CN106032329B - Ceramic base Meta Materials and its manufacturing method - Google Patents
Ceramic base Meta Materials and its manufacturing method Download PDFInfo
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- CN106032329B CN106032329B CN201510126267.XA CN201510126267A CN106032329B CN 106032329 B CN106032329 B CN 106032329B CN 201510126267 A CN201510126267 A CN 201510126267A CN 106032329 B CN106032329 B CN 106032329B
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- organic film
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Abstract
The purpose of the present invention is to provide a kind of new ceramic base Meta Materials and its manufacturing method.The manufacturing method of ceramic base Meta Materials of the invention, its main feature is that, comprising the following steps: flexible organic film is made with the tape casting, which has adhesion to the metal micro structure pattern slurry of silk-screen printing thereon；Metal micro structure pattern is printed with the method for silk-screen printing on the organic film on cast sheet carrier band, then drying the organic film makes the conductor paste of metal micro structure pattern not stick at finger；The organic film for carrying the metal micro structure pattern on cast sheet carrier band is attached to ceramic shell surface, so that the metal micro structure pattern is bonded in ceramic shell surface, and remove cast sheet carrier, the intensity of organic film is enough so far not will crack；Dumping is simultaneously sintered ceramic shell transferred with the metal micro structure pattern, and the organic film can volatilize during the dumping.
Description
Technical field
The present invention relates to ceramic base Meta Materials and its manufacturing methods.
Background technique
On organic composite material matrix micro-structure can be formed with the method for etching and chemical plating.And ceramic matrix, especially
It is endless fully dense ceramic surface, micro-structure cannot be formed with etching and electroless plating method, because electrolyte can penetrate into hole
In.In order to solve the problems, such as that curve ceramic surface difficulty directly prints micro-structure, before this, the side of the ceramic cast sheet of inventor
Method solves the problems, such as, a kind of Meta Materials and preparation method thereof is described in patent document CN103524136A, wherein ceramic case
The dielectric patch layer of internal side is spliced by multiple cast sheets, collectively constitute be similar to or corresponding to the ceramic shell shape
The space geometry structure of shape, with the ceramic shell blind-mate.But the method for ceramic cast sheet is not unique method, therefore
Develop other methods also it is necessary to.
Summary of the invention
The purpose of the present invention is to provide a kind of manufacturing methods of new ceramic base Meta Materials.
The manufacturing method of ceramic base Meta Materials of the invention, its main feature is that, comprising the following steps:
Flexible organic film is made with the tape casting；
Metal micro structure pattern is printed with the method for silk-screen printing on the organic film on cast sheet carrier band, then
The dry organic film, makes the conductor paste of metal micro structure pattern not stick at finger；
The organic film that the metal micro structure pattern is carried on cast sheet carrier band is attached to ceramic shell
Surface makes the metal micro structure pattern be bonded in ceramic shell surface, and removes cast sheet carrier；
Dumping and be sintered transferred with the metal micro structure pattern ceramic shell, the organic film is in the dumping mistake
It volatilizees in journey.
The manufacturing method of the ceramic base Meta Materials, further feature are the preparation methods of the organic film
Include:
Step 1 dissolves PVB with alcohol and butanone mixed solvent, PVB solution is made；
Step 2 is added plasticizer and is uniformly mixed in PVB solution；
Defoaming agent is added in step 2 obtained solution, and is uniformly mixed for step 3；
Step 4 defoams processing to step 3 obtained solution；
Step 5 forms cast sheet with step 4 obtained solution on casting machine, the organic film is made.
The manufacturing method of the ceramic base Meta Materials, further feature are that the content of PVB is 10- in PVB solution
20wt%.
The manufacturing method of the ceramic base Meta Materials, further feature are that in the step 2, plasticizer exists
Content in solution is 2-10wt%.
The manufacturing method of the ceramic base Meta Materials, further feature are that in the step 3, defoaming agent exists
Content in solution is 0.5-2wt%.
The manufacturing method of the ceramic base Meta Materials, further feature are that organic film arrives with a thickness of 50 μm
150μm。
The manufacturing method of the ceramic base Meta Materials, further feature are that goo is passed through on ceramic shell surface
After coating processing, then the organic film for carrying the metal micro structure pattern is attached to ceramic shell surface.
The manufacturing method of the ceramic base Meta Materials, further feature are that the goo is one layer of ceramic case
The PVB solution coated on body surface face, the PVB solution of the coating are solution of the PVB content in 5-20wt%.
The manufacturing method of the ceramic base Meta Materials, further feature are that the ceramic shell is curved body.
The manufacturing method of the ceramic base Meta Materials, further feature are to carry the metal micro structure pattern
The organic film attach on the inner surface of the ceramic housing or outer surface.
The manufacturing method of the ceramic base Meta Materials, further feature are that the cast sheet carrier band is to be poly- to benzene
Naphthalate.
The present invention also provides a kind of ceramic base Meta Materials, are manufactured by any method.
Present invention silk-screen metal micro structure pattern on organic film, then it is transferred to ceramic shell surface, therefore have
There are many advantages.The above and other features of the present invention, property and advantage will by with reference to the accompanying drawing and implement
Example description and become readily apparent from.
Detailed description of the invention
Fig. 1 is the flow diagram of the manufacturing method of ceramic base Meta Materials in one embodiment of the invention.
Fig. 2 is the schematic diagram that the tape casting prepares organic film in one embodiment of the invention.
Fig. 3 is the organic film schematic diagram in one embodiment of the invention on the tape casting carrier band.
Fig. 4 is the schematic diagram of the silk-screen micro structured pattern on organic film in one embodiment of the invention.
Fig. 5 is the schematic diagram for applying goo coating processing in one embodiment of the invention on ceramic shell.
Fig. 6 is the schematic diagram that the micro structured pattern on organic film is needed on to ceramic shell in one embodiment of the invention.
Fig. 7 is the schematic diagram of ceramic base Meta Materials in one embodiment of the invention.
Fig. 8 is the schematic diagram of ceramic base Meta Materials in another embodiment of the present invention.
Fig. 9 is the schematic diagram of ceramic base Meta Materials in further embodiment of this invention.
Specific embodiment
The invention will be further described with attached drawing combined with specific embodiments below, elaborates in the following description more
Details to facilitate a thorough understanding of the present invention, still the present invention obviously can be come with a variety of other ways different from this description it is real
It applies, those skilled in the art can make similar popularization according to practical situations without violating the connotation of the present invention, drill
It unravels silk, therefore should not be limited the scope of the invention with the content of this specific embodiment.
In an embodiment of the present invention, as shown in Figure 1, the manufacturing method of ceramic base Meta Materials includes later-mentioned step.
In a step 11, the tape casting preparation of flexible organic film is carried out, Fig. 2 further illustrates the details of step 11.
As shown in Fig. 2, being the alcohol and butanone with 3:2 (weight ratio) firstly, in a step 101, provide PVB solution
The PVB solution of 10-20wt% is made in mixed solvent polyethylene dissolving butyral (PVB).Alcohol and butanone are mixed and molten
Used mixed method can be any mixing method when solving PVB, such as magnetic agitation method, electric agitation method, bead mill mixing
Method etc..In other embodiments, mixed solvent can also be from being dissolved in ethyl alcohol, normal propyl alcohol, isopropanol, positive penta, benzyl alcohol, diacetone
Alcohol, propylene-glycol ethyl ether, methyl ether, propyl ether, acetone, methyl ethyl ketone, cyclohexanone, methylene chloride, chloroform, methyl acetate, ethyl acetate, second
It is selected in the combination of acid butyl ester, acetic acid etc..The PVB percentage of PVB solution can also according to subsequent silk-screen slurry or
Solvent type, intensity requirement etc. are adjusted or are changed.
Secondly, in a step 102, the plasticizer of 2-10wt% is added in gained PVB solution, such as two fourth of phthalic acid
Ester mixes at least 4 hours in ball mill.The low-temperature flexibility that plasticizer can increase organic film can or reduce solution
Viscosity.
Then, in step 103, the defoaming agent of 0.5-2wt% is added in the aforementioned mixed solution added with plasticizer, such as
Tributyl phosphate mixes at least 2 hours, and mixed method is best with bead mill (planetary) effect.
Then, at step 104, resulting solution is removed into bubble removing with vacuum degasing machine, vacuumizes 5-15 while stirring
Minute, it can then be cast.
On casting machine, the speed of travel of cast sheet carrier band (PET material) is set as 0.2-0.4m/ minutes, is not needed pre-
First heating cast sheet carrier band sets height of first scraper edge from PET film as 250-350 μm, 50-150 μ can be obtained after curtain coating
Flexible organic film after m.
Back to Fig. 1, the manufacturing method of ceramic base Meta Materials is continued to explain, in step 12, as shown in figure 3, keeping flexible
The fit-state of organic film 202 and cast sheet carrier band 201, as shown in Figure 4 using the method for silk-screen printing on organic film
Scheduled metal micro structure 203 is printed, is dried 8-12 hours at a temperature of 50 DEG C in air.In the present embodiment, to touch
Not sticking at when conductor paste is drying regime after finger.Metal micro structure with Ag base be it is common, but not limited to this.Micro-structure is
The conductive geometry for the plane or solid with certain geometrical shape being made of conductor silk, such as I-shaped, snowflake type,
The conduction geometry is suitable for enhancing the wave transparent performance of Meta Materials.The conductive geometry of the embodiment of the present invention is not limited to
This, can also be the conductive geometry that other respective actions are made to electromagnetic wave, e.g. enhancing absorbing property.
Next, as shown in figure 5, doing the painting of goo 205 on 204 surface of ceramic shell for needing to be arranged micro structured pattern
Processing is covered, such as coats very thin one layer of PVB (20wt%) solution, after slightly dry, if too dry, alcohol dampening used, guarantees
Surface toughness.
Ceramic shell 204, which can be, has burnt or has not burnt ceramic layer, and the preparation of ceramic shell 204 includes: that will contain ceramic powder
Expect (such as cordierite, aluminium oxide or nonmetal oxide Si3N4Deng) and the suspended substance of organic system deaerates, pre-polymerization obtains slurry, it will
Slurry cast is inserted into mold fuse into a mold, and the green compact of gel casting forming are obtained after solidification.Wherein detailed process
Are as follows: organic monomer and crosslinking agent are dissolved in the water, and water soluble polymer is added as dispersing agent, monomer solution is made；Again
Be added into monomer solution ceramic powder be sufficiently mixed, add initiator after vacuum outgas and catalyst stir evenly, pre-polymerization
Obtain required slurry；By obtained slurry cast into the mold, and it is inserted into mold fuse, obtains gel injection-moulding after room temperature curing
Molding green compact.In other embodiments of the invention, 204 surface of ceramic shell is that non-curved or curved surface is also possible.
As shown in fig. 6, the micro structured pattern 203 cast sheet carried on the organic film 202 on 201 is attached to ceramic case
On 204 surface of body, uniformly with certain pressure compaction, pressure, as Mobile phone screen pad pasting.After to be dried, it is bonded by goo 205
After securely, cast sheet of tearing carrier band leaves silk-screen micro structured pattern 203 on the surface of ceramic shell 204.
550 DEG C are heated in air furnace hereinafter, slow dumping, organic film 202 burns volatilization in this process, passes through
10 hours or more；Then it is sintered at high temperature, to different metal base conductor paste, the high temperature is different temperatures, such as
It is Ag base conductor paste, then high temperature refers to 900 DEG C or more.Due to having glass phase in conductor paste, it can make therein lead
Body is adhered on 204 surface of ceramic shell, thereby realizes micro structured pattern 203 being transferred to 204 surface of ceramic shell
Purpose, obtained ceramic base Meta Materials are as shown in fig. 7, be arranged micro structured pattern 203 on the surface of ceramic shell 204.Conductor slurry
Metal in material can be noble metal, be also possible to copper.
In other embodiments of the invention, organic film 202 is not limited to PVB film, can also be that other materials are made
Film, as long as its be flexible, in silk-screen printing process and when demoulding it is not easy to crack, have to conductor paste in silk-screen printing process
It is adhesion, readily volatilized (usually at 200 degrees Celsius or less) during dumping.
In another embodiment of the invention, micro-structure has been transferred by organic film 202 on a ceramic shell 204
After pattern 203, as shown in figure 8, can also in addition additional layer ceramic shell 204A be re-sintered after pressing, formed in this way
Multi-layer ceramics base Meta Materials.
In another embodiment of the invention, as shown in figure 9, passing through 202 turns of organic film on a ceramic shell 204
After having printed micro structured pattern 203 and dumping sintering, one layer of organic composite material 206 can also be covered, the organic composite material 206
The protection of mechanical, heat-resisting, corrosion-resistant etc. is formed to micro-structure, so that micro-structure is not easy to be heated, by damaged or aging.
Pass through previous embodiment it will be appreciated that the advantages of various embodiments of the present invention includes but is not limited to:
1. can solve conventional art cannot be the direct silk-screen micro structured pattern on curved surface the problem of；
Even if 2. in conventional art plane can direct silk-screen, but it is risky because once misprinting or defective, entire base
Body cannot be used, or be difficult to clean up, and the silk-screen on cheap organic film may be implemented in the embodiment of the present invention, such as
Fruit is broken one, can use instead one it is good.
Although the present invention is disclosed as above with preferred embodiment, it is not for limiting the present invention, any this field skill
Art personnel without departing from the spirit and scope of the present invention, can make possible variation and modification.Therefore, it is all without departing from
The content of technical solution of the present invention, according to the technical essence of the invention any modification to the above embodiments, equivalent variations
And modification, it each falls within the protection scope that the claims in the present invention are defined.
Claims (12)
1. a kind of manufacturing method of ceramic base Meta Materials, which comprises the following steps:
Flexible organic film is made with the tape casting；
Metal micro structure pattern is printed with the method for silk-screen printing on the organic film on cast sheet carrier band, is then dried
The organic film makes the conductor paste of metal micro structure pattern not stick at finger；
The organic film that the metal micro structure pattern is carried on cast sheet carrier band is attached to ceramic shell surface,
So that the metal micro structure pattern is bonded in ceramic shell surface, and removes cast sheet carrier；
Dumping and be sintered transferred with the metal micro structure pattern ceramic shell, the organic film is during the dumping
Volatilization.
2. the manufacturing method of ceramic base Meta Materials as described in claim 1, which is characterized in that the preparation side of the organic film
Method includes:
Step 1 dissolves PVB with alcohol and butanone mixed solvent, PVB solution is made；
Step 2 is added plasticizer and is uniformly mixed in PVB solution；
Defoaming agent is added in step 2 obtained solution, and is uniformly mixed for step 3；
Step 4 defoams processing to step 3 obtained solution；
Step 5 forms cast sheet with step 4 obtained solution on casting machine, the organic film is made.
3. the manufacturing method of ceramic base Meta Materials as claimed in claim 2, which is characterized in that the content of PVB is in PVB solution
10-20wt%.
4. the manufacturing method of ceramic base Meta Materials as claimed in claim 2, which is characterized in that in the step 2, plasticising
The content of agent in the solution is 2-10wt%.
5. the manufacturing method of ceramic base Meta Materials as claimed in claim 2, which is characterized in that in the step 3, defoaming
The content of agent in the solution is 0.5-2wt%.
6. the manufacturing method of ceramic base Meta Materials as claimed in claim 2, which is characterized in that organic film with a thickness of 50 μm
To 150 μm.
7. the manufacturing method of ceramic base Meta Materials as described in claim 1, which is characterized in that ceramic shell surface is by viscosity
After object coating processing, then the organic film for carrying the metal micro structure pattern is attached to ceramic shell surface.
8. the manufacturing method of ceramic base Meta Materials as claimed in claim 7, which is characterized in that the goo is one layer of ceramics
The PVB solution coated on surface of shell, the PVB solution of the coating are solution of the PVB content in 5-20wt%.
9. the manufacturing method of ceramic base Meta Materials as described in claim 1, which is characterized in that the ceramic shell is curved surface
Body.
10. the manufacturing method of ceramic base Meta Materials as described in claim 1, which is characterized in that carry the metal micro structure
The organic film of pattern attaches on the inner surface of the ceramic housing or outer surface.
11. the manufacturing method of ceramic base Meta Materials as described in claim 1, which is characterized in that the cast sheet carrier band is poly-
Ethylene glycol terephthalate.
12. a kind of ceramic base Meta Materials, which is characterized in that the manufacture of the method as described in any one of claims 1 to 11.
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| CN109130222B (en) * | 2017-06-27 | 2021-12-10 | 深圳光启高等理工研究院 | Metamaterial and manufacturing method thereof |
| CN113644433B (en) * | 2021-07-12 | 2024-02-13 | 航天特种材料及工艺技术研究所 | Preparation method of high-temperature-resistant FSS structure on outer surface of special-shaped radome |
| CN115094209A (en) * | 2022-06-02 | 2022-09-23 | 烟台杰瑞石油装备技术有限公司 | Preparation method and structure of wear-resistant surface, pipeline, connecting valve and operation equipment |
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| CN103373860A (en) * | 2012-04-27 | 2013-10-30 | 比亚迪股份有限公司 | Surface metalized coating composition of ceramic matrix, surface metalizing method of ceramic matrix, and coating and ceramic prepared from ceramic matrix |
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