CN104264283A - Metal micro/nano-tubes and preparation method thereof - Google Patents
Metal micro/nano-tubes and preparation method thereof Download PDFInfo
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- CN104264283A CN104264283A CN201410514217.4A CN201410514217A CN104264283A CN 104264283 A CN104264283 A CN 104264283A CN 201410514217 A CN201410514217 A CN 201410514217A CN 104264283 A CN104264283 A CN 104264283A
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Abstract
The invention provides metal micro/nano-tubes and a preparation method thereof. The method comprises the following steps: first, dissolving a degradable polymeric material in a spinning solvent to form a uniform and stable spinning solution; then, pouring the spinning solution into a syringe with a metal syringe needle, pushing the spinning solution out from the syringe needle at a constant speed through an injection pump, and drawing the spinning solution to a receiving pole plate through a high-voltage electric field formed between the metal syringe needle and the receiving pole plate to form micro/nano-spinning; next, sputtering metal on the surface of the obtained micro/nano-spinning; and finally, dissolving the degradable polymeric material in an organic solvent to obtain the metal micro/nano-tubes. According to the metal micro/nano-tubes prepared by the preparation method disclosed by the invention, the preparation method is simple and is easy to operate; the size parameters and the materials of the prepared metal micro/nano-tubes can be changed by changing spinning and sputtering metal parameters; the prepared metal micro/nano-tubes are wide in application field and low in preparation cost, and are favorable to large-scale repeated preparation.
Description
Technical field
The present invention relates to a kind of micro/nano structure preparation method of micro-, nanoscale science and technology field, particularly, relate to a kind of metal micro-/ nano tube preparation method.
Background technology
Nanometer science and technology to develop rapidly in recent years, diversified nano material and nanostructured because of its exclusive superior function be applied to multiple fields such as the energy, medical treatment, electronics research and in the middle of manufacturing.Metal Micro/nanotubes is as nano material, and sciemtifec and technical sphere is gathered around and had a wide range of applications ahead of the curve, comprising: micro-nano electronic device manufactures, energy resource collecting and storage and biomedical diagnostic and treatment.But most nano material and nanostructured preparation process are complicated, yield rate is low, cost is high, nanometer technology further develops and is thus restricted.Owing to having the advantage of the aspects such as preparation process is simple, production efficiency is high, cost is low, utilized the mode of electrostatic spinning to prepare in the last few years extensive concern that nano material is subject to researchers.The metal Micro/nanotubes manufacturing technique utilizing electrostatic spinning mode to prepare is simple, can prepare the dissimilar metals Micro/nanotubes of a greater number at lower cost.The metal Micro/nanotubes prepared have specific area large, can flexible transformation material and the special performance such as size, hollow conducting, can be applicable to micro-nano electronic manufacture, energy storage and the multinomial field such as conversion, biomedical diagnostic treatment.
Find by prior art documents, Zhang-Qi Feng etc. write articles " Highly aligned poly (3; 4-ethylene dioxythiophene) (PEDOT) nano-and microscale fibers and tubes " (" poly-(3,4-rthylene dioxythiophene) (PEDOT) nanometer of highly alignment and micrometer fibers and pipe " " polymer ") at POLYMER.54 (2013) 702-708.A kind of novel conductive polymer nanometer and micrometer fibers and pipe and technology of preparing thereof is referred in the document.This technology prepares the conducting polymer micron tube in consistent direction by electrostatic spinning on cylinder pole plate and the method for conducting polymer monomer liquid phase in-situ polymerization.Its shortcoming is that simple conducting polymer materials micron tube mechanical property is poor, easily occurs damaged and cracked; Liquid phase in-situ polymerization forms conducting polymer micron tube wall thickness dimension and not easily accurately controls, and the conducting polymer property management external diameter of preparation is micron-scale, is not classified as nano material.
Summary of the invention
For defect of the prior art, the object of this invention is to provide a kind of metal micro-/ nano tube preparation method, described metal micro-/ nano tube preparation method technical process is simple, electrostatic spinning and splash-proofing sputtering metal preparation technology is used to be easy to accurately control metal Micro/nanotubes material and the parameter of preparation, the wall thickness of metal Micro/nanotubes and internal diameter size parameter can be obtained by adjustment splash-proofing sputtering metal thickness and spinning diameter control respectively, are conducive to a large amount of duplication of production manufacture.
For realizing above object, the invention provides a kind of metal micro-/ nano tube preparation method, comprising the steps:
The first step, degradable polymeric material is dissolved in spin solvent, forms the spinning solution of stable homogeneous;
Second step, the spinning solution first step obtained pour in the syringe with metal needle, at the uniform velocity spinning solution is released from syringe needle with a speed by syringe pump, by the high voltage electric field formed between metal syringe needle and reception pole plate, spinning solution is drawn on reception pole plate, forms micro-/ nano spinning;
3rd step, the micro-/ nano spinning surface splash-proofing sputtering metal obtained at second step;
4th step, dissolve degradable polymeric material in organic solvent, obtain metal Micro/nanotubes.
Preferably, in the first step:
Described degradable polymeric material is PLA (PLA), any one of polyglycolic acid (PGA), polycaprolactone (PCL), polyethylene glycol (PEG) and polylactic acid-glycollic acid (PLGA) and copolymer thereof, selected degradable polymeric material all comparatively easily obtains, comparatively easily be made into spinning solution and be convenient to the enforcement of rear step electrostatic spinning step, and comparatively easily the enforcement of rear step dissolving step is convenient in dissolving in organic solvent;
Described spin solvent is chloroform (chloroform), dimethyl formamide (DMF) or both mixtures, and selected spin solvent is suitable for above-mentioned degradable polymeric material and dissolves formation spinning solution, and comparatively easily obtains;
The spinning solution of described stable homogeneous is that polymeric material is dissolved in the middle of spin solvent that uniform concentration distribution is without solid particle, and selected spinning solution state is convenient to the spinning that rear step electrostatic spinning step forms uniform-dimension.
Preferably, in the first step, described being dissolved as uses stirring and heating to make polymer dissolution in a solvent, and selected dissolving method is conducive in degradable polymeric material rapid solution and spin solvent.
Preferably, in second step;
Described metal needle to be internal diameter the be stainless steel hollow tube syringe needle of 0.1 millimeter to 2 millimeters, chosen technique needle sizes is conducive to the spinning forming setting diameter dimension in rear step electrostatic spinning process, and is conducive to high voltage electric field and is formed;
The spinning of described micro-/ nano spinning to be diameter be 10 nanometers to 10 micron, selected spinning diameter dimension scope directly determines the internal diameter of the metal Micro/nanotubes prepared;
The high voltage electric field that described metal syringe needle and receiving is formed between pole plate for using high-voltage power supply positive pole to be connected with metal syringe needle, receive pole plate with earth polar and be connected, the high voltage electric field formed between positive pole and earth polar, electric-field intensity is 0.1 kv/cm to 5 kv/cm, and selected electric field is configured with the electrostatic spinning being beneficial to and forming above-mentioned diameter dimension scope;
A described speed is 0.01 ml/hour to 10 mls/hour, and selected speed is conducive to the electrostatic spinning forming above-mentioned diameter dimension scope.
Preferably, in 3rd step, described metal is magnesium, aluminium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, zirconium, rhodium, palladium, silver, indium, tin, tungsten, iridium, platinum, gold and alloy thereof, any one of oxide and nitride, selected metal material is comparatively easily obtain, and can be deposited to the metal material on electrostatic spinning surface by sputtering technology.
Preferably, in the 3rd step, described metal thickness is 10 nanometer to 500 nanometers, and selected metal thickness size directly determines the wall thickness of the metal Micro/nanotubes prepared.
Preferably, in 4th step, described organic solvent is chloroform (chloroform), any one of dimethyl formamide (DMF), acetone, ethanol, isopropyl alcohol, benzinum and gasoline, selected organic solvent can dissolve electrospun material comparatively rapidly.
The metal Micro/nanotubes that the present invention also provides a kind of said method to prepare, described metal Micro/nanotubes is hollow structure, and material is metal, metal alloy, metal oxide or metal nitride material; The wall thickness of metal Micro/nanotubes is 10 nanometer to 500 nanometers, and internal diameter is 10 nanometers to 10 micron; The wall thickness of metal Micro/nanotubes and internal diameter size parameter can be obtained by adjustment splash-proofing sputtering metal thickness and spinning diameter control respectively.
Metal Micro/nanotubes is as nano material, and sciemtifec and technical sphere is gathered around and had a wide range of applications ahead of the curve, comprising: micro-nano electronic device manufactures, energy resource collecting and storage and biomedical diagnostic and treatment.The present invention is using electrostatic spinning as base material, and the metal Micro/nanotubes of preparation has good homogeneity and larger specific area; By converting the splash-proofing sputtering metal of sputtering technology and controlling sputtering parameter, the metal Micro/nanotubes of the different parameters of multiple unlike material can be prepared.
Compared with prior art, the present invention has following beneficial effect:
The present invention adopts the method for degradable polymer electrostatic spinning and splash-proofing sputtering metal to prepare metal micro-nano pipe, and the electrostatic spinning used and sputtering technology are all conducive to the size of metal micro-nano pipe prepared by precise hard_drawn tuhes, comprise internal diameter and wall thickness; Use the method for sputtering to prepare metal micro-nano pipe, be easy to conversion metal micro-nano tubing matter; The technical process preparing metal micro-nano pipe is simple, is easy to operation, and preparation cost is low, repeatability is high, is conducive to a large amount of preparation; The metal micro-nano pipe Application Areas made is extensive.
Accompanying drawing explanation
By reading the detailed description done non-limiting example with reference to the following drawings, other features, objects and advantages of the present invention will become more obvious:
Fig. 1 is that the present invention prepares metal Micro/nanotubes process schematic.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
Embodiment 1
As shown in Figure 1, the present embodiment provides a kind of metal micro-/ nano tube preparation method, comprising:
1. choose degradable polymer PLA, add chloroform, heat in 40 degrees Celsius of waters bath with thermostatic control and stir, until polymeric material is dissolved in uniform concentration distribution in the middle of spin solvent, without solid particle, form spinning solution;
2. being poured into by spinning solution with internal diameter is in the syringe of 0.1 millimeter of stainless steel hollow tube syringe needle, is at the uniform velocity released from syringe needle by spinning solution with 10 mls/hour by syringe pump;
3. the electric-field intensity by being formed between metal syringe needle and reception pole plate is that spinning solution is drawn on reception pole plate by the high voltage electric field of 0.1 kv/cm, forms the spinning that diameter is 10 microns;
4. the gold of 500 nanometers is sputtered at the micro-/ nano spinning surface obtained;
5. in chloroform, dissolve PLA spinning material, obtain golden micron tube.
Embodiment 2
As shown in Figure 1, the present embodiment provides a kind of metal micro-/ nano tube preparation method, comprising:
1. choose degradable polymer polycaprolactone, add chloroform and dimethyl formamide, stir under room temperature environment, until polymeric material is dissolved in uniform concentration distribution in the middle of spin solvent, without solid particle, form spinning solution;
2. being poured into by spinning solution with internal diameter is in the syringe of 0.4 millimeter of stainless steel hollow tube syringe needle, is at the uniform velocity released from syringe needle by spinning solution with 0.01 ml/hour by syringe pump;
3. the electric-field intensity by being formed between metal syringe needle and reception pole plate is that spinning solution is drawn on reception pole plate by the high voltage electric field of 5 kv/cm, forms the spinning that diameter is 10 nanometers;
4. the tin indium oxide of 10 nanometers is sputtered at the micro-/ nano spinning surface obtained;
5. dissolve polycaprolactone spinning material in acetone, obtain tin indium oxide nanotube.
Embodiment 3
As shown in Figure 1, the present embodiment provides a kind of metal micro-/ nano tube preparation method, comprising:
1. choose degradable polymer polylactic acid-glycollic acid, add dimethyl formamide, stir under room temperature environment, until polymeric material is dissolved in uniform concentration distribution in the middle of spin solvent, without solid particle, form spinning solution;
2. being poured into by spinning solution with internal diameter is in the syringe of 2 millimeters of stainless steel hollow tube syringe needles, is at the uniform velocity released from syringe needle by spinning solution with 0.2 ml/hour by syringe pump;
3. the electric-field intensity by being formed between metal syringe needle and reception pole plate is that spinning solution is drawn on reception pole plate by the high voltage electric field of 1 kv/cm, forms the spinning that diameter is 500 nanometers;
4. the platinumiridio of 200 nanometers is sputtered at the micro-/ nano spinning surface obtained;
5. in isopropyl alcohol, dissolve polylactic acid-glycollic acid spinning material, obtain platinumiridio nanotube.
Described in above-described embodiment, preparation method is using electrostatic spinning as base material, and the metal Micro/nanotubes of preparation has good homogeneity and larger specific area; By converting the splash-proofing sputtering metal of sputtering technology and controlling sputtering parameter, the metal Micro/nanotubes of the different parameters of multiple unlike material can be prepared.The metal Micro/nanotubes preparation process that the present invention proposes is simple, uses electrostatic spinning and splash-proofing sputtering metal preparation technology to be easy to accurately control metal Micro/nanotubes material and the parameter of preparation, is conducive to a large amount of duplication of production manufacture.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (10)
1. a metal micro-/ nano tube preparation method, is characterized in that, comprises the steps:
The first step, degradable polymeric material is dissolved in spin solvent, forms the spinning solution of stable homogeneous;
Second step, the spinning solution first step obtained pour in the syringe with metal needle, at the uniform velocity spinning solution is released from syringe needle with a speed by syringe pump, by the high voltage electric field formed between metal syringe needle and reception pole plate, spinning solution is drawn on reception pole plate, forms micro-/ nano spinning;
3rd step, the micro-/ nano spinning surface splash-proofing sputtering metal obtained at second step;
4th step, dissolve degradable polymeric material in organic solvent, obtain metal Micro/nanotubes.
2. a kind of metal micro-/ nano tube preparation method according to claim 1, is characterized in that, in the first step:
Described degradable polymeric material is any one in the copolymer of polylactic acid PLA, polyglycolic acid PGA, polycaprolactone (PCL), polyethylene glycol PEG, polylactic acid-glycollic acid PLGA and these degradable polymers;
Described spin solvent is chloroform, dimethyl formamide or both mixtures.
3. a kind of metal micro-/ nano tube preparation method according to claim 1 and 2, is characterized in that, in the first step, described being dissolved as uses stirring and heating to make polymer dissolution in a solvent.
4. a kind of metal micro-/ nano tube preparation method according to claim 1, is characterized in that, in second step:
Described metal needle to be internal diameter the be stainless steel hollow tube syringe needle of 0.1 millimeter to 2 millimeters;
The spinning of described micro-/ nano spinning to be diameter be 10 nanometers to 10 micron.
5. a kind of metal micro-/ nano tube preparation method according to claim 1 or 4, is characterized in that:
The high voltage electric field that described metal syringe needle and receiving is formed between pole plate for using high-voltage power supply positive pole to be connected with metal syringe needle, receive pole plate with earth polar and be connected, the high voltage electric field formed between positive pole and earth polar, electric-field intensity is 0.1 kv/cm to 5 kv/cm.
6. a kind of metal micro-/ nano tube preparation method according to claim 1 or 4, is characterized in that, in second step: described speed is 0.01 ml/hour to 10 mls/hour.
7. a kind of metal micro-/ nano tube preparation method according to claim 1, it is characterized in that, in 3rd step, described metal is magnesium, aluminium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, zirconium, rhodium, palladium, silver, indium, tin, tungsten, iridium, platinum, gold and alloy thereof, oxide and nitride.
8. a kind of metal micro-/ nano tube preparation method according to claim 1 or 7, is characterized in that, in the 3rd step, described metal thickness is 10 nanometer to 500 nanometers.
9. a kind of metal micro-/ nano tube preparation method according to claim 1, is characterized in that, in the 4th step, described organic solvent be in chloroform, dimethyl formamide DMF, acetone, ethanol, isopropyl alcohol, benzinum, gasoline any one.
10. the metal Micro/nanotubes that according to any one of claim 1-9 prepared by method, is characterized in that, described metal Micro/nanotubes is hollow structure, and material is metal, metal alloy, metal oxide or metal nitride material; The wall thickness of metal Micro/nanotubes is 10 nanometer to 500 nanometers, and internal diameter is 10 nanometers to 10 micron; The wall thickness of metal Micro/nanotubes and internal diameter size parameter can be obtained by adjustment splash-proofing sputtering metal thickness and spinning diameter control respectively.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107313022A (en) * | 2017-07-05 | 2017-11-03 | 中国石油大学(北京) | Caliber and the controllable metal micro pipe/nanotube of wall thickness and preparation method thereof |
| CN110790218A (en) * | 2019-10-31 | 2020-02-14 | 季华实验室 | Preparation method of circular micro-nano channel and product thereof |
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| US5352512A (en) * | 1989-03-15 | 1994-10-04 | The United States Of America As Represented By The Secretary Of The Air Force | Microscopic tube material and its method of manufacture |
| CN1657655A (en) * | 2004-02-18 | 2005-08-24 | 中国科学院金属研究所 | Preparation method of nano metal pipe |
| CN101545158A (en) * | 2009-05-07 | 2009-09-30 | 南京大学 | Tubular and tube-in-tube structure organic oxide and preparation method thereof |
| CN102786072A (en) * | 2012-08-16 | 2012-11-21 | 东华大学 | Method for preparing electrostatic spinning alumina hollow micro/nano tube |
| CN103409848A (en) * | 2013-08-11 | 2013-11-27 | 吉林大学 | Preparation method for metallic oxide composite nano fiber with core/casing idiosyncratic structure |
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2014
- 2014-09-29 CN CN201410514217.4A patent/CN104264283A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5352512A (en) * | 1989-03-15 | 1994-10-04 | The United States Of America As Represented By The Secretary Of The Air Force | Microscopic tube material and its method of manufacture |
| CN1657655A (en) * | 2004-02-18 | 2005-08-24 | 中国科学院金属研究所 | Preparation method of nano metal pipe |
| CN101545158A (en) * | 2009-05-07 | 2009-09-30 | 南京大学 | Tubular and tube-in-tube structure organic oxide and preparation method thereof |
| CN102786072A (en) * | 2012-08-16 | 2012-11-21 | 东华大学 | Method for preparing electrostatic spinning alumina hollow micro/nano tube |
| CN103409848A (en) * | 2013-08-11 | 2013-11-27 | 吉林大学 | Preparation method for metallic oxide composite nano fiber with core/casing idiosyncratic structure |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107313022A (en) * | 2017-07-05 | 2017-11-03 | 中国石油大学(北京) | Caliber and the controllable metal micro pipe/nanotube of wall thickness and preparation method thereof |
| CN107313022B (en) * | 2017-07-05 | 2019-08-02 | 中国石油大学(北京) | Caliber and the controllable metal micro pipe and preparation method thereof of wall thickness |
| CN110790218A (en) * | 2019-10-31 | 2020-02-14 | 季华实验室 | Preparation method of circular micro-nano channel and product thereof |
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