CN107313022B - Caliber and the controllable metal micro pipe and preparation method thereof of wall thickness - Google Patents
Caliber and the controllable metal micro pipe and preparation method thereof of wall thickness Download PDFInfo
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- CN107313022B CN107313022B CN201710542334.5A CN201710542334A CN107313022B CN 107313022 B CN107313022 B CN 107313022B CN 201710542334 A CN201710542334 A CN 201710542334A CN 107313022 B CN107313022 B CN 107313022B
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- wall thickness
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5873—Removal of material
Abstract
The present invention provides the controllable metal micro pipes and preparation method thereof of caliber and wall thickness.The preparation method of the caliber and the controllable metal micro pipe of wall thickness includes: successively to immerse polymer fiber material ultrasonic in acetone soln, ethanol solution and HCl solution, is cleaned, dry；The metal injection film on polymer fiber material；It is made annealing treatment in air atmosphere, obtains crude product；Crude product is impregnated in HCl solution, cleans, dry, obtains caliber and the controllable metal micro pipe of wall thickness.The present invention also provides the controllable metal micro pipes of the caliber and wall thickness that are obtained by above-mentioned preparation method.The easy to operate, condition of preparation method of the invention is controllable, safe and reliable, energy conservation and environmental protection, and very wide application prospect is possessed in fields such as metal catalytic, electronic device and clean energy resourcies.
Description
Technical field
The present invention relates to the controllable metal micros of a kind of preparation method of metal tube more particularly to a kind of caliber and wall thickness
Pipe/nanotube preparation method, belongs to technical field of inorganic material.
Background technique
The advantages that metal micro pipe/nanotube is because of its excellent mechanical property, good electric conductivity and bigger serface,
Before the fields such as catalytic field, electro-catalysis field, lithium ion battery, supercapacitor and fuel cell possess very wide application
Scape.
Metal micro pipe/nanotube preparation method mainly grows and etches at present.Wherein, growth mainly includes electricity
The technologies such as plating, chemical plating and atomic layer deposition, this makes preparation condition be difficult to control, and the caliber and wall thickness of obtained micron tube are difficult
With unified, dispersion is uneven, and certain technologies needs carry out in particular solution or particular atmosphere, the waste liquid exhaust gas of generation
Environment is not only polluted, is also easy to cause some safety accidents.Etching needs the coating for making special pattern in substrate or urges
Agent reduces working efficiency, while to obtain the control of higher precision, it is necessary to more to increase the complexity of operation
Accurate etching apparatus, this is undoubtedly added significantly to cost.
Therefore, find it is a kind of it is easy to operate, condition is controllable, safe and reliable, energy conservation and environmental protection, while can control metal micro again
Pipe/nanotube caliber, wall thickness, ingredient and the number of plies, and can guarantee that metal micro pipe/evenly dispersed method of nanotube becomes
It is necessary to.
Summary of the invention
In order to solve the above-mentioned technical problem, the purpose of the present invention is to provide a kind of easy to operate, conditions controllably, safely can
It leans on, energy conservation and environmental protection, while can control the preparation method of metal micro pipe/nanotube caliber, wall thickness, ingredient and the number of plies again.
In order to achieve the above technical purposes, the metal micro pipe/nanometer controllable the present invention provides a kind of caliber and wall thickness
Pipe and preparation method thereof, the caliber and the controllable metal micro pipe/nanotube preparation method of wall thickness the following steps are included:
5g polymer fiber material is immersed in acetone soln, the 50mL- of 50mL-100mL (preferably 60mL) respectively
Ultrasound 5min- in the ethanol solution of 100mL (preferably 60mL) and the HCl solution of 50mL-100mL (preferably 60mL)
20min (preferably 10min), cleaning, drying；
The metal injection film on polymer fiber material；
It is made annealing treatment in air atmosphere, obtains crude product；
Crude product is impregnated in HCl solution, cleans, dry, obtains caliber and the controllable metal micro pipe/nanometer of wall thickness
Pipe.
Specifically, when the diameter of the polymer fiber material selected is nanoscale, metal nano-tube can be obtained；It is elected
When the polymer fiber material selected is micron order, metal micro pipe can be obtained.
In the controllable metal micro pipe/nanotube preparation method of caliber and wall thickness of the invention, it is preferable that use
Polymer fiber material includes the linear polymerics material such as wet tissue, silk, polyacrylonitrile；It is highly preferred that polymer fiber material
For wet tissue.Specific embodiment according to the present invention, polymer fiber material are allowed to be paved into thin film when in use.
Specific embodiment according to the present invention, ultrasonic purpose are to remove organic additive and other impurities.
In the controllable metal micro pipe/nanotube preparation method of caliber and wall thickness of the invention, to preparing metal film
The metal of Shi Caiyong does not require, and can according to need the suitable metal species of selection, as long as can complete by sputtering technology
Plated film.
In the controllable metal micro pipe/nanotube preparation method of caliber and wall thickness of the invention, it is preferable that preparation gold
It when belonging to film is carried out in magnetron sputtering apparatus, wherein the air pressure of magnetron sputtering is 5.1 × 10-3Pa, argon flow are
15sccm-30sccm (more preferably 23.5sccm), sputtering power 100W-250W, sputtering time 0.5min-6min.
Specific embodiment according to the present invention, in the polymer fiber material for being paved into thin film when preparing metal film
The uniform sputtering metal membrane in two sides, the thickness of metal film can according to need to be adjusted by adjusting sputtering parameter.
In the controllable metal micro pipe/nanotube preparation method of caliber and wall thickness of the invention, it is preferable that use
The concentration of HCl solution is 0.1mol/L-5mol/L；It is highly preferred that the concentration of HCl solution is 1mol/L.Here to HCl solution
The restriction of concentration is used in HCl solution ultrasonic step suitable for above-mentioned preparation method and in HCl solution in soaking step
HCl solution.
In the controllable metal micro pipe/nanotube preparation method of caliber and wall thickness of the invention, it is preferable that at annealing
Reason is that 0.5h-2h is heated at 400 DEG C -500 DEG C, then with furnace natural cooling, wherein heating rate be 1 DEG C/min-10 DEG C/
min；It is highly preferred that annealing can carry out in tube furnace.
In the controllable metal micro pipe/nanotube preparation method of caliber and wall thickness of the invention, it is preferable that at annealing
Reason is that 1h is heated at 500 DEG C, then with furnace natural cooling, wherein heating rate is 2 DEG C/min.
Specific embodiment according to the present invention, the purpose of annealing are that polymer fiber material is pyrolyzed into water and titanium dioxide
Carbon, to obtain that there is the metal micro of specific caliber and wall thickness pipe/nanotube.
In the controllable metal micro pipe/nanotube preparation method of caliber and wall thickness of the invention, it is preferable that drying is
The dry 6h-24h at 50 DEG C -100 DEG C；It is highly preferred that drying is the dry 12h at 60 DEG C.Here to the restriction of drying process
All drying steps suitable for above-mentioned preparation method.
Specific embodiment according to the present invention, cleaning step is cleaning in deionized water 5 times or more times, with complete
Clear remaining impurity.
The present invention also provides the controllable metal micro pipe/nanotubes of a kind of caliber and wall thickness, and the caliber and wall thickness are controllable
Metal micro pipe/nanotube be to be prepared by above-mentioned preparation method.
Above-mentioned caliber of the invention and the controllable metal micro pipe/nanotube of wall thickness are in metal catalytic, electronic device and clear
The fields such as the clean energy have a wide range of applications.
The controllable metal micro pipe/nanotube preparation method of caliber and wall thickness provided by the invention, is a kind of sacrificial mold
Metal micro pipe/nanotube preparation method of plate is to sacrifice template with polymer fiber material.By selecting specific sacrifice
The diameter of template (polymer fiber material) indirectly controls micron tube/nanotube caliber, passes through the adjustment of magnetron sputtering parameter
Micron tube/nanotube wall thickness is controlled, metal micro pipe/nanotube of various calibers and wall thickness can be prepared.
The controllable metal micro pipe/nanotube preparation method of caliber and wall thickness of the invention sacrifices template by control
Diameter indirectly control metal micro pipe/nanotube caliber；Metal micro pipe/receive is controlled by the adjustment of magnetron sputtering parameter
The wall thickness of mitron can prepare metal micro pipe/nanotube of various calibers and wall thickness；By the target control for selecting unlike material
The ingredient of metal micro pipe/nanotube processed；Metal micro pipe/nanotube caliber number of plies is controlled by the number of control sputtering.
The controllable metal micro pipe/nanotube preparation method of caliber and wall thickness of the invention does not appoint the type of metal
What limit, micron tube/nanotube of various metals and alloy can be prepared, and can control its length, caliber, wall thickness, at
Point and the number of plies.
The controllable metal micro pipe/nanotube even thickness of caliber and wall thickness of the invention is uniformly dispersed, along length
Straight linear structure is presented in direction, is ideal one-dimentional structure.
The controllable metal micro pipe/nanotube preparation method of caliber and wall thickness of the invention, will not generate pollution waste liquid,
Expensive instrument and complicated operation are not needed yet.Preparation method of the invention is easy to operate, raw material is easy to get, environmental-friendly, is
Largely prepare metal micro pipe/ideal method of nanotube.
Detailed description of the invention
Fig. 1 is the SEM picture of the wet tissue template in embodiment 1.
Fig. 2 is the diameter dimension statistical chart of the wet tissue template in embodiment 1.
Fig. 3 is the SEM picture of the wet tissue for having sputtered silverskin in embodiment 1.
Fig. 4 is the SEM picture of the Silver microtube in embodiment 1.
Fig. 5 is the EDS curve of the Silver microtube in embodiment 1.
Fig. 6 is the SEM picture of the wet tissue for having sputtered copper film in embodiment 2.
Fig. 7 is the SEM picture of the copper micron tube in embodiment 2.
Fig. 8 is the EDS curve of the copper micron tube in embodiment 2.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out following detailed description, but should not be understood as the restriction to the enforceable range of this hair.
Embodiment 1
Present embodiments provide a kind of preparation method for the Silver microtube that caliber is about 5 μm and wall thickness is about 30nm, packet
Include following steps:
Wet tissue is selected to sacrifice template, it is spread out into a thin layer of film, SEM figure is as shown in Figure 1；Wet tissue template
Diameter is 11.10 μm, and diameter dimension statistics is as shown in Figure 2；
The HCl solution that 5g wet tissue is successively immersed in the acetone soln of 60mL, the ethanol solution of 60mL and 60mL is (dense
Then degree cleans 5 with deionized water to remove organic additive therein and other impurities for ultrasound 10min in 1mol/L)
It is secondary, with fully erased remaining impurity, dry 12h is put into baking oven at 60 DEG C；
Wet tissue is put into magnetron sputtering apparatus, sputters the silverskin that a layer thickness is 30nm on the two sides of film；Magnetic control splashes
The air pressure penetrated is set as 5.0 × 10-3Pa, argon flow are set as 23.5sccm, sputtering power 250W, and sputtering time is
1.5min, target are selected as 99.99% silver medal target；The SEM for having sputtered the wet tissue of silverskin is as shown in Figure 3；
Anneal at 500 DEG C 1h in the tube furnace of air atmosphere, and heating rate is set as 2 DEG C/min, naturally cold with furnace
But, make wet tissue pyrolysis at H2O and CO2It dissipates, to obtain crude product；
Obtained crude product is impregnated in HCl solution (concentration 1mol/L), to remove the oxidation of metal surface formation
Object obtains pure metal, is then cleaned 5 times with deionized water, is put into baking oven at 60 DEG C dry 12h, obtaining wall thickness is about 30nm
Silver microtube, since Silver microtube can be shunk in annealing process, obtained Silver microtube caliber is about 5 μm.Silver
The SEM image of micron tube is as shown in figure 4, the EDS curve of Silver microtube is as shown in Figure 5.
Embodiment 2
A kind of preparation method for the copper micron tube that caliber is about 3.6 μm and wall thickness is about 32nm is present embodiments provided,
The following steps are included:
It selects wet tissue to sacrifice template, it is spread out into a thin layer of film；The diameter of wet tissue template is 11.10 μm；
The HCl solution that 5g wet tissue is successively immersed in the acetone soln of 60mL, the ethanol solution of 60mL and 60mL is (dense
Then degree cleans 5 with deionized water to remove organic additive therein and other impurities for ultrasound 10min in 1mol/L)
It is secondary, with fully erased remaining impurity, dry 12h is put into baking oven at 60 DEG C；
Wet tissue is put into magnetron sputtering apparatus, sputters the copper film that a layer thickness is on the two sides of film；Magnetron sputtering
Air pressure is set as 5.0 × 10-3Pa, argon flow are set as 23.5sccm, sputtering power 100W, sputtering time 2min, target
Material is selected as 99.99% copper target；The SEM for having sputtered the wet tissue of copper film is as shown in Figure 6；
Anneal at 500 DEG C 1h in the tube furnace of air atmosphere, and heating rate is set as 2 DEG C/min, naturally cold with furnace
But, make wet tissue pyrolysis at H2O and CO2It dissipates, to obtain crude product；
Obtained crude product is impregnated in HCl solution (concentration 1mol/L), to remove the oxidation of metal surface formation
Object obtains pure metal, is then cleaned 5 times with deionized water, is put into baking oven at 60 DEG C dry 12h, obtaining wall thickness is about 32nm
Copper micron tube, since copper micron tube can be shunk in annealing process, obtained copper micron tube caliber is about 3.6 μm.
The SEM image of copper micron tube is as shown in fig. 7, the EDS curve of copper micron tube is as shown in Figure 8.
Embodiment 3
A kind of preparation method for the zinc micron tube that caliber is about 6.1 μm and wall thickness is about 175nm is present embodiments provided,
The following steps are included:
It selects wet tissue to sacrifice template, it is spread out into a thin layer of film；The diameter of wet tissue template is 11.10 μm；
The HCl solution that 5g wet tissue is successively immersed in the acetone soln of 60mL, the ethanol solution of 60mL and 60mL is (dense
Then degree cleans 5 with deionized water to remove organic additive therein and other impurities for ultrasound 10min in 1mol/L)
It is secondary, with fully erased remaining impurity, dry 12h is put into baking oven at 60 DEG C；
Wet tissue is put into magnetron sputtering apparatus, sputters the zinc film that a layer thickness is 175nm on the two sides of film；Magnetic control splashes
The air pressure penetrated is set as 5.0 × 10-3Pa, argon flow are set as 23.5sccm, sputtering power 200W, and sputtering time is
5min, target are selected as 99.99% zinc target；
Anneal at 500 DEG C 1h in the tube furnace of air atmosphere, and heating rate is set as 2 DEG C/min, naturally cold with furnace
But, make wet tissue pyrolysis at H2O and CO2It dissipates, to obtain crude product；
Obtained crude product is impregnated in HCl solution (concentration 1mol/L), to remove the oxidation of metal surface formation
Object obtains pure metal, is then cleaned 5 times with deionized water, is put into baking oven at 60 DEG C dry 12h, obtaining wall thickness is about 175nm
Zinc micron tube, since zinc micron tube can be shunk in annealing process, obtained zinc micron tube caliber is about 6.1 μm.
Embodiment 4
Present embodiments provide a kind of preparation method for the Silver microtube that caliber is about 5 μm and wall thickness is about 20nm, packet
Include following steps:
It selects wet tissue to sacrifice template, it is spread out into a thin layer of film；The diameter of wet tissue template is 11.10 μm；
The HCl solution that 5g wet tissue is successively immersed in the acetone soln of 60mL, the ethanol solution of 60mL and 60mL is (dense
Then degree cleans 5 with deionized water to remove organic additive therein and other impurities for ultrasound 10min in 1mol/L)
It is secondary, with fully erased remaining impurity, dry 12h is put into baking oven at 60 DEG C；
Wet tissue is put into magnetron sputtering apparatus, sputters the silverskin that a layer thickness is 20nm on the two sides of film；Magnetic control splashes
The air pressure penetrated is set as 5.0 × 10-3Pa, argon flow are set as 23.5sccm, sputtering power 250W, and sputtering time is
1min, target are selected as 99.99% silver medal target；
Anneal at 500 DEG C 1h in the tube furnace of air atmosphere, and heating rate is set as 2 DEG C/min, naturally cold with furnace
But, make wet tissue pyrolysis at H2O and CO2It dissipates, to obtain crude product；
Obtained crude product is impregnated in HCl solution (concentration 1mol/L), to remove the oxidation of metal surface formation
Object obtains pure metal, is then cleaned 5 times with deionized water, is put into baking oven at 60 DEG C dry 12h, obtaining wall thickness is about 20nm
Silver microtube, since Silver microtube can be shunk in annealing process, obtained Silver microtube caliber is about 5 μm.
Above embodiments explanation, caliber of the invention and the controllable metal micro pipe/nanotube preparation method of wall thickness
Easy to operate, raw material is easy to get, is environmental-friendly, is largely to prepare metal micro pipe/ideal method of nanotube.
Claims (6)
1. the preparation method of a kind of caliber and the controllable metal micro pipe of wall thickness, which is characterized in that the caliber and wall thickness are controllable
The preparation method of metal micro pipe the following steps are included:
5g wet tissue is immersed in the acetone soln of 50mL-100mL, the ethanol solution and 50mL- of 50mL-100mL respectively
Ultrasound 5min-20min in the HCl solution of 100mL, cleaning, drying；
The metal injection film in wet tissue；It is to be carried out in magnetron sputtering apparatus when preparing metal film, wherein the air pressure of magnetron sputtering
It is 5.1 × 10-3Pa, argon flow 15sccm-30sccm, sputtering power 100W-250W, sputtering time 0.5min-
6min；
It is made annealing treatment in air atmosphere, obtains crude product；Annealing is to heat 0.5h-2h at 400 DEG C -500 DEG C,
Then with furnace natural cooling, wherein heating rate is 1 DEG C/min-10 DEG C/min；
Crude product is impregnated in HCl solution, cleans, dry, obtains caliber and the controllable metal micro pipe of wall thickness.
2. the preparation method of caliber according to claim 1 and the controllable metal micro pipe of wall thickness, which is characterized in that HCl
The concentration of solution is 0.5mol/L-5mol/L.
3. the preparation method of caliber according to claim 1 or 2 and the controllable metal micro pipe of wall thickness, which is characterized in that
The concentration of HCl solution is 1mol/L.
4. the preparation method of caliber according to claim 1 and the controllable metal micro pipe of wall thickness, which is characterized in that annealing
Processing is to heat 1h at 500 DEG C, wherein heating rate is 2 DEG C/min.
5. the preparation method of caliber according to claim 1 and the controllable metal micro pipe of wall thickness, which is characterized in that described
Drying is the dry 6h-24h at 50 DEG C -100 DEG C.
6. the preparation method of caliber according to claim 1 and the controllable metal micro pipe of wall thickness, which is characterized in that dry
It is the dry 12h at 60 DEG C.
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| CN107313022B true CN107313022B (en) | 2019-08-02 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657655A (en) * | 2004-02-18 | 2005-08-24 | 中国科学院金属研究所 | Preparation method of nano metal pipe |
| CN103708416A (en) * | 2013-12-20 | 2014-04-09 | 武汉纺织大学 | Preparation method for electro-conductive magnetic nanotube |
| CN103990793A (en) * | 2014-05-09 | 2014-08-20 | 北京威士恩科技有限公司 | High-length-to-diameter-ratio solid-walled hollow gold/gold-silver nanotube and manufacturing method thereof |
| CN104264283A (en) * | 2014-09-29 | 2015-01-07 | 上海交通大学 | Metal micro/nano-tubes and preparation method thereof |
-
2017
- 2017-07-05 CN CN201710542334.5A patent/CN107313022B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657655A (en) * | 2004-02-18 | 2005-08-24 | 中国科学院金属研究所 | Preparation method of nano metal pipe |
| CN103708416A (en) * | 2013-12-20 | 2014-04-09 | 武汉纺织大学 | Preparation method for electro-conductive magnetic nanotube |
| CN103990793A (en) * | 2014-05-09 | 2014-08-20 | 北京威士恩科技有限公司 | High-length-to-diameter-ratio solid-walled hollow gold/gold-silver nanotube and manufacturing method thereof |
| CN104264283A (en) * | 2014-09-29 | 2015-01-07 | 上海交通大学 | Metal micro/nano-tubes and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| "化学镀模板法制备纳/微米金属管/空心金属微球及其催化性能研究";李小丽;《中国优秀硕士学位论文全文数据库•工程技术I辑》;20140115(第1期);第13页倒数第5行至第17页第11行 |
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