CN100402200C - Method for preparing nano metal pipe by template chemical plating process - Google Patents
Method for preparing nano metal pipe by template chemical plating process Download PDFInfo
- Publication number
- CN100402200C CN100402200C CNB2005100452457A CN200510045245A CN100402200C CN 100402200 C CN100402200 C CN 100402200C CN B2005100452457 A CNB2005100452457 A CN B2005100452457A CN 200510045245 A CN200510045245 A CN 200510045245A CN 100402200 C CN100402200 C CN 100402200C
- Authority
- CN
- China
- Prior art keywords
- nano
- fiber
- metal pipe
- preparation
- template
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The present invention provides a method for preparing a nano metal pipe by template chemical plating process, which comprises the following steps: a nano carbon fibre or a nano macromolecular fibre is adopted as a chemical plating template, and the surface of the nano carbon fibre or the nano macromolecular fibre is cleaned; surface coarsening modification is made in a strong acid solution; after the modified carbon fibre or nano macromolecular fibre is soaked in a surfactant solution under the condition of ultrasonic stirring, the activation treatment is carried out in the hydrochloric solutions of stannous chloride and palladium dichloride; the chemical plating treatment to the surface of the nano carbon fibre or the nano macromolecular fibre is carried out in a chemical plating liquid; the template is oxygenized and removed; metal oxide is reduced to obtain a nano metal pipe under hydrogen atmosphere. The method is simple, the size and the shape of the nano metal pipes are easy to control, the production capacity is high, and good controllability and batch production feasibility are given to the nano metal pipe.
Description
Technical field
The present invention relates to a kind of preparation method of nano metal pipe, be specifically related to a kind of templated chemistry and be coated with the fully preparation method of nano metal pipe, relate in particular to that a kind of thickness of coating is uniform, thickness of coating is controllable, the preparation method of the controllable nano metal pipe of pattern by having of forming of one or more metals.
Background technology
In recent years, owing to have particular structure and performance, and the potential application prospect in catalyst field, fuel cell, sensor and piece-rate system, the tubular material of nanoscale causes scientific research person's especially concern day by day.Since CNT is found, existing a lot of report about the nano metal pipe material preparation method.Because metal plays an important role at catalyst and field of nanometer technology, adopting nano-porous polymer and pellumina is template, utilizes method for electrodeposition successfully to prepare gold nanotubes, nickel nanotube, palladium nanotube and silver-colored nanotube.Yet, in the preparation technology of the nano metal pipe of finding report, exist complex process, nano metal pipe size and pattern control difficulty, problem such as yield poorly.
Summary of the invention
Problems such as complex process, nano metal pipe size and the pattern control that the present invention is directed to existence in the present nano metal pipe preparation is difficult, yield poorly, a kind of preparation method of preparing nano metal pipe by template chemical plating has been proposed, this method is simple, nano metal pipe size pattern is controlled easily, the output height, and give good controllability of nano metal pipe and prepared in batches feasibility.
For solving the problem that exists in the existing nano metal pipe preparation process, the present invention has adopted following technical proposals.
The invention discloses a kind of preparation method of templated chemistry plating nano-metal pipe, comprise the following order step:
(1) adopt carbon nano-fiber or nano-high molecule fiber as the chemical plating template, the surface washing of carbon nano-fiber or nano-high molecule fiber is clean;
(2) carrying out surface coarsening in strong acid solution modifies;
(3) will modify back carbon nano-fiber or nano-high molecule fiber under the ultrasonic wave stirring condition, in 0.01～0.02mol/L anion and/or nonionic surface active agent solution, soak; Afterwards, be that 0.10～0.50mol/L, concentration of hydrochloric acid are that the sensitization of carrying out 5～10min in 2.50～4.00mol/L mixed solution is handled in stannous chloride concentration earlier, deionized water rinsing is clean, is that 0.01～0.03mol/L, concentration of hydrochloric acid are the activation processing of carrying out 5～10min in 2.50～4.00mol/L mixed solution in the concentration of palladium chloride;
(4) in chemical plating fluid chemical plating being carried out on the surface of carbon nano-fiber or nano-high molecule fiber handles;
(5) template is removed in the carbon nano-fiber or the oxidation at high temperature of nano-high molecule fiber that are attached with the coat of metal of chemical plating rear surface;
(6) under hydrogen atmosphere, the high temperature reduction metal oxide obtains nano metal pipe.
In the technique scheme,, removed the various organic molecule pollutants that the surface may be infected with, avoided the influence of pollutant quality of coating by washing to carbon nano-fiber or nano-high molecule fiber surface; In strong acid carbon nano-fiber or nano-high molecule fiber are carried out roughening treatment, its surface is modified, improved the wetability of carbon nano-fiber or nano-high molecule fiber, the time of roughening treatment and temperature can be adjusted as required; Carbon nano-fiber after the modification or nano-high molecule fiber carry out sensitization, activation respectively in the hydrochloric acid solution of stannous chloride and palladium chloride, made on its surface deposition the reactive metal palladium; In the process of chemical plating, the kind and the proportioning of the metal ion by adjusting plating bath, the acid-base value of plating bath and temperature can obtain uniform nano metal pipe/carbon nano-fiber of thickness or nano-high molecule fiber composite pipe; With nano metal pipe/carbon nano-fiber or the heat treatment under air atmosphere earlier of nano-high molecule fiber composite pipe, then reduction is handled under hydrogen atmosphere, has just obtained nano metal pipe; The pattern of product nano metal pipe is identical with template, adopts the carbon nano-fiber of different-shape to make template, can obtain the nano metal pipe of different-shape.
Chemical plating fluid can be selected one or more metal ion solutions, to obtain nano metal pipe or Nanoalloy pipe.
The template carbon nano-fiber is to adopt chemical vapour deposition technique to be prepared from, and its exterior appearance is linear pattern or spiral line type, is monodimension nanometer material; Template nano-high molecule fiber is to adopt polymerization to be prepared from, and is monodimension nanometer material.
Nano material is meant the material that has at least one dimension to be in nanoscale (≤100 nanometer) scope or to be made of as elementary cell them in three dimensions.If press dimension, the elementary cell of nano material can be divided three classes: zero dimension; One dimension; Two dimension.Wherein, one dimension is meant has bidimensional to be in nanoscale in the space, as nanofiber, nanometer rods, nanotube etc.
The surface of carbon nano-fiber or nano-high molecule fiber can influence the formation of carbon nano-fiber or nano-high molecule fiber coating in the chemical plating process if there is organic molecule; Therefore preferred among the present invention: carbon nano-fiber or nano-high molecule fiber wash in the mixed liquor of butanols and dimethylbenzene respectively at absolute ethyl alcohol, remove surperficial organic molecule pollutant.N-butanol and dimethylbenzene, absolute ethyl alcohol are not unique solvents, and acetone also is the solvent of using always, and best kind of solvent and proportioning generally are specifically to determine according to the composition of template; Studies show that n-butanol and dimethylbenzene mix the result of use ideal, the general mixing uses.The organic molecule pollutant also can clean by other organic matter solvents, as organic solvents such as lipid, mystery class etc.
Among the present invention, for having improved the wetability of carbon nano-fiber or nano-high molecule fiber, need to carry out surface coarsening and handle in strong acid solution, preferred: described strong acid is red fuming nitric acid (RFNA) and/or concentrated sulfuric acid mixed liquor; Adopt nitric acid/chromic anhydride solution also to can be used for roughening treatment.
In the above-mentioned preparation process, what carbon nano-fiber or the washing of nano-high molecule fiber surface were adopted is absolute ethyl alcohol and butanols/dimethylbenzene mixed solution, and wherein, the volume ratio of butanols/dimethylbenzene is 1: 3～1: 5.
Preferably: described strong acid is the mixture of nitric acid and sulfuric acid, and the volume ratio of nitric acid, sulfuric acid is 3: 1～1: 1, and treatment temperature is 65～75 ℃, processing time 10～20min.
Among the present invention, before being activated, fiber needs fiber is soaked in anion, nonionic surface active agent solution, common anion and non-ionic surface active agent all can be used for above-mentioned steps, as anion surfactant commonly used: lauryl sodium sulfate; Sodium dodecyl benzenylsulfonate etc., non-ionic surface active agent: AEO, or NPE etc., among the present invention, preferred: described surfactant is: lauryl sodium sulfate; Sodium dodecyl benzenylsulfonate; AEO; In the NPE one or more, soak time are 1.0～1.5h.Soak time can be carried out suitable adjustment, to satisfy the preceding fiber surface physico-chemical property needs of activation.
The chemical plating rear surface is attached with the carbon nano-fiber or the oxidation at high temperature of nano-high molecule fiber of the coat of metal and removes template, removes template in 300～450 ℃ of high-temperature process 60～180min oxidation in the preferred steps (5).
Under hydrogen atmosphere, the high temperature reduction metal oxide obtains nano metal pipe.Preferably: under hydrogen atmosphere, at 300～400 ℃ of high-temperature process 60～120min, reducing metal oxide obtains nano metal pipe in the step (6).
With the nano metal pipe of method preparation of the present invention, to compare with the nano metal pipe of report, this method is simple, and nano metal pipe size pattern is controlled easily, the output height, and give good controllability of nano metal pipe and prepared in batches feasibility.
Description of drawings
Fig. 1 is the scanning electron microscope diagram sheet by the nano metal pipe of the inventive method preparation.
Fig. 2 is the picture by the projection electron microscope of the nano metal pipe of the inventive method preparation.
The specific embodiment
The specific embodiment 1:
A kind of preparation method of preparing nano metal pipe by template chemical plating comprises the following order step:
(1) carbon nano-fiber is washed in absolute ethyl alcohol, in n-butanol, dimethylbenzene volume ratio are 1: 3 mixed solution, wash afterwards, the carbon nano-fiber surface is comprised that organic micromolecular impurity cleans up;
(2) in glass container, it is～1: 1 that the carbon nano-fiber of cleaning is placed the volume ratio of nitric acid, sulfuric acid, and treatment temperature is 70～75 ℃, processing time 10min.
(3) will modify the back carbon nano-fiber under the ultrasonic wave stirring condition, in the lauryl sodium sulfate surfactant solution of 0.01mol/L, soak 1.5h; Afterwards, be that 0.30mol/L, concentration of hydrochloric acid are that the sensitization of carrying out 8min in the 2.50mol/L mixed solution is handled in stannous chloride concentration earlier, after adopting deionized water rinsing three times, be that 0.01mol/L, concentration of hydrochloric acid are the activation processing of carrying out 5min in the 2.50mol/L mixed solution in the concentration of palladium chloride;
(4) carbon nano-fiber that activates is placed, concentration of nickel sulfate is 25gL
-1, sodium hypophosphite concentration is 25gL
-1, sodium acetate concentration is 12gL
-1With lactic acid concn be 30mlL
-1Acid solution in, carry out chemical plating, the temperature of plating bath is 75 ℃, the chemical plating time is 10min, obtains the Ni-P alloy layer on the carbon nano-fiber surface;
(5) carbon nano-fiber that chemical plating is handled places the baking box of air atmosphere to heat-treat, and temperature is 350～400 ℃, and the time is 120min; Then product is put in the reduction furnace of hydrogen atmosphere, treatment temperature is 300～350 ℃, and the time is 60min, and reducing metal oxide obtains nano metal pipe.
The specific embodiment 2:
A kind of preparation method of preparing nano metal pipe by template chemical plating comprises the following order step:
(1) the nano polyaniline fiber is washed in acetone, in n-butanol, dimethylbenzene volume ratio are 1: 4 mixed solution, wash afterwards, the nano polyaniline fiber surface is comprised that organic micromolecular impurity cleans up;
(2) in glass container, it is that to carry out surface treatment be 20min for 1: 1 mixed solution room temperature that the nano polyaniline fiber of cleaning is placed red fuming nitric acid (RFNA) and concentrated sulfuric acid volume ratio;
(3) will modify back nano polyaniline fiber under the ultrasonic wave stirring condition, in the NPE solution of the lauryl sodium sulfate of 0.01mol/L and 0.01mol/L, soak 1.0h; Afterwards, be that 0.50mol/L, concentration of hydrochloric acid are that the sensitization of carrying out 10min in the 4.00mol/L mixed solution is handled in stannous chloride concentration earlier, after adopting deionized water rinsing three times, be that 0.02mol/L, concentration of hydrochloric acid are the activation processing of carrying out 7min in the 3.00mol/L mixed solution in the concentration of palladium chloride;
(4) the nano polyaniline fiber that activates is placed, cobalt sulfate concentration is 25gL
-1, sodium hypophosphite concentration is 25gL
-1, sodium acetate concentration is 12gL
-1With citric acid concentration be 30mlL
-1Acid solution in, carry out chemical plating, the temperature of plating bath is 80 ℃, the chemical plating time is 12min, obtains the Co-P alloy layer at the nano polyaniline fiber surface;
(5) the nano polyaniline fiber that chemical plating is handled places the baking box of air atmosphere to heat-treat, temperature is 400～450 ℃ of high-temperature process 120min, then product is put in the reduction furnace of hydrogen atmosphere, treatment temperature is at 450 ℃ of high-temperature process 60min, reducing metal oxide obtains nano metal pipe.
The specific embodiment 3:
A kind of preparation method of preparing nano metal pipe by template chemical plating comprises the following order step:
(1) carbon nano-fiber is washed in absolute ethyl alcohol, in n-butanol, dimethylbenzene volume ratio are 1: 5 mixed solution, wash afterwards, the carbon nano-fiber surface is comprised that organic micromolecular impurity cleans up;
(2) in glass container, it is that to carry out surface treatment be 15min for 2: 1 mixed solution room temperature that the carbon nano-fiber of cleaning is placed red fuming nitric acid (RFNA) and concentrated sulfuric acid volume ratio;
(3) will modify the back carbon nano-fiber under the ultrasonic wave stirring condition, in the AEO surfactant solution of 0.015mol/L, soak 1.2h; Afterwards, be that 0.40mol/L, concentration of hydrochloric acid are that the sensitization of carrying out 7min in the 3.00mol/L mixed solution is handled in stannous chloride concentration earlier, after adopting deionized water rinsing three times, be that 0.01mol/L, concentration of hydrochloric acid are the activation processing of carrying out 5min in the 3.50mol/L mixed solution in the concentration of palladium chloride;
(4) carbon nano-fiber that activates is placed, concentration of copper sulfate is 15gL
-1, sodium citrate concentration is 20gL
-1, ammonium chloride concentration is 12gL
-1With concentration of formaldehyde be 30mlL
-1Solution in, carry out chemical plating, the temperature of plating bath is 25 ℃, the chemical plating time is 8min, obtains Cu coating on the carbon nano-fiber surface;
(5) carbon nano-fiber that chemical plating is handled places the baking box of air atmosphere to heat-treat, temperature is 500 ℃ of high-temperature process 100min, then product is put in the reduction furnace of hydrogen atmosphere, treatment temperature is at 300 ℃ of high-temperature process 120min, reducing metal oxide obtains nano metal pipe.
According to method disclosed by the invention, can process nano metal pipe 1 as shown in Figure 1 and Figure 2.
Claims (10)
1. the preparation method of a templated chemistry plating nano-metal pipe comprises the following order step:
(1) adopt carbon nano-fiber or nano-high molecule fiber as the chemical plating template, the surface washing of carbon nano-fiber or nano-high molecule fiber is clean;
(2) carrying out surface coarsening in strong acid solution modifies;
(3) will modify back carbon nano-fiber or nano-high molecule fiber under the ultrasonic wave stirring condition, in 0.01～0.02mol/L anion and/or nonionic surface active agent solution, soak; Afterwards, be that 0.10～0.50mol/L, concentration of hydrochloric acid are that the sensitization of carrying out 5～10min in 2.50～4.00mol/L mixed solution is handled in stannous chloride concentration earlier, deionized water rinsing is clean, is that 0.01～0.03mol/L, concentration of hydrochloric acid are the activation processing of carrying out 5～10min in 2.50～4.00mol/L mixed solution in the concentration of palladium chloride;
(4) in chemical plating fluid chemical plating being carried out on the surface of carbon nano-fiber or nano-high molecule fiber handles;
(5) template is removed in the carbon nano-fiber or the oxidation at high temperature of nano-high molecule fiber that are attached with the coat of metal of chemical plating rear surface;
(6) under hydrogen atmosphere, the high temperature reduction metal oxide obtains nano metal pipe.
2. the preparation method of templated chemistry plating nano-metal pipe according to claim 1 is characterized in that: chemical plating fluid can be selected one or more metal ion solutions, to obtain nano metal pipe or Nanoalloy pipe.
3. the preparation method of templated chemistry plating nano-metal pipe according to claim 2 is characterized in that: the template carbon nano-fiber is to adopt chemical vapour deposition technique to be prepared from, and its exterior appearance is linear pattern or spiral line type, is monodimension nanometer material; Template nano-high molecule fiber is to adopt polymerization to be prepared from, and is monodimension nanometer material.
4. the preparation method of templated chemistry plating nano-metal pipe according to claim 1, it is characterized in that: carbon nano-fiber or nano-high molecule fiber wash in absolute ethyl alcohol, in the mixed solution of butanols and dimethylbenzene, wash afterwards, remove surperficial organic molecule pollutant.
5. the preparation method of templated chemistry plating nano-metal pipe according to claim 1 is characterized in that:
Described strong acid is nitric acid and/or sulfuric acid.
6. the preparation method of templated chemistry plating nano-metal pipe according to claim 4 is characterized in that: the volume ratio of butanols, dimethylbenzene is 1: 3～1: 5.
7. the preparation method of templated chemistry plating nano-metal pipe according to claim 5, it is characterized in that: described strong acid is the mixture of nitric acid and sulfuric acid, the volume ratio of nitric acid, sulfuric acid is 3: 1～1: 1, and treatment temperature is 65～75 ℃, processing time 10～20min.
8. the preparation method of templated chemistry plating nano-metal pipe according to claim 1 is characterized in that:
Described surfactant is: lauryl sodium sulfate; Sodium dodecyl benzenylsulfonate; AEO; In the NPE one or more, soak time are 1.0～1.5h.
9. the preparation method of templated chemistry plating nano-metal pipe according to claim 1 is characterized in that:
Remove template in 300～450 ℃ of high-temperature process 60～180min oxidation in the step (5).
10. the preparation method of templated chemistry plating nano-metal pipe according to claim 1 is characterized in that:
Under hydrogen atmosphere, at 300～400 ℃ of high-temperature process 60～120min, reducing metal oxide obtains nano metal pipe in the step (6).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100452457A CN100402200C (en) | 2005-11-21 | 2005-11-21 | Method for preparing nano metal pipe by template chemical plating process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100452457A CN100402200C (en) | 2005-11-21 | 2005-11-21 | Method for preparing nano metal pipe by template chemical plating process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1775427A CN1775427A (en) | 2006-05-24 |
| CN100402200C true CN100402200C (en) | 2008-07-16 |
Family
ID=36765214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100452457A Expired - Fee Related CN100402200C (en) | 2005-11-21 | 2005-11-21 | Method for preparing nano metal pipe by template chemical plating process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100402200C (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436701C (en) * | 2006-11-03 | 2008-11-26 | 湘潭大学 | Method for preparing super fine light conductive fibre |
| CN101122574B (en) * | 2007-09-13 | 2010-08-25 | 山西大学 | Modified palladium electrode preparation method |
| CN101736402B (en) * | 2008-11-19 | 2011-11-30 | 中国科学院合肥物质科学研究院 | Method for preparing bamboo-shaped three-dimensional branched nano-wire |
| KR101305072B1 (en) * | 2009-12-30 | 2013-09-11 | 제일모직주식회사 | Carbon nanofiber-metal composite and method for preparing the same |
| CN102191489B (en) * | 2011-04-28 | 2012-10-10 | 上海交通大学 | Method for preparing metal material with biomorphic fine hierarchical structural morphology |
| US8833434B2 (en) * | 2012-06-08 | 2014-09-16 | GM Global Technology Operations LLC | Pt nanotubes |
| CN103708416A (en) * | 2013-12-20 | 2014-04-09 | 武汉纺织大学 | Preparation method for electro-conductive magnetic nanotube |
| CN106365210A (en) * | 2016-08-29 | 2017-02-01 | 浙江工业大学 | Preparation and application of shape-controlled cobaltosic oxide nano array |
| CN106917076B (en) * | 2017-01-24 | 2020-04-28 | 齐鲁工业大学 | Conical nano nickel and preparation method thereof |
| CN106917080B (en) * | 2017-03-06 | 2019-03-12 | 齐鲁工业大学 | The preparation method of Ni-Au alloy nanotube |
| CN106917079B (en) * | 2017-03-06 | 2019-03-12 | 齐鲁工业大学 | Chemically plating for Au-Pt alloy nanotube method |
| CN106890997B (en) * | 2017-03-06 | 2019-04-02 | 齐鲁工业大学 | The preparation method of Ni-Pd nano metal pipe |
| CN107475697B (en) * | 2017-08-14 | 2019-10-11 | 江苏大学 | A kind of carbon nano tube surface chemical Ni-P plating plating solution and method |
| JP7083483B2 (en) * | 2018-02-09 | 2022-06-13 | 学校法人福岡大学 | Modification method of polypropylene resin molded article, modified polypropylene resin molded article and its manufacturing method |
| CN110653379A (en) * | 2018-06-28 | 2020-01-07 | 宁波山功新材料科技有限公司 | Preparation method of degradable metal nanowires |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011375A1 (en) * | 2002-07-26 | 2004-02-05 | Eidgenössische Technische Hochschule Zürich | Method for the production of transition metal oxide nanotubes and nanotubes produced according to the method |
| CN1487108A (en) * | 2003-07-28 | 2004-04-07 | 南京大学 | Ordered 2D and 3D nano structure metal material comprising hollow metal spheres and its prepn process |
| WO2004106231A1 (en) * | 2003-05-29 | 2004-12-09 | Riken | Method for producing nanotube material and nanotube material |
| CN1657655A (en) * | 2004-02-18 | 2005-08-24 | 中国科学院金属研究所 | Preparation method of nano metal pipe |
-
2005
- 2005-11-21 CN CNB2005100452457A patent/CN100402200C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011375A1 (en) * | 2002-07-26 | 2004-02-05 | Eidgenössische Technische Hochschule Zürich | Method for the production of transition metal oxide nanotubes and nanotubes produced according to the method |
| WO2004106231A1 (en) * | 2003-05-29 | 2004-12-09 | Riken | Method for producing nanotube material and nanotube material |
| CN1487108A (en) * | 2003-07-28 | 2004-04-07 | 南京大学 | Ordered 2D and 3D nano structure metal material comprising hollow metal spheres and its prepn process |
| CN1657655A (en) * | 2004-02-18 | 2005-08-24 | 中国科学院金属研究所 | Preparation method of nano metal pipe |
Non-Patent Citations (2)
| Title |
|---|
| 纳米螺旋碳纤维表面金属涂层的制备. 宋瑞霞，谢广文，崔作林，石玉龙.青岛科技大学学报(自然科学版)，第26卷第5期. 2005 |
| 纳米螺旋碳纤维表面金属涂层的制备. 宋瑞霞，谢广文，崔作林，石玉龙.青岛科技大学学报(自然科学版)，第26卷第5期. 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1775427A (en) | 2006-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100402200C (en) | Method for preparing nano metal pipe by template chemical plating process | |
| CN100564595C (en) | The method of multiple-wall carbon nanotube chemical nickel plating on surface zinc | |
| CN1312034C (en) | Process for preparing monocrystalline silicon nano line array with single axial arranging | |
| CN1150997C (en) | Method for coating mono-metal particles on carbon nano tube surface | |
| CN106493386A (en) | The octahedral shape Nanoalloy of octahedra Nanoalloy and porous, Preparation Method And The Use | |
| CN105458292B (en) | A kind of carbon nano tube/copper raw powder's production technology | |
| CN105251480B (en) | A kind of preparation method of palladium mesopore silicon oxide core-shell nano catalysis material | |
| CN102732863A (en) | Method for preparing magnetic-field-assisted graphite carbon material chemical plating magnetic metal | |
| CN106994347A (en) | A kind of method for preparing square copper nano-particle grapheme foam nickel material | |
| CN110344040A (en) | A kind of preparation method of the ultralight high-entropy alloy with microarray structure | |
| CN111041459A (en) | Hollow tube micro-lattice material with nano gradient structure and preparation method thereof | |
| CN113290242A (en) | Micro-nano porous functional device, additive manufacturing method and application thereof | |
| Liu et al. | Mechanism of ultrasonic treatment under nickel salt solution and its effect on electroless nickel plating of carbon fibers | |
| CN109913893A (en) | A kind of ferriferous oxide micron chip self-supporting electrode and its synthetic method | |
| CN100569361C (en) | Pd carried iolite honeycomb ceramic catalyze material and preparation method thereof | |
| CN102153129A (en) | Method and device for continuously synthesizing spherical micro-nano cuprous oxide powder | |
| US20100266846A1 (en) | Method of producing metal nanoparticles continuously and metal nanoparticles produced thereby | |
| CN106283615B (en) | A kind of compliant conductive polyimide/silver composite nano tube and preparation method thereof | |
| KR101628362B1 (en) | Porous metal/cnt composite and method for manufacturing the same | |
| CN105776200B (en) | A kind of photo catalytic reduction continuously prepares the device and method of graphene | |
| CN101306832A (en) | Method for preparing hollow multilevel copper oxide nano material | |
| CN110385135A (en) | A kind of carbon-coated method of transition metal oxide self assembly | |
| CN104674199A (en) | Method for performing palladium-free activation electroless copper plating on basalt fiber | |
| CN107857250A (en) | A kind of melamine foam in-situ growing carbon nano tube composite superhydrophobic material and preparation method thereof | |
| TWI414481B (en) | Combined Preparation of Carbon Nanotube Composite Conductive Films with Metal Nanoparticles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: QINGDAO UNIVERSITY OF SCIENCE AND TECHNOLOGY Free format text: FORMER OWNER: XIE GUANGWEN Effective date: 20080711 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20080711 Address after: No. 53, Zhengzhou Road, Sifang District, Shandong, Qingdao Patentee after: Qingdao University of Science & Technology Address before: No. 53, Zhengzhou Road, Sifang District, Shandong, Qingdao Patentee before: Xie Guangwen |
|
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |