CN102480003B - Preparation method of metamaterial and metamaterial - Google Patents
Preparation method of metamaterial and metamaterial Download PDFInfo
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- CN102480003B CN102480003B CN 201110074095 CN201110074095A CN102480003B CN 102480003 B CN102480003 B CN 102480003B CN 201110074095 CN201110074095 CN 201110074095 CN 201110074095 A CN201110074095 A CN 201110074095A CN 102480003 B CN102480003 B CN 102480003B
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- super material
- metamaterial
- function plate
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q15/00—Devices for reflection, refraction, diffraction or polarisation of waves radiated from an antenna, e.g. quasi-optical devices
- H01Q15/0006—Devices acting selectively as reflecting surface, as diffracting or as refracting device, e.g. frequency filtering or angular spatial filtering devices
- H01Q15/0086—Devices acting selectively as reflecting surface, as diffracting or as refracting device, e.g. frequency filtering or angular spatial filtering devices said selective devices having materials with a synthesized negative refractive index, e.g. metamaterials or left-handed materials
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- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The invention provides a preparation method of a metamaterial and the metamaterial, wherein the dielectric constant and the magnetic conductivity of the metamaterial can be set flexibly in the preparation method. The metamaterial prepared by the method is formed by combining multiple layers of metamaterial functional plates. Each of the metamaterial functional plates comprises a dielectric substrate and a plurality of artificial microstructures arranged in arrays on the dielectric substrate. Integrally formed materials are formed among the metamaterial functional plates. The integrally formed materials are prepared by a sol-gel process. By means of the preparation method of the metamaterial and the metamaterial provided by the invention, the dielectric constant and the magnetic conductivity of the metamaterial can be designed flexibly, and wider material selectivity is realized, so that the functional application range of the metamaterial is greatly expanded.
Description
[technical field]
The present invention relates to super Material Field, relate to particularly the compound technology of preparing of super material.
[background technology]
So-called super material refers to artificial composite structure or composite material that some have the not available extraordinary physical property of natural material.Structurally ordered design by on the key physical yardstick of material can break through the restriction of some apparent natural law, thereby obtains to exceed the intrinsic common meta-materials function of nature.As, super material has the super material function flaggy of multilayer to fold or array forms, and super material function plate forms the material behavior that super material can provide various common materials to have and do not have by medium substrate and a plurality of metal micro structures that are arranged on the medium substrate.Single metal micro-structural size is generally less than 1/10 wavelength, and it has electroresponse or magnetic response to extra electric field or magnetic field, thereby has the effective dielectric constant of showing or equivalent permeability, perhaps wave impedance.The effective dielectric constant of metal micro structure and equivalent permeability (or wave impedance) are determined by the cell geometry dimensional parameters, can artificially design and control.And metal micro structure can have the electromagnetic parameter of artificial design, thereby produces the phenomenon of many novelties.
The general array of artificial micro-structural of existing super material function plate is in surface or the inside of medium substrate, the super material function plate of each layer combined closely and formed whole super material, the effective dielectric constant of its unit or equivalent permeability are the stack of dielectric constant or the magnetic permeability of medium substrate and artificial micro-structural, because the restriction that the selection of medium substrate is used by super material function, its dielectric constant and magnetic permeability alternative limited, so can only realize by changing artificial micro-structural the change of effective dielectric constant or the equivalent permeability of whole super material, although and artificial micro-structural can realize electromagnetic wave is produced specific response by the rule of specifically arranging, but dielectric constant and the magnetic permeability of the whole super material of impact that can not be in a big way, therefore the still flexibility of design of the size of whole super material monolithic dielectric constant and magnetic permeability is inadequate, has a lot of limitation.
[summary of the invention]
Technical problem to be solved by this invention provides a kind of super material preparation method that can set flexibly super material dielectric constant and magnetic permeability size, and a kind of super material that is obtained by this preparation method is provided.
The present invention realizes that the technical scheme that goal of the invention adopts is that a kind of super material preparation method may further comprise the steps:
A. a plurality of artificial micro-structurals of array on the medium substrate of super material function plate form super material function plate;
B. a plurality of super material function plates are fixed in the mould by predetermined spacing;
C. the reactant of selecting to be used for solgel reaction according to dielectric constant and/or the magnetic permeability of super material require;
D. reactant is mixed the precursor liquid that obtains solgel reaction;
E. precursor liquid is injected in the described mould, carry out solgel reaction;
F. the super material of solgel reaction in the mould after fully carried out drying, obtain super material after the demoulding.
Solgel reaction process in the described e step is that precursor liquid obtains colloidal sol through hydrolysis first, then obtains wet gel through condensation or polymerization reaction.
Preferably, also comprise a heat treatment step behind the drying steps in the described f step, described heat treatment step is the high temperature sintering step to described super material.
Preferably, among the described step a, by chemical etching, plating, brill quarter, photoetching, electronics is carved or ion is carved a plurality of artificial micro-structurals of method array on the medium substrate of super material function plate.
The present invention also provides a kind of super material, combined by the super material function plate of multilayer, described super material function plate comprises medium substrate and the array a plurality of artificial micro-structural on medium substrate, it is characterized in that: be formed with the integrated molding material between the described super material function plate, described integrated molding material is prepared by sol gel process.
Use super material preparation method of the present invention and super material, can at random design by dielectric constant and the magnetic permeability of sol gel process technology to super material, has widely material selectivity, thereby greatly expanded the function range of application of super material, simultaneously the present invention can reach Nano grade by the interval insulant between the prepared super material function plate of sol gel process technology, have good homogeneity, thereby make super material more accurate in the control of overall dielectric constant and magnetic permeability.
[description of drawings]
Fig. 1, the structure chart of super material function plate.
Fig. 2, the super material function plate in the mould of packing into.
Fig. 3, the super material in the solgel reaction.
Fig. 4, the cut-away view of super material.
Among the figure, 1 surpass material function plate, 2 xerogel materials, 3, collosol and gel, 4 moulds, 11 medium substrates, 12 artificial micro-structurals.
[embodiment]
The present invention is described in detail below in conjunction with drawings and Examples.
Super material is combined by the super material function plate of multilayer, super material function plate comprises medium substrate and the array a plurality of artificial micro-structural on medium substrate, the main effect of medium substrate is to adapt to the needs of applied environment with fixing artificial micro structure array in mechanical performance, in selection, can select pottery, macromolecular material, polytetrafluoroethylene, ferroelectric material, ferrite material, ferromagnetic material etc., can select on demand according to different applications.Artificial micro-structural can be selected various metal materials, by designing the concrete structure of each artificial micro-structural, can make artificial micro-structural present on the whole certain rule of arranging, and then electromagnetic wave is formed some specific response, uses to reach concrete function.Existing super material structurally generally is that the super material function plate of multilayer closely is laminated, and depend on the material of medium substrate in the size that has satisfied its overall dielectric constant of applicable while of merit and magnetic permeability, thereby selectivity is limited.
Take super material with macromolecular material medium substrate as example, although macromolecular material has good mechanical performance, but the general dielectric constant of macromolecular material is low, for obtaining higher dielectric constant, adopt method of the present invention can select easily to have the CaCu 3 Ti 4 O (CaCu of high-k
3Ti
4O
12) by the super material of sol gel process preparation, its concrete preparation process is as follows:
A. a plurality of artificial micro-structurals of array on the medium substrate of super material function plate form super material function plate;
B. a plurality of super material function plates are fixed in the mould by predetermined spacing;
C. Ca: Cu: Ti is that 1: 3: 4 the accurate weighing calcium nitrate of ratio (concentration 99%), copper nitrate (concentration 99.5%), butyl titanate (analyzing pure) is stand-by in molar ratio, with absolute ethyl alcohol as solvent, take glacial acetic acid as chelating agent, prepare stand-by take citric acid as the colloid complexing agent;
D. add fast butyl titanate in the absolute ethyl alcohol, add a certain amount of glacial acetic acid behind the rapid stirring, obtain the mixed solution of homogeneous transparent, then add nitric acid control solution system for acid, after 1 hour calcium nitrate and copper nitrate are slowly joined in the butyl titanate solution, slowly stirring reaction added citric acid after 1 hour, and the molal quantity that the molal quantity of citric acid and GOLD FROM PLATING SOLUTION belong to ion is suitable, obtains the precursor liquid of solgel reaction;
E. precursor liquid is injected in the mould, at room temperature carry out solgel reaction and obtain the transparent glaucous wet gel that is;
F. to wet gel place 35 the degree drying boxes in about 18 hours, obtain super material after the demoulding.
The process schematic representation of present embodiment can be referring to accompanying drawing 1-accompanying drawing 3, Fig. 1 is the structure chart of super material function plate, Fig. 2 is the interior super material function plate of mould of packing into, Fig. 3 is the super material in the solgel reaction, the cut-away view of the super material that is made by said method can be with reference to the accompanying drawings 4, xerogel material 2 between the super material function plate 1 of each layer forms by the super material function plate 1 of multilayer and integrated molding, super material function plate 1 comprises medium substrate 11 and the array a plurality of artificial micro-structural 12 on medium substrate, because be formed with xerogel material 2 between the super material function plate 1, so by should being improved at the dielectric constant of integral body by super material that said method makes, not only material selectivity is large, and preparation technology is simple and convenient.
Should be appreciated that when the less dielectric constant of super material require those skilled in the art can according to the performance parameter of material, be prepared by sol gel process after suitably selecting fully.
Embodiment 2
Sometimes, obtain higher magnetic permeability for making super material, can realize easily after adopting method of the present invention, to have the cobalt Ni ferrite (Co of high magnetic permeability
1-xNi
xFe
2O
4) be example, as follows by the detailed process of the super material of sol gel process preparation:
A. a plurality of artificial micro-structurals of array on the medium substrate of super material function plate form super material function plate;
B. a plurality of super material function plates are fixed in the mould by predetermined spacing;
C. at first take by weighing a certain amount of citric acid and join in the distilled water heated at constant temperature in 80 ℃ water bath with thermostatic control, after dissolving fully, citric acid adds successively ferric nitrate, cobalt nitrate and nickel nitrate, wherein, the mol ratio of cobalt nickel ion is 0.5: 0.5, and the mol ratio of ferric nitrate and citric acid is 1: 1;
D. it is mixed the mentioned solution strong stirring, obtain precursor liquid;
E. precursor liquid is injected in the mould, at room temperature carry out the transparent wet gel that solgel reaction obtains brown color, place 80 ℃ baking oven drying to obtain xerogel on mould;
F. mould is placed Muffle furnace 300 ℃ temperature lower calcination 1 hour, obtain super material after the demoulding.
The super material that is made by said method is formed with the cobalt Ni ferrite (Co with high magnetic permeability owing between the super material function plate
0.5Ni
0.5Fe
2O
4), so the whole magnetic permeability of super material is improved, should be appreciated that by sol gel process and can select for super material provides various suitable magnetic permeabilitys that it designs quite flexible, preparation technology is simple and convenient.
In the above-described embodiments, only the present invention has been carried out exemplary description, but those skilled in the art can carry out various modifications to the present invention after reading present patent application in the situation that does not break away from the spirit and scope of the present invention.
Claims (4)
1. super material preparation method may further comprise the steps:
A. a plurality of artificial micro-structurals of array on the medium substrate of super material function plate form super material function plate;
B. a plurality of super material function plates are fixed in the mould by predetermined spacing;
C. the reactant of selecting to be used for solgel reaction according to dielectric constant and/or the magnetic permeability of super material require;
D. reactant is mixed the precursor liquid that obtains solgel reaction;
E. precursor liquid is injected in the described mould, carry out solgel reaction;
F. the super material of solgel reaction in the mould after fully carried out drying, obtain super material after the demoulding.
2. a kind of super material preparation method according to claim 1 is characterized in that: the solgel reaction process in the described e step is that precursor liquid obtains colloidal sol through hydrolysis first, then obtains wet gel through condensation or polymerization reaction.
3. a kind of super material preparation method according to claim 1, it is characterized in that: also comprise a heat treatment step behind the drying steps in the described f step, described heat treatment step is the high temperature sintering step to described super material.
4. according to claim 1 to 3 arbitrary described a kind of super material preparation methods, it is characterized in that: among the described step a, by chemical etching, plating, brill quarter, photoetching, electronics is carved or ion is carved a plurality of artificial micro-structurals of method array on the medium substrate of super material function plate.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110074095 CN102480003B (en) | 2011-03-25 | 2011-03-25 | Preparation method of metamaterial and metamaterial |
| PCT/CN2011/084493 WO2012129944A1 (en) | 2011-03-25 | 2011-12-23 | Metamaterial manufacturing method and metamaterial |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110074095 CN102480003B (en) | 2011-03-25 | 2011-03-25 | Preparation method of metamaterial and metamaterial |
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| Publication Number | Publication Date |
|---|---|
| CN102480003A CN102480003A (en) | 2012-05-30 |
| CN102480003B true CN102480003B (en) | 2013-02-13 |
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|---|---|---|---|
| CN 201110074095 Active CN102480003B (en) | 2011-03-25 | 2011-03-25 | Preparation method of metamaterial and metamaterial |
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| CN (1) | CN102480003B (en) |
| WO (1) | WO2012129944A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321117A (en) * | 1999-09-16 | 2001-11-07 | 日本板硝子株式会社 | Method for producing article having predetermined surface shape, and optical waveguide element |
| CN1778742A (en) * | 2004-10-18 | 2006-05-31 | 三星电子株式会社 | Sol-gel process and method for manufacturing optical crystal fiber using the same |
| CN101774769A (en) * | 2010-02-05 | 2010-07-14 | 中国科学院广州能源研究所 | Method for preparing sandwich freeze-dried gel heat insulating glass |
| CN102109685A (en) * | 2009-12-29 | 2011-06-29 | 中国科学院物理研究所 | Multilayer electromagnetism modulating structure and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2003213609A1 (en) * | 2002-02-28 | 2003-09-16 | University Of Delaware | Left handed materials using magnetic composites |
| US7256753B2 (en) * | 2003-01-14 | 2007-08-14 | The Penn State Research Foundation | Synthesis of metamaterial ferrites for RF applications using electromagnetic bandgap structures |
| EP1887843A1 (en) * | 2005-04-28 | 2008-02-13 | Mitsui Mining & Smelting Co., Ltd. | Method for oxide dielectric layer formation, and capacitor layer forming material comprising oxide dielectric layer formed by said formation method |
| US7301493B1 (en) * | 2005-11-21 | 2007-11-27 | The United States Of America As Represented By The Secretary Of The Army | Meta-materials based upon surface coupling phenomena to achieve one-way mirror for various electro-magnetic signals |
| JP2008147737A (en) * | 2006-12-06 | 2008-06-26 | Yamaguchi Univ | One-dimensional left-hand system metamaterial |
-
2011
- 2011-03-25 CN CN 201110074095 patent/CN102480003B/en active Active
- 2011-12-23 WO PCT/CN2011/084493 patent/WO2012129944A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321117A (en) * | 1999-09-16 | 2001-11-07 | 日本板硝子株式会社 | Method for producing article having predetermined surface shape, and optical waveguide element |
| CN1778742A (en) * | 2004-10-18 | 2006-05-31 | 三星电子株式会社 | Sol-gel process and method for manufacturing optical crystal fiber using the same |
| CN102109685A (en) * | 2009-12-29 | 2011-06-29 | 中国科学院物理研究所 | Multilayer electromagnetism modulating structure and preparation method thereof |
| CN101774769A (en) * | 2010-02-05 | 2010-07-14 | 中国科学院广州能源研究所 | Method for preparing sandwich freeze-dried gel heat insulating glass |
Non-Patent Citations (2)
| Title |
|---|
| 孙义传.Sol-gel法制备低温共烧多层陶瓷基板用高硅玻璃.《现代技术陶瓷》.1995,(第3期),19-21. * |
| 徐政 * |
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| Publication number | Publication date |
|---|---|
| WO2012129944A1 (en) | 2012-10-04 |
| CN102480003A (en) | 2012-05-30 |
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