CN106299714A - Meta Materials and preparation method thereof - Google Patents
Meta Materials and preparation method thereof Download PDFInfo
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- CN106299714A CN106299714A CN201510253436.6A CN201510253436A CN106299714A CN 106299714 A CN106299714 A CN 106299714A CN 201510253436 A CN201510253436 A CN 201510253436A CN 106299714 A CN106299714 A CN 106299714A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 69
- 239000000463 material Substances 0.000 title abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 252
- 239000000919 ceramic Substances 0.000 claims abstract description 144
- 239000011521 glass Substances 0.000 claims abstract description 135
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000011230 binding agent Substances 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 18
- 238000005266 casting Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 9
- 230000001070 adhesive effect Effects 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000010030 laminating Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 8
- 239000002912 waste gas Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 3
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000533950 Leucojum Species 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
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- 238000002844 melting Methods 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- 230000008646 thermal stress Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 238000010345 tape casting Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
The invention provides a kind of Meta Materials and preparation method thereof.This Meta Materials includes glass substrate, ceramic substrate and connects glass substrate and the articulamentum of ceramic substrate, is additionally provided with conduction geometry between glass substrate and ceramic substrate.Glass substrate and ceramic substrate is included due in the Meta Materials that the present invention provides, so that the Meta Materials formed is not only able to effectively scavenge, decrease the Organic substance of residual in Meta Materials, reduce Meta Materials water absorption, and improve the corrosion stability of Meta Materials, and then make Meta Materials have low-loss, improve the wave transparent performance of Meta Materials.
Description
Technical Field
The invention relates to the technical field of new materials, and particularly relates to a metamaterial and a preparation method thereof.
Background
The meta-materials based on resin-based composite materials have been extensively and intensively studied. The metamaterial based on the resin-based composite material has the advantages of high strength, convenience in processing and good electrical property, but has the defect of no high temperature resistance. And the ceramic-based metamaterial can meet the characteristics of high temperature resistance, flow corrosion resistance, load resistance, high-temperature glass transmission and the like.
In the prior art, the material for preparing the ceramic-based metamaterial is usually glass or ceramic, and although the components of the glass or ceramic are the same, the properties of the glass or ceramic are greatly different. The ceramic-based metamaterial made of the glass substrate has the advantages that the compactness of the glass is high, the strength is high, the dielectric constant is large, and the glass has moisture resistance, so that the problems that the metamaterial is difficult to remove waste gas, residual organic matters are carbonized and the like easily occur; the ceramic is porous, low in compactness, low in strength, small in dielectric constant and easy to absorb moisture, so that the ceramic plate used as the ceramic-based metamaterial also has the problems that the metamaterial is easy to absorb water and is not corrosion-resistant.
Disclosure of Invention
The invention mainly aims to provide a metamaterial and a preparation method thereof, so that the metamaterial has higher performance.
In order to achieve the above object, according to one aspect of the present invention, there is provided a metamaterial including a glass substrate, a ceramic substrate, and a connection layer connecting the glass substrate and the ceramic substrate, with a conductive geometry disposed therebetween.
Further, a recessed structure located outside the periphery of the connection layer is formed between surfaces of the edge portion of the glass substrate and the edge portion of the ceramic substrate that correspond to each other.
Furthermore, the thickness of the glass substrate ranges from 0.5 mm to 30mm, the thickness of the ceramic substrate ranges from 0.5 mm to 30mm, and the thickness of the connecting layer ranges from 10 μm to 300 μm.
Furthermore, the metamaterial comprises at least two layers of glass substrates and at least two layers of ceramic substrates, the glass substrates and the ceramic substrates are arranged at intervals, a connecting layer is arranged between every two adjacent glass substrates and ceramic substrates, and a conductive geometric structure is arranged between at least one group of adjacent glass substrates and ceramic substrates; or the metamaterial comprises two layers of glass substrates and at least one layer of ceramic substrate, the ceramic substrates are arranged between the glass substrates, a connecting layer is arranged between each adjacent glass substrate and the ceramic substrate, and a conductive geometric structure is arranged between at least one group of adjacent glass substrates and the ceramic substrates.
Furthermore, the conductive geometric structure is arranged on the surface of the glass substrate or the ceramic substrate and is connected with the connecting layer; or the conductive geometric structure is arranged inside the connecting layer and is not connected with the glass substrate or the ceramic substrate.
According to another aspect of the present invention, there is provided a method for preparing a metamaterial, the method comprising the steps of: sequentially laminating a glass substrate, a connection preparation layer and a ceramic substrate to form a preparation metamaterial, wherein a conductive geometric structure is arranged between the glass substrate and the ceramic substrate; and performing heat treatment on the preliminary metamaterial to enable the connection preliminary layer to form a connection layer, and sequentially laminating the glass substrate, the connection layer and the ceramic substrate to form the metamaterial.
Further, the connection preparation layer is an adhesive, and the step of forming the preparation metamaterial comprises the following steps: and forming a conductive geometric structure in the binder, on the surface of the glass substrate or on the surface of the ceramic substrate, then placing the binder between the glass substrate and the ceramic substrate, and laminating the glass substrate, the connection preparation layer and the ceramic substrate to form the preparation metamaterial.
Further, the binder is slurry formed by mixing and reacting alumina, zirconia and phosphoric acid.
Further, heat treatment is performed to cure the adhesive to form a connection layer.
Further, the connection preparation layer is a casting sheet, and the step of forming the preparation metamaterial comprises the following steps: forming a conductive geometry on a surface of a glass substrate, a ceramic substrate, or a cast sheet, and then sequentially laminating the glass substrate, the cast sheet, and the ceramic substrate to form a preliminary metamaterial.
Further, heat treatment is performed to sinter the cast sheet to form a connection layer.
By applying the technical scheme, the metamaterial comprises a quartz glass substrate, a ceramic substrate and a connecting layer for connecting the glass substrate and the ceramic substrate, and the glass substrate and the ceramic substrate are included in the metamaterial, so that the formed metamaterial not only can effectively remove waste gas, reduce residual organic matters in the metamaterial, reduce the water absorption of the metamaterial, but also improve the corrosion resistance of the metamaterial, further enable the metamaterial to have low loss and improve the wave transmission performance of the metamaterial.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic cross-sectional view of a metamaterial having a recessed structure located outside the periphery of a connection layer according to an embodiment of the present invention;
FIG. 2 is a schematic cross-sectional view of a metamaterial having a conductive geometry disposed on a surface of a glass substrate according to an embodiment of the present invention;
FIG. 3 is a schematic cross-sectional view of a metamaterial with a conductive geometry disposed inside of a connection layer provided by an embodiment of the present invention;
FIG. 4 is a schematic structural diagram of a square ring set provided by an embodiment of the present invention;
fig. 5 is a schematic structural diagram of a square ring set provided with a first conductive strip according to an embodiment of the present invention;
FIG. 6 is a schematic structural diagram illustrating a cross-shaped structure with four ends provided with a straight structure according to an embodiment of the present invention;
FIG. 7 illustrates a schematic diagram of a conductive geometry provided by an embodiment of the present invention;
FIG. 8 is a schematic structural view of a cross-shaped structure provided with four end portions provided with quadrilateral structures according to an embodiment of the invention; and
FIG. 9 is a schematic flow chart illustrating a method for preparing a metamaterial according to an embodiment of the present invention; and
fig. 10 is a graph showing the comparison of the wave-transparent test results of example 1 of the present invention and comparative example 1.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As known in the background art, the materials for preparing the ceramic-based metamaterial in the prior art are generally glass or ceramic, and the two materials have the same composition but have larger difference in performance. The problems that the waste gas of the metamaterial is difficult to remove, residual organic matters are carbonized and the like easily occur when the ceramic-based metamaterial is made of the glass substrate; the ceramic plate is used as the ceramic-based metamaterial, and the problems that the metamaterial is easy to absorb water and is not corrosion-resistant can also occur. The inventors of the present invention have studied the above problems and have provided a metamaterial having a structure as shown in fig. 1 to 3, which includes a glass substrate 10, a ceramic substrate 20, and a connection layer 30 connecting the glass substrate 10 and the ceramic substrate 20, and a conductive geometry 40 disposed between the glass substrate 10 and the ceramic substrate 20.
Because the metamaterial comprises the glass substrate and the ceramic substrate, the glass has the advantages of high compactness, high strength, large dielectric constant and moisture resistance, and the ceramic has the advantages of low compactness, low strength, small dielectric constant and easy moisture absorption, the formed metamaterial can effectively remove waste gas, reduce residual organic matters in the metamaterial, reduce the water absorption of the metamaterial, improve the corrosion resistance of the metamaterial, further ensure that the metamaterial has low loss and improve the wave transmission performance of the metamaterial.
In the metamaterial according to the present invention, the glass substrate 10 and the ceramic substrate 20 may have the same shape and size, or may have different shapes and sizes. The connection layer 30 may be partially or fully disposed between the glass substrate 10 and the ceramic substrate 20, while the conductive geometry 40 is disposed between the glass substrate 10 and the ceramic substrate 20. Preferably, a concave structure located outside the peripheral edge of the connection layer 30 is formed between the surfaces of the edge portion of the glass substrate 10 and the edge portion of the ceramic substrate 20 corresponding to each other, and the structure thereof is as shown in fig. 1. More preferably, the edges of the glass substrate 10, the ceramic substrate 20 and the connection layer 30 are flush, and the structure thereof is as shown in fig. 2 and 3.
In the metamaterial according to the present invention, the thicknesses of the glass substrate 10, the ceramic substrate 20, and the connection layer 30 may be set according to actual requirements. Preferably, the thickness of the glass substrate 10 is 0.5 to 30mm, the thickness of the ceramic substrate 20 is 0.5 to 30mm, and the thickness of the connection layer 30 is 10 to 300 μm.
In the above-described metamaterial of the present invention, the material of the connection layer 30 may be set according to the prior art. Preferably, the connection layer 30 is formed by curing the adhesive. More preferably, the binder is composed of a material comprising aluminum phosphate and zirconium phosphate. Aluminum phosphate and zirconium phosphate are binder phases obtained by reacting aluminum oxide and zirconium oxide with phosphoric acid. Wherein, preferably, the alumina is particles with the particle size of 5-50 nm, the zirconia is particles with the particle size of 5-50 nm, the concentration of the phosphoric acid is 50-85 wt%, and the specification is analytical purity. Meanwhile, the connection layer 30 may be formed by sintering a casting sheet.
In the metamaterial of the present invention, the conductive geometric structure 40 may be disposed on the surface of the glass substrate 10 or the ceramic substrate 20, and the conductive geometric structure 40 is connected to the connection layer 30. The arrangement of the conductive geometry 40 can be set according to the prior art. Preferably, the conductive geometric structure 40 may be firstly disposed on the surfaces of the glass substrate 10 and the ceramic substrate 20, and after the glass substrate 10, the microstructure connection layer 30 and the ceramic substrate 20 are sequentially connected in a laminated manner, the conductive geometric structure 40 is also disposed on the surface of the connection layer 30; when the connection layer 30 is formed by sintering a casting sheet, the conductive geometry 40 may be first disposed on the surface of the casting sheet, and after the glass substrate 10, the sintered casting sheet, and the ceramic substrate 20 are sequentially laminated and connected, the conductive geometry 40 is similarly disposed on the surfaces of the glass substrate 10 and the ceramic substrate 20, and the structure thereof is as shown in fig. 1 to 2.
In the metamaterial of the present invention, the conductive geometric structure 40 may be disposed inside the connection layer 30, and the conductive geometric structure 40 is not connected to the glass substrate 10 or the ceramic substrate 20. That is, the conductive geometric structure 40 is disposed in a binder, the binder is disposed between the glass substrate 10 and the ceramic substrate 20, and then the binder is cured to form the connection layer 30, and the connection layer 30 connects the glass substrate 10 and the ceramic substrate 20, which is shown in fig. 3.
The conductive geometry 40 can be made of any conductive material, and can be a metallic material, such as gold, silver or copper or a mixture of several metals, preferably copper, and the original form of the metallic material used can be solid, liquid, fluid or powder; but also non-metallic materials such as conductive inks.
The number of the conductive geometric structures 40 may be multiple, and the conductive geometric structures 40 are plane or three-dimensional structures with certain geometric shapes, such as i-shaped structures, snowflake structures, and the like, made of metal. The conductive geometry 40 serves to enhance the wave-transparent properties of the metamaterial. The conductive geometry 40 is not limited to the above-described configurations, but may be other conductive geometries that respond to electromagnetic waves, such as wave-absorbing enhancement.
The conductive geometry 40 may comprise a plurality of non-connected square ring sets 41, each square ring set 41 comprising a plurality of connected square rings. The plurality of connected square rings comprises: a central square ring 411 and four outer square rings 412 connected at the four corners of the central square ring 411. Further, the size of the central square ring 411 and the outer square ring 412 may be the same or different, and it is preferable that the size of the central square ring 411 and the outer square ring 412 are the same, and the structure thereof is as shown in fig. 4. At least one first conductive strip 413 is disposed in the outer square ring 412. The first conductive strips 413 are straight conductive strips or cross conductive strips or grid conductive strips. The number and the arrangement position of the first conductive strips 413 directly affect the ranges of the low-loss band and the rejection band of the metamaterial. In the present embodiment, the first conductive strips 413 are cross-shaped conductive strips, which divide the outer square ring 412 into four square holes with the same size, and the structure thereof is shown in fig. 5.
Preferably, the conductive geometry 40 further comprises a plurality of unconnected cross-shaped structures 42 connected to and arranged in parallel with the set of square rings 41. The center of the central square ring 411 corresponds to the centers of the adjacent four cross structures 42. That is, the square ring group 41 and the cross-shaped structure 42 are arranged in a staggered manner.
In a preferred embodiment, a straight structure 43 is provided at each of the four ends of each cross structure 42, and the middle of the straight structure 43 is connected to the ends of the cross structure 43, as shown in fig. 6.
As shown in fig. 7, a cross-shaped structure 42 having the above structure and four outer square rings 412 having the above structure form a conductive geometry 40, and the structural parameters of the conductive geometry 40 are as follows: the area of the conductive geometry 40 is between 4.0mm and 6.0 mm. The thickness of the conductive geometry 40 is between 0.01 and 0.02 mm. The width of the cross-shaped structure is between 0.25mm and 0.35mm, and the length of the linear structure of the cross-shaped structure is between 3.0mm and 4.0 mm.
In another preferred embodiment, four ends of each cross 42 of the conductive geometry 40 are provided with a quadrilateral 421, and the middle of the quadrilateral 421 is connected to the ends of the cross. At this time, the first conductive strip 413 is no longer disposed in the outer square ring 412, and the structure thereof is as shown in fig. 4. The metamaterial with the structure can be transparent to waves at 0GHz to 1GHz and has low loss, and can be inhibited at 8GHz to 18 GHz.
More preferably, at least one second conductive strip 422 is disposed in the quadrilateral structure 421. Further, the second conductive strips 422 are linear conductive strips, and divide the quadrilateral structure 421 into two quadrilateral structures; alternatively, second conductive strips 422 are cross-shaped conductive strips, and a plurality of second conductive strips 422 divide quadrilateral structure 421 into grids, which is shown in fig. 8. The number and placement of second conductive strips 422 directly affect the range of the low-loss band and the rejection band of the metamaterial.
A cross-shaped structure 42 having the above-described structure and four outer square rings 412 having the above-described structure form a conductive geometry 40, the structural parameters of the conductive geometry 40 being as follows: the area of the conductive geometry 40 is between 4.0mm and 6.0mm, and the thickness of the conductive geometry 40 is between 0.0016 and 0.02 mm. When the conductive geometries 40 are plural, the distance between the conductive geometries 40 is between 1.6mm and 2.0 mm.
In the metamaterial according to the present invention, the number and arrangement of the glass substrates 10 and the ceramic substrates 20 may be set according to actual requirements. Preferably, the metamaterial comprises at least two layers of glass substrates 10 and at least two layers of ceramic substrates 20, the glass substrates 10 and the ceramic substrates 20 are arranged at intervals, a connecting layer 30 is arranged between each adjacent glass substrate 10 and ceramic substrate 20, and a conductive geometric structure 40 is arranged between at least one group of adjacent glass substrates 10 and ceramic substrates 20. Namely, the arrangement relationship of the glass substrate 10 and the ceramic substrate 20 in the metamaterial from top to bottom is A// B// A// B, wherein A is the glass substrate 10, and B is the ceramic substrate 20. As the glass substrate 10 and the ceramic substrate 20 in the metamaterial are of a symmetrical structure, the generation of macroscopic thermal stress of the metamaterial can be reduced, and the probability of forming cracks between the substrates in the metamaterial is reduced.
In the metamaterial of the present invention, the metamaterial may further include two layers of glass substrates 10 and at least one layer of ceramic substrate 20, the ceramic substrate 20 is disposed between the glass substrates 10, a connection layer 30 is disposed between each adjacent glass substrate 10 and ceramic substrate 20, and a conductive geometric structure 40 is disposed between at least one group of adjacent glass substrates 10 and ceramic substrates 20. Namely, the arrangement relationship of the glass substrate 10 and the ceramic substrate 20 in the metamaterial from top to bottom is A// B// A or A// B// B// A, wherein A is the glass substrate 10, and B is the ceramic substrate 20. As the glass substrate 10 and the ceramic substrate 20 in the metamaterial are of symmetrical structures, the macroscopic thermal stress of cracks formed between the substrates in the metamaterial can be reduced, and the probability of substrate warping in the metamaterial is reduced.
According to another aspect of the present invention, a method for preparing a metamaterial is provided, as shown in fig. 9. The preparation method comprises the following steps: sequentially laminating a glass substrate, a connection preparation layer and a ceramic substrate to form a preparation metamaterial, wherein a conductive geometric structure is arranged between the glass substrate and the ceramic substrate; and performing heat treatment on the preliminary metamaterial to enable the connection preliminary layer to form a connection layer, and sequentially laminating the glass substrate, the connection layer and the ceramic substrate to form the metamaterial.
According to the preparation method, the glass substrate and the ceramic substrate form the metamaterial, the glass has high compactness, high strength, large dielectric constant and moisture resistance, and the ceramic has low compactness, low strength, small dielectric constant and easy moisture absorption, so that the formed metamaterial can effectively remove waste gas, reduce organic matters remained in the metamaterial, reduce the water absorption of the metamaterial and improve the corrosion resistance of the metamaterial, and further the metamaterial has low loss and the wave transmission performance of the metamaterial.
An exemplary embodiment of a method for preparing a metamaterial according to the present invention will be described in more detail with reference to fig. 1 to 3. These exemplary embodiments may, however, be embodied in many different forms and should not be construed as limited to only the embodiments set forth herein. It should be understood that these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of these exemplary embodiments to those skilled in the art.
First, the glass substrate 10, the connection preparation layer, and the ceramic substrate 20 are sequentially laminated to form a preparation metamaterial, and the conductive geometry 40 is further provided between the glass substrate 10 and the ceramic substrate 20. The conductive geometric structure 40 is a planar or three-dimensional structure with a certain geometric shape, such as an i-shape and a snowflake shape, which is formed by metal particles. The conductive geometry 40 enhances the wave-transparent properties of the formed metamaterial. The conductive geometry 40 is not limited to the above-described configuration, but may be any other suitable conductive geometry for electromagnetic waves, such as wave-absorbing enhancement.
The process for forming the connection preparation layer can be various, in a preferred embodiment, the connection preparation layer is an adhesive, and the step of forming the preparation metamaterial comprises the following steps: forming a conductive geometric structure 40 in the adhesive, on the surface of the glass substrate 10 or on the surface of the ceramic substrate 20, then placing the adhesive between the glass substrate 10 and the ceramic substrate 20, and then pressing the glass substrate 10, the connection preparation layer and the ceramic substrate 20 to form a preparation metamaterial. Further, in the step of pressing, the pressure may be 5-20 mpa. The preferable pressing pressure enables the glass substrate 10, the connection preparatory layer, and the ceramic substrate 20 to be connected more densely.
In the above preferred embodiment, the preparation process of the binder may be set according to the prior art. Preferably, the binder is slurry formed by mixing and reacting alumina, zirconia and phosphoric acid. The alumina and zirconia react with the phosphoric acid to form aluminum phosphate and zirconium phosphate with a binder phase. More preferably, the alumina is particles with a particle size of 5-50 nm, the zirconia is particles with a particle size of 5-50 nm, the concentration of the phosphoric acid is 50-85 wt%, and the specification is analytical purity. The above preferred material properties enable the prepared binder to have stronger binding properties and to withstand sintering at higher temperatures.
In the step of forming the connection preparation layer, another preferred embodiment is: the connection preparation layer can be a casting sheet, and the step of forming the preparation metamaterial comprises the following steps: the conductive geometry 40 is formed on the surface of the glass substrate 10, the ceramic substrate 20 or the cast sheet, after which the glass substrate 10, the cast sheet and the ceramic substrate 20 are laminated in sequence to form a preliminary metamaterial. The casting sheet is prepared by mixing ceramic powder and organic polymer and casting, wherein the organic polymer solvent can be a resin solvent with epoxy resin. The tape-casting sheet prepared from the material can be compatible with Ag-Pd slurry sintering, so that the integrity of a conductive geometric structure can be ensured, and the Ag-Pd slurry is prevented from flowing, breaking, permeating or melting. Further, the cast sheet can be bonded or bonded to the base phase of the glass substrate 10 and the ceramic substrate 20.
After the step of sequentially laminating the glass substrate 10, the connection preparation layer and the ceramic substrate 20 to form the preparation metamaterial with the conductive geometry 40 disposed between the glass substrate 10 and the ceramic substrate 20, the preparation metamaterial is subjected to a heat treatment so that the connection preparation layer forms the connection layer 30, and the glass substrate 10, the connection layer 30 and the ceramic substrate 20 are sequentially laminated to form the metamaterial.
The process of forming the bonding layer 30 may be varied depending on the process of forming the bonding preparation layer, and in a preferred embodiment, a heat treatment is performed to cure the adhesive to form the bonding layer 30. The temperature and time of the heat treatment can be set according to actual requirements. Preferably, the treatment temperature is 800-900 ℃, and the treatment time is 5-30 minutes. More preferably, the heat treatment comprises a first heat treatment and a second heat treatment, wherein the temperature of the first heat treatment can be 800-850 ℃, and the time of the first heat treatment can be 5-15 minutes; the temperature of the second heat treatment can be 850-900 ℃, and the time of the first heat treatment can be 5-15 minutes. The two increases in temperature may further allow the mixture in the binder to react to form a bound phase.
In the step of forming the connection layer 30, another preferred embodiment is: a heat treatment is performed to sinter the cast sheet to form the connecting layer 30. The temperature and time of the heat treatment can be set according to actual requirements. Preferably, the treatment temperature is 800-920 ℃, and the treatment time is 5-30 minutes. More preferably, the heat treatment comprises a first heat treatment and a second heat treatment, wherein the temperature of the first heat treatment can be 800-850 ℃, and the time of the first heat treatment can be 5-15 minutes; the temperature of the second heat treatment can be 850-920 ℃, and the time of the first heat treatment can be 5-15 minutes. The two temperature increases can further sinter and densify the powder (containing glass or other low melting point oxides) in the cast sheet.
The preparation method of the metamaterial provided by the present application will be further described with reference to the following examples.
Example 1
The preparation method of the metamaterial provided by the embodiment comprises the following steps:
firstly, mixing and reacting alumina, zirconia and phosphoric acid to form a binder, and coating the binder between a glass substrate and a ceramic substrate to serve as a connection preparation layer, wherein the surface of the glass substrate is provided with a conductive geometric structure, and the glass substrate, the conductive geometric structure, the connection preparation layer and the ceramic substrate form a preparation metamaterial; and then, carrying out heat treatment on the prepared metamaterial at 800 ℃ for 5 minutes to enable the connection preparation layer to form a connection layer, wherein the glass substrate, the connection layer and the ceramic substrate are sequentially laminated and connected to form the metamaterial, and the metamaterial is provided with a conductive geometric structure.
Example 2
The preparation method of the metamaterial provided by the embodiment comprises the following steps:
firstly, mixing and reacting alumina, zirconia and phosphoric acid to form a binder, and coating the binder among a glass substrate, a ceramic substrate and the glass substrate which are sequentially arranged to serve as a connection preparation layer, wherein a conductive geometric structure is placed in the binder, and the glass substrate, the conductive geometric structure, the connection preparation layer and the ceramic substrate form a preparation metamaterial; and then, carrying out heat treatment on the prepared metamaterial at 900 ℃ for 30 minutes to enable the connection preparation layer to form a connection layer, wherein the glass substrate, the connection layer and the ceramic substrate are sequentially laminated and connected to form the metamaterial, and the metamaterial is provided with a conductive geometric structure.
Example 3
The preparation method of the metamaterial provided by the embodiment comprises the following steps:
firstly, arranging a casting sheet among a glass substrate, a ceramic substrate, the glass substrate and the ceramic substrate which are sequentially arranged as a connection preparation layer, wherein the casting sheet is prepared by mixing ceramic powder and epoxy resin and adopting a casting method, a conductive geometric structure is arranged on the surface of the casting sheet, and the glass substrate, the conductive geometric structure, the connection preparation layer and the ceramic substrate form a preparation metamaterial; and then, carrying out heat treatment on the prepared metamaterial at 800 ℃ for 5 minutes to enable the connection preparation layer to form a connection layer, wherein the glass substrate, the connection layer and the ceramic substrate are sequentially laminated and connected to form the metamaterial, and the metamaterial is provided with a conductive geometric structure.
Example 4
The preparation method of the metamaterial provided by the embodiment comprises the following steps:
firstly, arranging a casting sheet between a glass substrate, two ceramic substrates and the glass substrate which are sequentially arranged as a connection preparation layer, wherein the casting sheet is prepared by mixing ceramic powder and epoxy resin and performing a casting method, conductive geometric structures are arranged on the surfaces of the glass substrate and the ceramic substrate, and the glass substrate, the conductive geometric structures, the connection preparation layer and the ceramic substrate form a preparation metamaterial; and then, carrying out heat treatment on the prepared metamaterial at 920 ℃ for 30 minutes to enable the connection preparation layer to form a connection layer, wherein the glass substrate, the microstructure connection layer and the ceramic substrate are sequentially laminated and connected to form the metamaterial, and the metamaterial is provided with a conductive geometric structure.
Comparative example 1
The preparation method of the metamaterial provided by the embodiment comprises the following steps:
firstly, mixing and reacting alumina, zirconia and phosphoric acid to form a binder, and coating the binder between two ceramic substrates to serve as a connection preparation layer, wherein a conductive geometric structure is arranged on the surface of each ceramic substrate, and the ceramic substrates, the conductive geometric structures and the connection preparation layer form a preparation metamaterial; then, the prepared metamaterial was subjected to a heat treatment at 800 ℃ for 5 minutes to allow the connection preparation layers to form connection layers, wherein the ceramic substrate, the connection layers and the ceramic substrate are sequentially laminated and connected to form the metamaterial, a conductive geometric structure is provided in the metamaterial, and the metamaterial prepared in the present comparative example has the same physical dimensions as those of the metamaterials prepared in examples 1 to 4.
The metamaterial provided in the above examples 1 to 4 and comparative example 1 was subjected to a wave-transmissivity performance test, and the test results are shown in the following table:
as can be seen from the table above, the wave-transparent rate of the metamaterial prepared by the method is obviously improved within the frequency range of 3-5.5 GHz. Fig. 10 is a graph comparing the results of the wave-transparent test of example 1 and comparative example 1.
From the above description, it can be seen that the present invention provides a metamaterial including a glass substrate, a ceramic substrate and a connection layer connecting the glass substrate and the ceramic substrate, wherein the metamaterial includes the glass substrate and the ceramic substrate, and the glass has high compactness, high strength, large dielectric constant and moisture resistance, and the ceramic has low compactness, low strength, small dielectric constant and moisture absorption resistance, so that the formed metamaterial can effectively remove waste gas, reduce organic matters remaining in the metamaterial, reduce the water absorption of the metamaterial, and improve the corrosion resistance of the metamaterial, thereby making the metamaterial have low loss and improving the wave transmission performance of the metamaterial.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. Metamaterial, characterized in that the metamaterial comprises a glass substrate (10), a ceramic substrate (20) and a connection layer (30) connecting the glass substrate (10) and the ceramic substrate (20), wherein a conductive geometric structure (40) is further arranged between the glass substrate (10) and the ceramic substrate (20).
2. Metamaterial according to claim 1, characterized in that a recessed structure outside the periphery of the connection layer (30) is formed between the surfaces of the edge portion of the glass substrate (10) and the edge portion of the ceramic substrate (20) corresponding to each other.
3. The metamaterial according to claim 1, wherein the glass substrate (10) has a thickness in a range of 0.5 to 30mm, the ceramic substrate (20) has a thickness in a range of 0.5 to 30mm, and the connection layer (30) has a thickness in a range of 10 to 300 μm.
4. A metamaterial according to any one of claims 1 to 3,
the metamaterial comprises at least two layers of glass substrates (10) and at least two layers of ceramic substrates (20), the glass substrates (10) and the ceramic substrates (20) are arranged at intervals, the connecting layer (30) is arranged between every two adjacent glass substrates (10) and every two adjacent ceramic substrates (20), and the conductive geometric structures (40) are arranged between at least one group of adjacent glass substrates (10) and every two adjacent ceramic substrates (20); or,
the metamaterial comprises two layers of glass substrates (10) and at least one layer of ceramic substrates (20), the ceramic substrates (20) are arranged between the glass substrates (10), the glass substrates (10) are adjacent to each other, the connecting layer (30) is arranged between the ceramic substrates (20), and at least one group of adjacent glass substrates (10) and conductive geometric structures (40) are arranged between the ceramic substrates (20).
5. A metamaterial according to any one of claims 1 to 3,
the conductive geometry (40) is arranged on the surface of the glass substrate (10) or the ceramic substrate (20), and the conductive geometry (40) is connected with the connecting layer (30); or
The conductive geometry (40) is arranged inside the connection layer (30), and the conductive geometry (40) is not connected to the glass substrate (10) or the ceramic substrate (20).
6. A preparation method of a metamaterial is characterized by comprising the following steps:
sequentially laminating a glass substrate (10), a connection preparation layer and a ceramic substrate (20) to form a preparation metamaterial, wherein a conductive geometric structure (40) is arranged between the glass substrate (10) and the ceramic substrate (20);
and performing heat treatment on the prepared metamaterial to enable the connection preparation layer to form a connection layer (30), and enabling the glass substrate (10), the connection layer (30) and the ceramic substrate (20) to be sequentially stacked to form the metamaterial.
7. The method according to claim 6, wherein the connection preparation layer is an adhesive, and the step of forming the preparation metamaterial comprises: forming the conductive geometric structure (40) in the binder, on the surface of the glass substrate (10) or on the surface of the ceramic substrate (20), then placing the binder between the glass substrate (10) and the ceramic substrate (20), and then pressing the glass substrate (10), the connection preparation layer and the ceramic substrate (20) to form the preparation metamaterial.
8. The method according to claim 7, wherein the binder is a slurry formed by mixing and reacting alumina, zirconia and phosphoric acid.
9. The method of manufacturing according to claim 7, wherein the heat treatment is performed to cure the adhesive to form the connection layer (30).
10. A manufacturing method according to claim 6, wherein the connection preparation layer is a cast sheet, and the step of forming the preparation metamaterial includes: forming the conductive geometry (40) on a surface of the glass substrate (10), the ceramic substrate (20), or the cast sheet, followed by sequentially laminating the glass substrate (10), the cast sheet, and the ceramic substrate (20) to form the preliminary metamaterial.
11. A production method according to claim 10, wherein said heat treatment is performed so that said casting sheet is sintered to form said connection layer (30).
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| CN102480053A (en) * | 2011-09-05 | 2012-05-30 | 深圳光启高等理工研究院 | Preparation method of meta-material and meta-material |
| CN102731102A (en) * | 2012-05-30 | 2012-10-17 | 深圳光启创新技术有限公司 | Harmonic oscillator and preparation method thereof |
| CN104557053A (en) * | 2013-10-29 | 2015-04-29 | 深圳光启创新技术有限公司 | Ceramic-based metamaterial and preparation method thereof |
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| CN102480053A (en) * | 2011-09-05 | 2012-05-30 | 深圳光启高等理工研究院 | Preparation method of meta-material and meta-material |
| CN102731102A (en) * | 2012-05-30 | 2012-10-17 | 深圳光启创新技术有限公司 | Harmonic oscillator and preparation method thereof |
| CN104557053A (en) * | 2013-10-29 | 2015-04-29 | 深圳光启创新技术有限公司 | Ceramic-based metamaterial and preparation method thereof |
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| WO2024195270A1 (en) * | 2023-03-20 | 2024-09-26 | Ａｇｃ株式会社 | Electromagnetic wave-reflecting panel, electromagnetic wave-reflecting device, electromagnetic wave-reflecting fence, and method for manufacturing electromagnetic wave-reflecting panel |
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