method of pure nano W-Cu composite powder |
| CN111020329B (en) * | 2019-11-22 | 2021-02-19 | 武汉理工大学 | Method for preparing porous tungsten material based on W-Fe-C system corrosion method |
| CN113333748B (en) * | 2021-05-10 | 2022-11-25 | 武汉理工大学 | Two-stage pore porous tungsten and preparation method thereof |
| CN113458393B (en) * | 2021-06-16 | 2022-09-13 | 中国科学院金属研究所 | Construction method of block nano porous metal |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0297607A (en) * | 1988-10-04 | 1990-04-10 | Osaka Gas Co Ltd | Manufacture of fine powder of stainless alloy steel |
| CN101885070A (en) * | 2009-07-05 | 2010-11-17 | 张雪云 | Method for comprehensively utilizing tungsten, nickel and iron in tungsten heavy alloy scrap |
| CN102363217A (en) * | 2011-10-26 | 2012-02-29 | 济南大学 | Method for preparing nanometer porous copper powder |
| CN102161510B (en) * | 2011-04-28 | 2012-09-05 | 北京工业大学 | Preparation method of hollow porous tungsten oxide sphere |
| CN104630538A (en) * | 2015-02-12 | 2015-05-20 | 张忠华 | Multicomponent nano porous palladium-base alloy and preparation method thereof |
-
2017
- 2017-03-31 CN CN201710206247.2A patent/CN106799490B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0297607A (en) * | 1988-10-04 | 1990-04-10 | Osaka Gas Co Ltd | Manufacture of fine powder of stainless alloy steel |
| CN101885070A (en) * | 2009-07-05 | 2010-11-17 | 张雪云 | Method for comprehensively utilizing tungsten, nickel and iron in tungsten heavy alloy scrap |
| CN102161510B (en) * | 2011-04-28 | 2012-09-05 | 北京工业大学 | Preparation method of hollow porous tungsten oxide sphere |
| CN102363217A (en) * | 2011-10-26 | 2012-02-29 | 济南大学 | Method for preparing nanometer porous copper powder |
| CN104630538A (en) * | 2015-02-12 | 2015-05-20 | 张忠华 | Multicomponent nano porous palladium-base alloy and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106799490A (en) | 2017-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106799490B (en) | The method that room temperature aqueous solution prepares three-dimensional bicontinuous structure nanoporous tungsten | |
| CN107170998B (en) | A kind of preparation method of black phosphorus graphene composite material supported precious metal nano-particle | |
| CN105197992B (en) | A kind of stratiform accumulates the preparation method of titania nanoparticles | |
| Li et al. | Gold nanodendrities on graphene oxide nanosheets for oxygen reduction reaction | |
| Wang et al. | Novel Raney-like nanoporous Pd catalyst with superior electrocatalytic activity towards ethanol electro-oxidation | |
| CN106960965B (en) | A kind of preparation method of the different structural material supported precious metal nano-particle processed of black phosphorus titanium dioxide | |
| CN102363217B (en) | Method for preparing nanometer porous copper powder | |
| CN104831104B (en) | Preparation method of three dimensional nanometer porous titanium and alloy thereof | |
| CN107419128B (en) | Using the method for three-dimensional communication nano porous metal preparation electrolysis water cathode hydrogen evolution electrode | |
| CN105855566B (en) | A kind of tantalum, niobium or its alloy increase the manufacturing method of material | |
| CN106916988A (en) | A kind of preparation method of nano porous metal film | |
| CN105399100A (en) | Preparation method for nanoporous silicon | |
| Kong et al. | Bulk hierarchical nanoporous palladium prepared by dealloying PdAl alloys and its electrochemical properties | |
| CN111020329B (en) | Method for preparing porous tungsten material based on W-Fe-C system corrosion method | |
| CN110396705B (en) | Method for preparing nano porous silver by electrodeposition | |
| CN101433959A (en) | Method for preparing hollow nano gold powder material | |
| CN107433328B (en) | A kind of flake copper powder and preparation method thereof carrying nanometer copper crystal | |
| Ribeiro et al. | MOF-derived PtCo/Co 3 O 4 nanocomposites in carbonaceous matrices as high-performance ORR electrocatalysts synthesized via laser ablation techniques | |
| Zheng et al. | Growth mechanism of core–shell PtNi–Ni nanoparticles using in situ transmission electron microscopy | |
| CN106011554B (en) | A kind of hydrolytic hydrogen production aluminium alloy and preparation method thereof | |
| CN110302799A (en) | Electrochemically reducing carbon dioxide is the catalyst and preparation method thereof of carbon monoxide | |
| CN106847528B (en) | A kind of preparation method of novel nano oxide super capacitor electrode material | |
| CN105798319B (en) | Preparation method of silver-tungsten electrical contact material, electrical contact material and electrical contact | |
| CN101139663A (en) | Preparation method of silver nickel composite material | |
| CN105970031B (en) | A kind of hydrolytic hydrogen production aluminium alloy and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210204 Address after: No. 300, kejingshe, Haicang District, Xiamen City, Fujian Province, 361000 Patentee after: XIAMEN TUNGSTEN Co.,Ltd. Address before: 100124 No. 100 Chaoyang District Ping Tian Park, Beijing Patentee before: Beijing University of Technology |