CN1787123A - Method for preparing coaxial nano cable with polymer covering layer - Google Patents
Method for preparing coaxial nano cable with polymer covering layer Download PDFInfo
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- CN1787123A CN1787123A CN 200410075522 CN200410075522A CN1787123A CN 1787123 A CN1787123 A CN 1787123A CN 200410075522 CN200410075522 CN 200410075522 CN 200410075522 A CN200410075522 A CN 200410075522A CN 1787123 A CN1787123 A CN 1787123A
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Abstract
一种聚合物包覆层同轴纳米电缆的制备方法，用多孔材料为模板，市售通用聚合物为聚合物材料，通过熔融法、溶液法或化学合成法将聚合物大分子植入多孔材料模板中，形成聚合物纳米管，然后以此含有聚合物纳米管的多孔材料模板为“二次模板”，通过电化学沉积等方法在聚合物纳米管中植入异质材料，形成聚合物为包覆层的同轴纳米电缆，其工艺简单，操作性强，适用面广，可选择不同聚合物包覆层和被包覆材料的品种，具有密封性强，电绝缘和柔性好的特点。可根绝各种有害物质对纳米电缆中金属等纳米线的侵蚀，阵列型同轴纳米电缆相互接触时绝缘，可适应纳米器件制备的需要而弯曲且不致损坏，可在电子纳米器件领域中广泛应用。A method for preparing polymer-coated coaxial nanocables, using porous materials as templates, commercially available general-purpose polymers as polymer materials, and implanting polymer macromolecules into porous materials by melting method, solution method or chemical synthesis In the template, polymer nanotubes are formed, and then the porous material template containing polymer nanotubes is used as a "secondary template", and heterogeneous materials are implanted in polymer nanotubes by electrochemical deposition and other methods to form polymers as The coated coaxial nano-cable has the advantages of simple process, strong operability, and wide application range. Different polymer coating layers and types of coated materials can be selected. It has the characteristics of strong sealing, good electrical insulation and flexibility. It can eradicate the erosion of metal and other nanowires in nanocables by various harmful substances. The array-type coaxial nanocables are insulated when they are in contact with each other. They can adapt to the needs of nanodevices without being damaged. They can be widely used in the field of electronic nanodevices. .
Description
Technical field:
The present invention relates to a kind of application technology of nano material, particularly a kind of preparation method of polymers for general use coating layer coaxial nano cable.
Technical background:
Metal nanometer line is subjected to people's great attention as the most important material of nano-device.A large amount of studies show that metal nanometer line combines nanometer size effect, metalline and big aspect ratio together, as quasi-one-dimensional quantized system, has significant non-linear and quantum effect.It has great potential practical value in fields such as super large integrated circuit, optical fiber, microelectronics, electroluminescence, micro-electron beam, single-electron device, chemical sensor, perpendicular magnetic recording instrument, selective solar absorber, catalysis.In recent years, the research in this field launched rapidly, utilized chemistry and physical method successfully to assemble various metal nanometer lines, studied the focus that its various properties have become nanosecond science and technology circle.Data shows that up to the present, the metal nanometer line of being developed comprises Pd, Cd, Mo, Au, Ag, Cu, Ni, Fe, Co or the like is nearly all has the metal of using value all to make nano wire, and has found their the numerous unusual character at aspects such as electricity, magnetics, optics.Undoubtedly, metal nanometer line will be played the part of unusual important role in following nano electron device.
Yet well-known, most of metal all compares vivaciously, oxidized easily and corrosion; And the surface activity of metal nanometer line is high unusually, very easily oxidized and corrosion during the contact malaria.Even make nano-device, also be easy to the performance and the reduction of service life of reducing nano-device significantly owing to oxide etch.Also there be (especially array structures) such as electric insulation problems in addition.This is the great difficult problem of pendulum in face of the scientific worker, also is the strategic problem in exploitation of metal Nano structure device and the application, needs to be resolved hurrily.The optimal path that addresses this problem is exactly that these nano metal lines are put on " coat " that can play a protective role---Here it is coaxial nano cable (Coaxial Nanocable).
Coaxial nano cable (Coaxial Nanocable) is meant that core is the nano wire of semiconductor or conductor, coats heterogeneous nanometer housing (conductor or non-conductor) outward, and external shell and core line form coaxial complex.Because this class material has particular performances, abundant scientific meaning, application prospects, and in following nano structure device, occupy an important strategic position, caused the great interest of people in recent years.The relevant semiconductor of the research of this aspect is more as heart yearn, and for example, 1997, French scientist C.Colliex etc. found the coaxial nano cable of C-BN-C structure the earliest.After, as the coaxial nano cable of SiC/BN of ZnO/SiO2, the Linlin Chen of the U.S. etc. of the β-SiC/SIO2 of the Zhang Yuegang of Japan and Iijima etc. (arrange from inside to outside, down with), L.Dai etc. or the like.China nano material expert Zhang Lide etc. uses colloidal sol-gel and carbon thermal reduction and evaporation-coacervation, has successfully synthesized the coaxial nano cable of β-SiC/SIO2 insulator.Or the like.
Yet most important and have that the using value content---metal is the coaxial nano cable of heart yearn most as coaxial nano cable, research is just at the early-stage, and majority is all not satisfactory.In only several pieces of documents, studying more is with inorganic material clad metal nano wire, and secondly being has two pieces with conducting polymer clad metal nano wire, only has one piece to be document with non-conductive polymer clad metal nano wire, because preparation method's problem, the result is not ideal enough.Prepared the coaxial nano cable that BN coats Fe as Renzhi Ma etc.; Konstantin B. etc. has prepared the coaxial nano cable of BN coating copper etc.J.-X.Zhang etc. coat nanowires of gold with the poly-thiophene phenol of template preparation; Huaqiang Cao etc. have prepared polyaniline with template and have coated Fe nanowire; But it is big that the Inorganic Non-metallic Materials clad metal prepares difficulty, complex process, and the high temperature that needs that has could be realized, especially because the very much not flexible and easy fracture of Inorganic Non-metallic Materials fragility.Even the Inorganic Non-metallic Materials that has and melts combine are not firm, and there is the slit centre, does not have due protective effect.Easily oxidation of conducting polymer itself, and naked are difficult to play due anti-oxidant and insulation protection effect.Haoqing Hou etc. makes nano wire with polylactic acid electrospinning, utilize chemical vapor deposition method that Parylene is deposited on the polylactic acid nano line then, making solvent with platinic acid extracts PLA and displacement out, form the coaxial nano cable that Parylene coats platinum by high annealing again, this is one piece of unique document with non-conductive polymer clad metal nano wire.But the electromicroscopic photograph from document as can be seen, though external diameter all compares evenly in the PPX nanotube before annealing, but the annealed size of handling the formed Parylene in back/platinum coaxial nano cable is but very inhomogeneous, this be since under the high temperature annealing in process make due to the product distortion.
Summary of the invention:
The objective of the invention is to overcome the shortcoming that prior art exists, seek to provide a kind of simple, the polymers for general use that raw material is easy to get is the preparation method of the coaxial nano cable of coating layer.Is template with porous material earlier, commercially available polymers for general use is a polymeric material, polymer macromolecule is implanted in the porous material template formation polymer nanotube by fusion method or solwution method or chemical synthesis; Be " secondary template " with this porous material template that contains polymer nanotube then, implant dissimilar materials through methods such as electrochemical depositions in polymer nanotube again, forming polymer is the coaxial nano cable of coating layer.This method technology is simple, workable, widely applicable.Can select the kind of different polymer covering layers and encapsulated material as required, particularly as the coaxial nano cable of polymer-coated metal, it is strong to have sealing, electric insulation and flexible good characteristics.Can stop the erosion of various harmful substances to nano wires such as metals in the nano-cable, insulation when the array type coaxial nano cable is in contact with one another can adapt to the needs of nano-device preparation and crooked and unlikely damage.Be expected to be used widely in fields such as electronics nano-devices.The external diameter of polymer nanotube is that the external diameter of coaxial nano cable can be controlled by the template of selecting different apertures, and the internal diameter of polymer nanotube can be by the concentration of polymer solution, implant temperature, implant number of times etc. controls.Coaxial nano cable can be a multilayer, promptly can make the many coating layers of a core, and its outermost layer is a polymeric material, and nexine and sandwich layer are other polymer or dissimilar materials.
" secondary template " that preparation contains polymer nanotube is core of the present invention, its preparation method is, at first polymer is implanted in the porous material by fusion method or solwution method or chemical synthesis, polymer enters in the hole by self assembly and forms nanotube, and then through means such as solution erosion and grindings, the excess polymer material on porous material two sides is removed, exposed the nanometer pore, promptly get " secondary template ".
The polymer that the present invention adopts is meant commercially available melting or soluble polymer, comprises TPO, polyamide-based, polystyrene type, polyacrylate, polyesters, polyethers, fluoropolymers, chlorine-containing polymer, polyurethanes etc.; Or the multicomponent polymer that can react, comprise epoxy resin, phenolic resins class etc.; Or the alloy of above-mentioned mixture of polymers or above-mentioned polymer and other material etc.
The porous material that the present invention adopts is meant inorganic porous material and organic porous materials such as Merlon, polyester such as glass of multiaperture pellumina, porous silica material, porous channel array, the aperture of porous material is preferably in the 50-1000 nanometer in the 30-3000 nanometer.
The step of solwution method preparation " secondary template " is: earlier with polymer dissolution in corresponding solvent, be made into certain density polymer solution, with a little this drips of solution on the porous material template, normal pressure or apply certain outer depressing (flowability on polymer solution is decided), polymer solution can enter in the hole of template automatically, and in solvent evaporates, polymer macromolecule is deposited on the template hole wall, after treating that solution evaporation finishes, promptly form polymer nanotube.The concentration range of polymer solution is 0.1-99wt%, is preferably in 0.2-50wt%.
The step of fusion method preparation " secondary template " is: but a little polymer is heated to flow regime, be placed on then on the foraminous die plate or and be placed on the polymer melt foraminous die plate, normal pressure or apply certain outer depressing (flowability on polymer melt is decided), polymer can enter in the pattern hole automatically, and polymer macromolecule forms polymer nanotube by self assembly in template.The polymer heating-up temperature with its complete fusion, have good mobilely and be difficult for being decomposed into principle, general temperature controlling range can be at 10-800 ℃.
The step of chemical synthesis preparation " secondary template " is: but template is put into organic monomer or corresponding additive systems such as reacting oligomer and initator thereof, when realizing polymerization reaction, polymer is implanted in the porous material template, and polymer macromolecule forms polymer nanotube by self assembly in template.
In the preparation process of " secondary template ", the external diameter of polymer nanotube can be controlled by the template of selecting different apertures, and the internal diameter of polymer nanotube can be by the concentration of polymer solution, implant temperature, implant number of times etc. controls.
After " secondary template " made, can implant different polymer once more, make the multiple layer polymer nanotube, carry out the preparation that multilayer coats coaxial nano cable as template again with it.
Second step of preparation coaxial nano cable is to implant dissimilar materials in " secondary template ", and dissimilar materials is full of polymer nanotube, forms coaxial nano cable.Dissimilar materials wherein comprises metal and alloy, polymer and blend thereof, inorganic non-metallic compound etc.; The method for implantation of dissimilar materials comprises electrochemical deposition method, colloidal sol-gel implantation, fusion implantation, solution implantation, chemical synthesis implantation etc. in the coaxial nano cable.
Specific embodiments:
Embodiment 1
With the example that is prepared as of nylon 66 clad metal platinum coaxial nano cables, illustrate that polymer of the present invention is the preparation method and the submicroscopic structure thereof of the coaxial nano cable of coating layer.
1, raw material component
1. raw material: commercially available injection molding grade nylon 66; Commercially available formic acid; Commercially available NaOH;
2. foraminous die plate: porous alumina formwork (AAO template), Whatman company produces, template diameter 13mm; Thickness 60 μ m; Normal pore size 200nm.
2, test apparatus
1. JSM-840 (JEOL) type scanning electron microscopy.
2. JEM-2000EX (JEOL) transmission electron microscope.
3, the preparation of " secondary template "
1. prepare: with the AAO template with ultrasonic waves for cleaning to remove surface blot; And nylon 66 is dissolved in makes 5% solution in the formic acid;
2. nylon 66 is implanted the AAO templates: nylon 66 drips of solution that prepare on slide, are lain in the AAO template on the drop again, stop experiment when solution infiltrates into the template upper surface, place stand-by.
3. the preparation of " secondary template ": grind off the nylon 66 on above-mentioned AAO template two sides with superfine alumina powder, make the two sides all expose nano-pore, this template is " secondary template ";
4. ESEM (SEM) test: will be fixed on the slide with double faced adhesive tape with the AAO of nanotube, remove partial oxidation aluminium after, vacuum metallizing is observed with scanning electron microscopy;
5. transmission electron microscope (TEM) test: the AAO template that will have nanotube places the NaOH solution of 3.0M (mole), leave standstill the AAO template is dissolved fully, again with this drips of solution having on the copper mesh of film, under transmission electron microscope, observe.
By scanning and transmission electron microscope observing as can be known, about 250 nanometers of nylon 66 nanotube external diameters of method for preparing, about 70 nanometers of wall thickness.
4, nylon 66 coats the preparation of platinum coaxial nano cable
With conducting resinl " secondary template " is fixed on the electro-conductive glass as work electrode, carries out electro-deposition in three-electrode system, used electrolyte is 0.2mM H
4PtCl
6+ 0.2M NaH
2PO
4+ 0.2M Na
2HPO
4, deposition potential is-0.5V to deposit 24 hours.Can make the nylon 66 that is included in the template and coat the platinum coaxial nano cable, remove alumina formwork with the sodium hydroxide solution dissolving again, can obtain nylon 66 and coat the platinum coaxial nano cable.
By transmission electron microscope and sem observation, can clearly observe the formation of coaxial nano cable.
Embodiment 2
With the example that is prepared as of thermoplastic polyurethane clad metal platinum coaxial nano cable, illustrate that polymer of the present invention is the preparation method and the submicroscopic structure thereof of the coaxial nano cable of coating layer.
1, raw material component
1. raw material: commercially available injection grade thermoplastic polyurethane; Commercially available NaOH;
2. foraminous die plate: porous alumina formwork (AAO template), Whatman company produces, template diameter 13mm; Thickness 60 μ m; Normal pore size 200nm.
2, test apparatus
With embodiment 1.
3, the preparation of " secondary template "
1. prepare: with the AAO template with ultrasonic waves for cleaning to remove surface blot;
2. polyurethane is implanted the AAO template: the polyurethane section is placed on the controllable temperature heating platform, be warming up to happy and harmonious state, the AAO template is lain on the molten drop, melt infiltration stops experiment to the template upper surface, place stand-by.
3. the preparation of " secondary template ": grind off the layer of polyurethane on above-mentioned AAO template two sides with superfine alumina powder, make the two sides all expose nano-pore, this template is " secondary template ";
4. ESEM (SEM) test: will be fixed on the slide with double faced adhesive tape with the AAO of nanotube, remove partial oxidation aluminium after, vacuum metallizing is observed with scanning electron microscopy;
5. transmission electron microscope (TEM) test: the AAO template that will have nanotube places the NaOH solution of 3.0M (mole), leave standstill the AAO template is dissolved fully, again with this drips of solution having on the copper mesh of film, under transmission electron microscope, observe.By scanning and transmission electron microscope observing as can be known, about 260 nanometers of thermoplastic polyurethane nanotube external diameter of method for preparing, about 75 nanometers of wall thickness.
4, polyurethane coats the preparation of platinum coaxial nano cable
With conducting resinl " secondary template " is fixed on the electro-conductive glass as work electrode.Carry out electro-deposition in three-electrode system, used electrolyte is 0.2mM H
4PtCl
6+ 0.2M NaH
2PO
4+ 0.2M Na
2HPO
4, deposition potential is-0.5V, deposits 24 hours, can make the polyurethane that is included in the template and coat the platinum coaxial nano cable, removes alumina formwork with the sodium hydroxide solution dissolving again, can obtain polyurethane and coat the platinum coaxial nano cable.
By transmission electron microscope and sem observation, can clearly observe and form coaxial nano cable.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410075522 CN1787123A (en) | 2004-12-12 | 2004-12-12 | Method for preparing coaxial nano cable with polymer covering layer |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102723500A (en) * | 2012-06-15 | 2012-10-10 | 武汉理工大学 | Three-dimensional (3D) array metal-proton conductor high polymer coaxial nanowire single electrode and ordering membrane electrode and preparation method thereof |
| TWI417904B (en) * | 2007-03-15 | 2013-12-01 | Union Carbide Chem Plastic | A power cable with reduced electrical treeing and a method for reducing electrical treeing |
| CN103482565A (en) * | 2013-09-16 | 2014-01-01 | 中国工程物理研究院激光聚变研究中心 | Method for preparing porous array polyethylene template |
| CN106928613A (en) * | 2017-04-12 | 2017-07-07 | 中国科学院化学研究所 | Multicomponent cable-type nanofiber array and preparation method thereof |
-
2004
- 2004-12-12 CN CN 200410075522 patent/CN1787123A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI417904B (en) * | 2007-03-15 | 2013-12-01 | Union Carbide Chem Plastic | A power cable with reduced electrical treeing and a method for reducing electrical treeing |
| US8680399B2 (en) | 2007-03-15 | 2014-03-25 | Union Carbide Chemicals & Plastics Technology Llc | Cable insulation with reduced electrical treeing |
| CN102723500A (en) * | 2012-06-15 | 2012-10-10 | 武汉理工大学 | Three-dimensional (3D) array metal-proton conductor high polymer coaxial nanowire single electrode and ordering membrane electrode and preparation method thereof |
| CN103482565A (en) * | 2013-09-16 | 2014-01-01 | 中国工程物理研究院激光聚变研究中心 | Method for preparing porous array polyethylene template |
| CN103482565B (en) * | 2013-09-16 | 2015-07-22 | 中国工程物理研究院激光聚变研究中心 | Method for preparing porous array polyethylene template |
| CN106928613A (en) * | 2017-04-12 | 2017-07-07 | 中国科学院化学研究所 | Multicomponent cable-type nanofiber array and preparation method thereof |
| CN106928613B (en) * | 2017-04-12 | 2019-03-26 | 中国科学院化学研究所 | Multicomponent cable-type nanofiber array and preparation method thereof |
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