CN107313022A - Caliber and the controllable metal micro pipe/nanotube of wall thickness and preparation method thereof - Google Patents

Caliber and the controllable metal micro pipe/nanotube of wall thickness and preparation method thereof Download PDF

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CN107313022A
CN107313022A CN201710542334.5A CN201710542334A CN107313022A CN 107313022 A CN107313022 A CN 107313022A CN 201710542334 A CN201710542334 A CN 201710542334A CN 107313022 A CN107313022 A CN 107313022A
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nanotube
wall thickness
caliber
preparation
metal micro
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CN107313022B (en
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杨峰
张晓峰
崔立山
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China University of Petroleum Beijing
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China University of Petroleum Beijing
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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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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  • Nanotechnology (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
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Abstract

The invention provides controllable metal micro pipe/nanotube of caliber and wall thickness and preparation method thereof.The preparation method of the caliber and the controllable metal micro pipe/nanotube of wall thickness includes：Polymer fiber material is immersed to ultrasonic in acetone soln, ethanol solution and HCl solution successively, cleans, dries；Metal injection film on to polymer fiber material；Made annealing treatment in air atmosphere, obtain crude product；Crude product is soaked in HCl solution, cleans, dry, obtain caliber and the controllable metal micro pipe/nanotube of wall thickness.Present invention also offers the controllable metal micro pipe/nanotube of the caliber and wall thickness obtained by above-mentioned preparation method.The simple to operate of preparation method of the present invention, condition are controllable, safe and reliable, energy-conserving and environment-protective, and very wide application prospect is possessed in fields such as metal catalytic, electronic device and clean energy resourcies.

Description

Caliber and the controllable metal micro pipe/nanotube of wall thickness and preparation method thereof
Technical field
The present invention relates to a kind of preparation method of metal tube, more particularly to a kind of caliber and the controllable metal micro of wall thickness The preparation method of pipe/nanotube, belongs to technical field of inorganic material.
Background technology
The advantages of metal micro pipe/nanotube is because of its excellent mechanical property, good electric conductivity and bigger serface, The fields such as catalytic field, electro-catalysis field, lithium ion battery, ultracapacitor and fuel cell possess before very wide application Scape.
The preparation method of current metal micro pipe/nanotube is mainly growth and etched.Wherein, grow main including electricity The technologies such as plating, chemical plating and ald, this causes preparation condition to be difficult control, and the caliber and wall thickness of obtained micron tube are difficult With unification, disperse uneven, and some technologies need to carry out in particular solution or particular atmosphere, the waste liquid waste gas of generation Environment is not only polluted, also easily triggers some security incidents.Etching needs to make the coating of special pattern in substrate or urged Agent, so as to add the complexity of operation, reduces operating efficiency, while to obtain the control of higher precision, it is necessary to more Accurate etching apparatus, this is undoubtedly added significantly to cost.
Therefore, find that a kind of simple to operate, condition is controllable, safe and reliable, energy-conserving and environment-protective, while metal micro can be controlled again Caliber, wall thickness, composition and the number of plies of pipe/nanotube, and can guarantee that metal micro pipe/dispersed method of nanotube becomes It is necessary.
The content of the invention
In order to solve the above-mentioned technical problem, it is an object of the invention to provide a kind of simple to operate, condition is controllable, safety can Lean on, energy-conserving and environment-protective, while the preparation method of the caliber of metal micro pipe/nanotube, wall thickness, composition and the number of plies can be controlled again.
In order to realize above-mentioned technical purpose, the invention provides the controllable metal micro pipe/nanometer of a kind of caliber and wall thickness Pipe and preparation method thereof, the preparation method of the caliber and the controllable metal micro pipe/nanotube of wall thickness comprises the following steps：
5g polymer fiber materials are immersed in acetone soln, the 50mL- of 50mL-100mL (being preferably 60mL) respectively Ultrasound 5min- in 100mL (being preferably 60mL) ethanol solution and 50mL-100mL (being preferably 60mL) HCl solution 20min (being preferably 10min), cleans, dries；
Metal injection film on to polymer fiber material；
Made annealing treatment in air atmosphere, obtain crude product；
Crude product is soaked in HCl solution, cleans, dry, obtain caliber and the controllable metal micro pipe/nanometer of wall thickness Pipe.
Specifically, when a diameter of nanoscale of the polymer fiber material of selection, you can obtain metal nano-tube；It is elected The polymer fiber material selected for micron order when, you can obtain metal micro pipe.
In the caliber of the present invention and the preparation method of the controllable metal micro pipe/nanotube of wall thickness, it is preferable that use Polymer fiber material includes the linear polymeric materials such as wet tissue, silk, polyacrylonitrile；It is highly preferred that polymer fiber material For wet tissue.According to the embodiment of the present invention, polymer fiber material is allowed to be paved into thin film when in use.
According to the embodiment of the present invention, ultrasonic purpose is to remove organic additive and other impurities.
In the caliber of the present invention and the preparation method of the controllable metal micro pipe/nanotube of wall thickness, to preparing metal film Shi Caiyong metal is not required, suitable metal species can be selected as needed, as long as can be completed by sputtering technology Plated film just can be with.
In the caliber of the present invention and the preparation method of the controllable metal micro pipe/nanotube of wall thickness, it is preferable that prepare gold During category film carried out in magnetron sputtering apparatus, wherein, the air pressure of magnetron sputtering is 5.1 × 10-3Pa, argon flow amount is 15sccm-30sccm (more preferably 23.5sccm), sputtering power is 100W-250W, and sputtering time is 0.5min-6min.
According to the embodiment of the present invention, the polymer fiber material of thin film is being paved into when preparing metal film The uniform sputtering metal membrane in two sides, the thickness of metal film can be adjusted as desired by adjustment sputtering parameter.
In the caliber of the present invention and the preparation method of the controllable metal micro pipe/nanotube of wall thickness, 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 caliber of the present invention and the preparation method of the controllable metal micro pipe/nanotube of wall thickness, it is preferable that at annealing Reason is that 0.5h-2h is heated at 400 DEG C -500 DEG C, then with stove natural cooling, wherein, heating rate be 1 DEG C/min-10 DEG C/ min；It is highly preferred that annealing can be carried out in tube furnace.
In the caliber of the present invention and the preparation method of the controllable metal micro pipe/nanotube of wall thickness, it is preferable that at annealing Reason is that 1h is heated at 500 DEG C, then with stove natural cooling, wherein, heating rate is 2 DEG C/min.
According to the embodiment of the present invention, the purpose of annealing is that polymer fiber material is pyrolyzed into water and titanium dioxide Carbon, so as to obtain metal micro pipe/nanotube with specific caliber and wall thickness.
In the caliber of the present invention and the preparation method of the controllable metal micro pipe/nanotube of wall thickness, it is preferable that drying is 6h-24h is dried at 50 DEG C -100 DEG C；It is highly preferred that drying is that 12h is dried at 60 DEG C.Here to the restriction of drying process All drying steps suitable for above-mentioned preparation method.
According to the embodiment of the present invention, cleaning step is to clean in deionized water 5 times or more times, with complete The impurity clearly remained.
Present invention also offers the controllable metal micro pipe/nanotube of a kind of caliber and wall thickness, the caliber and wall thickness are controllable Metal micro pipe/nanotube prepared by above-mentioned preparation method.
The controllable metal micro pipe/nanotube of above-mentioned caliber and wall thickness of the present invention is in metal catalytic, electronic device and clear The fields such as the clean energy have a wide range of applications.
The preparation method of the controllable metal micro pipe/nanotube of caliber and wall thickness that the present invention is provided, is a kind of sacrificial mold The preparation method of metal micro pipe/nanotube of plate, using polymer fiber material as sacrifice template.Sacrificed by the way that selection is specific The caliber of diameter indirect control micron tube/nanotube of template (polymer fiber material), passes through the adjustment of magnetron sputtering parameter The wall thickness of micron tube/nanotube is controlled, metal micro pipe/nanotube of various calibers and wall thickness can be prepared.
The preparation method of the controllable metal micro pipe/nanotube of caliber and wall thickness of the invention, passes through and controls to sacrifice template Diameter indirect 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 composition of metal micro pipe/nanotube processed；By controlling the number of times of sputtering to control the caliber number of plies of metal micro pipe/nanotube.
The preparation method of the controllable metal micro pipe/nanotube of caliber and wall thickness of the invention is not appointed to the species of metal What limit, micron tube/nanotube of various metals and alloy can be prepared, and can control its length, caliber, wall thickness, into Divide and the number of plies.
The even thickness of the controllable metal micro pipe/nanotube of caliber and wall thickness of the present invention, it is uniformly dispersed, along length Straight linear structure is presented in direction, is preferable one-dimentional structure.
The preparation method of the controllable metal micro pipe/nanotube of caliber and wall thickness of the invention, will not produce pollution waste liquid, Also without expensive instrument and complicated operation.Preparation method of the invention is simple to operate, raw material is easy to get, environment-friendly, is Largely prepare metal micro pipe/preferable method of nanotube.
Brief description of the drawings
Fig. 1 be embodiment 1 in wet tissue template SEM pictures.
Fig. 2 be embodiment 1 in wet tissue template diameter dimension statistical chart.
Fig. 3 be embodiment 1 in the wet tissue for having sputtered silverskin SEM pictures.
Fig. 4 be embodiment 1 in Silver microtube SEM pictures.
Fig. 5 be embodiment 1 in Silver microtube EDS curves.
Fig. 6 be embodiment 2 in the wet tissue for having sputtered copper film SEM pictures.
Fig. 7 be embodiment 2 in copper micron tube SEM pictures.
Fig. 8 be embodiment 2 in copper micron tube EDS curves.
Embodiment
In order to which technical characteristic, purpose and beneficial effect to the present invention are more clearly understood from, now to the skill of the present invention Art scheme carry out it is described further below, but it is not intended that to this hair can practical range restriction.
Embodiment 1
The preparation method that a kind of caliber is about the Silver microtube that 5 μm and wall thickness are about 30nm is present embodiments provided, it is wrapped Include following steps：
Select wet tissue to sacrifice template, it is spread out into a thin layer of film, its SEM figures are as shown in Figure 1；Wet tissue template A diameter of 11.10 μm, its diameter dimension statistics is as shown in Figure 2；
The HCl solution that 5g wet tissues are immersed in into 60mL acetone soln, 60mL ethanol solution and 60mL successively is (dense Spend for 1mol/L) in ultrasound 10min, to remove organic additive therein and other impurities, then clean 5 with deionized water It is secondary, with the impurity of fully erased residual, it is put into baking oven at 60 DEG C and dries 12h；
Wet tissue is put into magnetron sputtering apparatus, the silverskin that a layer thickness is 30nm is sputtered on the two sides of film；Magnetic control splashes The air pressure penetrated is set to 5.0 × 10-3Pa, argon flow amount is set to 23.5sccm, and sputtering power is 250W, and sputtering time is 1.5min, target selection is 99.99% silver medal target；The SEM for having sputtered the wet tissue of silverskin is as shown in Figure 3；
Anneal 1h in the tube furnace of air atmosphere at 500 DEG C, and heating rate is set to 2 DEG C/min, naturally cold with stove But, wet tissue is made to be pyrolyzed into H2O and CO2Dissipate, so as to obtain crude product；
Obtained crude product is soaked in HCl solution (concentration is 1mol/L), to remove the oxidation of metal surface formation Thing, obtains simple metal, is then cleaned with deionized water 5 times, is put into baking oven at 60 DEG C and dries 12h, obtains wall thickness about 30nm Silver microtube, because Silver microtube can be shunk in annealing process, therefore obtained Silver microtube caliber is about 5 μm.Silver The SEM image of micron tube is as shown in figure 4, the EDS curves of Silver microtube are as shown in Figure 5.
Embodiment 2
The preparation method that a kind of caliber is about the copper micron tube that 3.6 μm and wall thickness are about 32nm is present embodiments provided, its Comprise the following steps：
Select wet tissue to sacrifice template, it is spread out into a thin layer of film；A diameter of 11.10 μm of wet tissue template；
The HCl solution that 5g wet tissues are immersed in into 60mL acetone soln, 60mL ethanol solution and 60mL successively is (dense Spend for 1mol/L) in ultrasound 10min, to remove organic additive therein and other impurities, then clean 5 with deionized water It is secondary, with the impurity of fully erased residual, it is put into baking oven at 60 DEG C and dries 12h；
Wet tissue is put into magnetron sputtering apparatus, the copper film that a layer thickness is is sputtered on the two sides of film；Magnetron sputtering Air pressure is set to 5.0 × 10-3Pa, argon flow amount is set to 23.5sccm, and sputtering power is 100W, and sputtering time is 2min, target Material selection is 99.99% copper target；The SEM for having sputtered the wet tissue of copper film is as shown in Figure 6；
Anneal 1h in the tube furnace of air atmosphere at 500 DEG C, and heating rate is set to 2 DEG C/min, naturally cold with stove But, wet tissue is made to be pyrolyzed into H2O and CO2Dissipate, so as to obtain crude product；
Obtained crude product is soaked in HCl solution (concentration is 1mol/L), to remove the oxidation of metal surface formation Thing, obtains simple metal, is then cleaned with deionized water 5 times, is put into baking oven at 60 DEG C and dries 12h, obtains wall thickness about 32nm Copper micron tube, because copper micron tube can be shunk in annealing process, therefore 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 curves of copper micron tube are as shown in Figure 8.
Embodiment 3
The preparation method that a kind of caliber is about the zinc micron tube that 6.1 μm and wall thickness are about 175nm is present embodiments provided, its Comprise the following steps：
Select wet tissue to sacrifice template, it is spread out into a thin layer of film；A diameter of 11.10 μm of wet tissue template；
The HCl solution that 5g wet tissues are immersed in into 60mL acetone soln, 60mL ethanol solution and 60mL successively is (dense Spend for 1mol/L) in ultrasound 10min, to remove organic additive therein and other impurities, then clean 5 with deionized water It is secondary, with the impurity of fully erased residual, it is put into baking oven at 60 DEG C and dries 12h；
Wet tissue is put into magnetron sputtering apparatus, the zinc film that a layer thickness is 175nm is sputtered on the two sides of film；Magnetic control splashes The air pressure penetrated is set to 5.0 × 10-3Pa, argon flow amount is set to 23.5sccm, and sputtering power is 200W, and sputtering time is 5min, target selection is 99.99% zinc target；
Anneal 1h in the tube furnace of air atmosphere at 500 DEG C, and heating rate is set to 2 DEG C/min, naturally cold with stove But, wet tissue is made to be pyrolyzed into H2O and CO2Dissipate, so as to obtain crude product；
Obtained crude product is soaked in HCl solution (concentration is 1mol/L), to remove the oxidation of metal surface formation Thing, obtains simple metal, is then cleaned with deionized water 5 times, is put into baking oven at 60 DEG C and dries 12h, obtains wall thickness about 175nm Zinc micron tube, because zinc micron tube can be shunk in annealing process, therefore obtained zinc micron tube caliber is about 6.1 μm.
Embodiment 4
The preparation method that a kind of caliber is about the Silver microtube that 5 μm and wall thickness are about 20nm is present embodiments provided, it is wrapped Include following steps：
Select wet tissue to sacrifice template, it is spread out into a thin layer of film；A diameter of 11.10 μm of wet tissue template；
The HCl solution that 5g wet tissues are immersed in into 60mL acetone soln, 60mL ethanol solution and 60mL successively is (dense Spend for 1mol/L) in ultrasound 10min, to remove organic additive therein and other impurities, then clean 5 with deionized water It is secondary, with the impurity of fully erased residual, it is put into baking oven at 60 DEG C and dries 12h；
Wet tissue is put into magnetron sputtering apparatus, the silverskin that a layer thickness is 20nm is sputtered on the two sides of film；Magnetic control splashes The air pressure penetrated is set to 5.0 × 10-3Pa, argon flow amount is set to 23.5sccm, and sputtering power is 250W, and sputtering time is 1min, target selection is 99.99% silver medal target；
Anneal 1h in the tube furnace of air atmosphere at 500 DEG C, and heating rate is set to 2 DEG C/min, naturally cold with stove But, wet tissue is made to be pyrolyzed into H2O and CO2Dissipate, so as to obtain crude product；
Obtained crude product is soaked in HCl solution (concentration is 1mol/L), to remove the oxidation of metal surface formation Thing, obtains simple metal, is then cleaned with deionized water 5 times, is put into baking oven at 60 DEG C and dries 12h, obtains wall thickness about 20nm Silver microtube, because Silver microtube can be shunk in annealing process, therefore obtained Silver microtube caliber is about 5 μm.
Above example explanation, the preparation method of the controllable metal micro pipe/nanotube of caliber and wall thickness of the invention Simple to operate, raw material is easy to get, environment-friendly, is largely to prepare metal micro pipe/preferable method of nanotube.

Claims (10)

1. the preparation method of a kind of caliber and the controllable metal micro pipe/nanotube of wall thickness, it is characterised in that the caliber and wall thickness The preparation method of controllable metal micro pipe/nanotube comprises the following steps：
5g polymer fiber materials are immersed in 50mL-100mL acetone soln, 50mL-100mL ethanol solution respectively With ultrasound 5min-20min in 50mL-100mL HCl solution, clean, dry；
Metal injection film on to polymer fiber material；
Made annealing treatment in air atmosphere, obtain crude product；
Crude product is soaked in HCl solution, cleans, dry, obtain caliber and the controllable metal micro pipe/nanotube of wall thickness.
2. the preparation method of caliber according to claim 1 and the controllable metal micro pipe/nanotube of wall thickness, its feature exists In the polymer fiber material includes wet tissue, silk or polyacrylonitrile.
3. the preparation method of caliber according to claim 1 or 2 and the controllable metal micro pipe/nanotube of wall thickness, it is special Levy and be, the polymer fiber material is wet tissue.
4. the preparation method of caliber according to claim 1 and the controllable metal micro pipe/nanotube of wall thickness, its feature exists In, it is to be carried out in magnetron sputtering apparatus when preparing metal film, wherein, the air pressure of magnetron sputtering is 5.1 × 10-3Pa, argon gas stream Measure as 15sccm-30sccm, sputtering power is 100W-250W, and sputtering time is 0.5min-6min.
5. the preparation method of caliber according to claim 1 and the controllable metal micro pipe/nanotube of wall thickness, its feature exists In the concentration of HCl solution is 0.5mol/L-5mol/L.
6. the preparation method of caliber and the controllable metal micro pipe/nanotube of wall thickness according to claim 1 or 5, it is special Levy and be, the concentration of HCl solution is 1mol/L.
7. the preparation method of caliber according to claim 1 and the controllable metal micro pipe/nanotube of wall thickness, its feature exists In, annealing is that 0.5h-2h is heated at 400 DEG C -500 DEG C, then with stove natural cooling, wherein, heating rate be 1 DEG C/ min-10℃/min。
8. the preparation method of the controllable metal micro pipe/nanotube of caliber and wall thickness according to claim 1 or 7, it is special Levy and be, annealing is to heat 1h at 500 DEG C, wherein, heating rate is 2 DEG C/min.
9. the preparation method of caliber according to claim 1 and the controllable metal micro pipe/nanotube of wall thickness, its feature exists In the drying is that 6h-24h is dried at 50 DEG C -100 DEG C；
Preferably, drying is that 12h is dried at 60 DEG C.
10. a kind of caliber and the controllable metal micro pipe/nanotube of wall thickness, it is characterised in that the caliber and the controllable gold of wall thickness It is by the controllable metal micro pipe/nanotube of the caliber and wall thickness described in claim any one of 1-9 to belong to micron tube/nanotube Preparation method prepare.
CN201710542334.5A 2017-07-05 2017-07-05 Caliber and the controllable metal micro pipe and preparation method thereof of wall thickness Expired - Fee Related CN107313022B (en)

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