CN103289316B - The preparation method and Super-material antenna of a kind of metamaterial substrate - Google Patents
The preparation method and Super-material antenna of a kind of metamaterial substrate Download PDFInfo
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- CN103289316B CN103289316B CN201210183314.0A CN201210183314A CN103289316B CN 103289316 B CN103289316 B CN 103289316B CN 201210183314 A CN201210183314 A CN 201210183314A CN 103289316 B CN103289316 B CN 103289316B
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Abstract
The invention discloses a kind of preparation method of metamaterial substrate, including sediment will be obtained in the alkaline solution of the zinc salt place of being slowly added to stirring, sediment is dried, Zinc oxide powder is obtained after cooling；Zinc oxide powder is added in isopropanol, the first mixed solution is formed, coupling agent is added in acetone, the second mixed solution is mixing uniformly to form；First mixed solution is slowly added in the second mixed solution, then filtered, modified zinc oxide is obtained after drying；Will modified zinc oxide add organic solvent in carry out for the first time it is ultrasonically treated, then add high polymer, the 3rd mixed solution obtained after stirring；3rd mixed solution is stirred and second ultrasonically treated, is then dried, obtains super material mixture；Super material mixture is hot-forming, obtain metamaterial substrate.The invention also discloses a kind of Super-material antenna.The present invention can prepare high performance metamaterial substrate by the way that modified zinc oxide is manually combined with high polymer.
Description
Technical field
The present invention relates to Meta Materials field, the preparation method and Super-material antenna of more particularly to a kind of metamaterial substrate.
Background technology
As modern electronic technology is developed rapidly, the processing of digital circuit, the high frequency stage is transferred into, people are for holding
The requirement more and more higher of the substrate of circuit is carried, the performance of substrate will have a strong impact on circuit characteristic, wherein with dielectric properties, heat-resisting
Several performances such as property, dimensional stability, moisture-proof, intensity are particularly important.And the performance of substrate depends primarily on material used.
In the prior art, generally using common high polymer, such as epoxy resin and phenolic resin make substrate, but these height are poly-
Thing poor heat resistance and dielectric properties are poor, are not suitable for very much high-frequency circuit.So, industry starts to turn the material for preparing of substrate
Move on on Meta Materials.
Meta Materials refer to artificial composite structure or composite with the extraordinary physical property not available for natural material.
By the structurally ordered design on the key physical yardstick of material, the limitation of some apparent natural laws can be broken through, so that
Obtain the meta-materials function beyond the intrinsic common property of nature.The property and function of Meta Materials are mostly come from inside it
Structure rather than constitute their material.
Zinc oxide is a kind of white or micro- yellowy fine-powder, is easily dispersed in rubber and latex, with nontoxic, height
Effect and high photo-thermal temperature and there is low-down dielectric constant, and high polymer has good plasticity.If by oxygen
Change zinc and be combined into Meta Materials with high polymer, not only with anti-ultraviolet aging ability and antistatic effect, moreover it is possible to strengthen mechanical property
Energy.But, the manufacture not on such metamaterial substrate in the prior art.
The content of the invention
The present invention solves the technical problem of provide a kind of preparation method and Super-material antenna of metamaterial substrate, energy
It is enough that modified zinc oxide and high polymer are combined into metamaterial substrate.
In order to solve the above technical problems, the invention provides a kind of preparation method of metamaterial substrate, including：Zinc salt is delayed
Sediment is obtained in alkaline solution at slow addition with stirring, sediment is dried, Zinc oxide powder is obtained after cooling；
Zinc oxide powder is added in isopropanol, the first mixed solution is formed, coupling agent is added in acetone, the is mixing uniformly to form
Two mixed solutions；First mixed solution is slowly added in the second mixed solution, then filtered, obtains being modified oxygen after drying
Change zinc；Modified zinc oxide is added in organic solvent and carries out ultrasonically treated for the first time, high polymer is then added, after stirring
To the 3rd mixed solution；3rd mixed solution is stirred and second ultrasonically treated, is then dried, obtains Meta Materials
Mixture；Super material mixture is hot-forming, obtain metamaterial substrate.
Wherein, sediment will be obtained in the zinc salt place of being slowly added to alkaline solution with stirring, sediment is dried,
The step of Zinc oxide powder is obtained after cooling includes：Alkaline solution is stirred on magnetic stirring apparatus, will be analyzed more than pure
The zinc salt place of being slowly added to alkaline solution with stirring in obtain white depositions, by white depositions with 4 ~ 5 DEG C/min's
Heating rate is warming up to 350 ~ 1200 DEG C and is dried, and is incubated 2 ~ 5h, Zinc oxide powder is obtained after naturally cooling to 18 ~ 25 DEG C.
Wherein, the mol ratio of zinc salt and alkaline solution is 1:1.
Wherein, zinc salt is zinc nitrate or zinc chloride, and alkaline solution is sodium hydroxide or sodium carbonate liquor.
Wherein, the ratio of the quality of Zinc oxide powder and the volume of isopropanol is 1g:80ml~2g:80ml, coupling agent is titanium
The ratio of the volume of acid esters, its quality and acetone is 0.01g:80ml~0.05g:80ml.
Wherein, will modified zinc oxide add organic solvent in carry out for the first time it is ultrasonically treated, then add high polymer, stir
In the step of obtaining three mixed solutions after uniform, the volume ratio of modified zinc oxide and organic solvent is 1:19~1:99, modified oxygen
The mass ratio for changing zinc and high polymer is 30%:70%~0.5%:95.5%.
Wherein, organic solvent be methyl hexahydrophthalic anhydride or tetrahydrofuran, high polymer be bisphenol A epoxide resin, polyvinyl chloride,
Polystyrene, polyethylene or polypropylene.
Wherein, the 3rd mixed solution is stirred and second ultrasonically treated, be then dried, obtained Meta Materials and mix
In the step of compound, mixing time is 30 ~ 40min, and second of sonication treatment time is 30 ~ 40min, and drying temperature is 80 ~ 100
DEG C, the time be 5 ~ 5.5h.
Wherein, super material mixture is hot-forming, the step of obtaining metamaterial substrate includes：Super material mixture is put
Hot-forming in mould, the metamaterial substrate of shape needed for obtaining is placed in, wherein, hot pressing temperature is the vitrifying temperature of high polymer
Degree, its error is+5 ~+10 DEG C, and hot pressing pressure is 20 ~ 45MPa.
In order to solve the above technical problems, present invention also offers a kind of Super-material antenna, including copper foil and PUR, this surpasses
Material antenna also includes the metamaterial substrate prepared according to any of the above-described kind of method, and copper foil is bonded in Meta Materials base by PUR
On plate.
The beneficial effects of the invention are as follows：It is different from the situation of prior art, the preparation method of metamaterial substrate of the invention
And Super-material antenna is by the way that modified zinc oxide and high polymer are combined, can prepare with anti-ultraviolet aging ability,
The metamaterial substrate of the advantages of antistatic effect, high plasticity and good mechanical property.
Brief description of the drawings
Fig. 1 is the preparation method flow chart of the metamaterial substrate of first embodiment of the invention；
Fig. 2 is the structural representation of the Super-material antenna of third embodiment of the invention；
Fig. 3 is the structural representation of the Super-material antenna of fourth embodiment of the invention；
Fig. 4 is the manufacture craft schematic diagram of the Super-material antenna of fifth embodiment of the invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
Fig. 1 is referred to, Fig. 1 show the preparation method flow chart of the metamaterial substrate of first embodiment of the invention, this surpasses
The preparation method flow of material substrate comprises the following steps：
Step S 101：Sediment will be obtained in the alkaline solution of the zinc salt place of being slowly added to stirring, sediment is carried out
Dry, Zinc oxide powder is obtained after cooling.
Step S101 includes：Alkaline solution is stirred on magnetic stirring apparatus, pure zinc salt above will be analyzed slow
White depositions are obtained in alkaline solution at addition with stirring, by white depositions with 4 ~ 5 DEG C/min heating rate liter
Temperature is dried to 350 ~ 1200 DEG C, is incubated 2 ~ 5h, Zinc oxide powder is obtained after naturally cooling to 18 ~ 25 DEG C, wherein, zinc salt with
The mol ratio of alkaline solution is 1:1.In the present embodiment, zinc salt be zinc nitrate or zinc chloride, alkaline solution be sodium hydroxide or
Sodium carbonate liquor.
Be stirred on magnetic stirring apparatus is to make reactant well mixed according to the principle in magnetic field and whirlpool and make temperature
Uniformly.In the present embodiment, zinc salt and alkaline solution are stirred and zinc salt can be made to be sufficiently mixed with alkaline solution, promote chemistry
Reaction.
Step S102：Zinc oxide powder is added in isopropanol, the first mixed solution is formed, coupling agent is added into acetone
In, it is mixing uniformly to form the second mixed solution.
Wherein, the ratio of the quality of Zinc oxide powder and the volume of isopropanol is 1g:80ml~2g:80ml, the matter of coupling agent
The ratio of amount and the volume of acetone is 0.01g:80ml~0.05g:80ml.In the present embodiment, coupling agent is titanate esters.
Step S103：First mixed solution is slowly added in the second mixed solution, then filtered, is obtained after drying
Modified zinc oxide.
Step S104：Will modified zinc oxide add organic solvent in carry out for the first time it is ultrasonically treated, then add high polymer,
The 3rd mixed solution is obtained after stirring.
Wherein, the volume ratio of modified zinc oxide and organic solvent is 1:19~1:99, the quality of modified zinc oxide and high polymer
Than for 30%:70%~0.5%:95.5%.In the present embodiment, organic solvent is methyl hexahydrophthalic anhydride or tetrahydrofuran, and high polymer is
Bisphenol A epoxide resin, polyvinyl chloride, polystyrene, polyethylene or polypropylene.
It is ultrasonically treated to refer to promote the anti-of material using the mechanism of ultrasound, cavitation, fuel factor and chemical effect
Should, ultrasonically treated can be such as ultrasonic disperse.In the present embodiment, progress is ultrasonically treated for the first time makes modified zinc oxide equal
It is even to disperse in organic solvent.
Step S105：3rd mixed solution is stirred and second ultrasonically treated, is then dried, obtains super material
Expect mixture.
Wherein, mixing time is 30 ~ 40min, and second of sonication treatment time is 30 ~ 40min, and drying temperature is 80 ~ 100
DEG C, the time be 5 ~ 5.5h.
It is ultrasonically treated by stirring and second, modified zinc oxide can be made fully to be dispersed in high polymer.
Step S106：Super material mixture is hot-forming, obtain metamaterial substrate.
Step S106 includes：Super material mixture is positioned over to hot-forming in mould, the Meta Materials of shape needed for obtaining
Substrate, wherein, hot pressing temperature is the glass transition temperature of high polymer, and its error is+5 ~+10 DEG C, and hot pressing pressure is 20 ~ 45MPa.
The metamaterial substrate has an extraordinary physical property that natural material does not possess, such as antistatic, anti-ultraviolet aging,
It can be used in carrying a variety of circuits, be particularly suitable for high-frequency circuit.
Second embodiment
A kind of preparation method of metamaterial substrate, including：
Step one：Alkaline solution containing 0.08mol sodium hydroxides is positioned on magnetic stirring apparatus and stirred, stirred
It is slowly added to analyze the 0.08mol zinc nitrates more than pure in journey, the white depositions of zinc oxide precursor is obtained, by white precipitate
Thing centrifugation, washing, then be warming up to 1200 DEG C with 5 DEG C/min heating rate and be dried, 5h is incubated, 25 are then naturally cooled to
Zinc oxide powder is obtained after DEG C.
Step 2：5g Zinc oxide powders are added in 400ml isopropanols, the first mixed solution are formed, by 0.05g metatitanic acids
Ester coupling agent is added in 400ml acetone, is mixing uniformly to form the second mixed solution.
Step 3：First mixed solution is slowly added in the second mixed solution, then filtered, dry after changed
Property zinc oxide.
Step 4：Modified zinc oxide is added in tetrahydrofuran and carries out ultrasonically treated 30min for the first time, bis-phenol is then added
A epoxy resin, obtains the 3rd mixed solution after stirring.Wherein, the volume ratio of modified zinc oxide and tetrahydrofuran is 1:99,
The mass ratio of modified zinc oxide and bisphenol A epoxide resin is 30%:70%.
Step 5：3rd mixed solution is positioned on magnetic stirring apparatus and stirs 30min, then is carried out ultrasonically treated for the second time
30min, 5h is then dried at 80 DEG C, super material mixture is obtained.
Step 6：Super material mixture is positioned over hot-forming in mould, obtains metamaterial substrate, i.e. modified zinc oxide
With high polymer composite material substrate.Wherein, hot pressing temperature is the glass transition temperature of high polymer, and error is+5 DEG C, and hot pressing pressure is
20MPa。
Fig. 2 is referred to, Fig. 2 show the structural representation of the Super-material antenna of third embodiment of the invention.
Super-material antenna 200 is that one side covers copper antenna, and it includes copper foil 201, PUR 202 and metamaterial substrate 203, surpasses
The preparation method of material 203 uses the preparation method of the metamaterial substrate shown in Fig. 1.PUR 202 is a kind of the viscous of plasticity
Mixture, it forms liquid after heating power colloidal sol, and bonding is completed after cooling.Copper foil 201 is bonded in super by PUR 202
On material substrate 203, the specific preparation method of Super-material antenna 200 is：
PUR 202 is coated on to the surface of metamaterial substrate 203, copper is formed using process for copper is covered on PUR 202
Paper tinsel 201；
Hot pressing is carried out to copper foil 201, PUR 202 and metamaterial substrate 203 using vacuum press, copper-clad plate is formed, its
In, hot pressing temperature is 85 ~ 95 DEG C, and hot pressing pressure is 1 ~ 1.5MPa, and hot pressing time is 30 ~ 90min, and vacuum is less than 25mbar；
Working line is etched in copper-clad plate using etch process, structure Super-material antenna as shown in Figure 2 is formed
200。
Fig. 3 is referred to, Fig. 3 show the structural representation of the Super-material antenna of fourth embodiment of the invention.
Super-material antenna 300 is the double-sided copper-clad antenna made based on the Super-material antenna 200 of 3rd embodiment, its
Including copper foil 301, copper foil 305, PUR 302, PUR 304 and metamaterial substrate 303.Copper foil 301 and copper foil 305 lead to respectively
Cross PUR 302 and PUR 304 is bonded in two surfaces of metamaterial substrate 303.
The structure of Super-material antenna 300 is followed successively by copper foil 301, PUR 302, metamaterial substrate 303, the and of PUR 304
Copper foil 305, its specific preparation method is similar with the specific preparation method of the Super-material antenna 200 of 3rd embodiment, therefore herein not
Repeat again.
Fig. 4 is referred to, Fig. 4 show the manufacture craft schematic diagram of the Super-material antenna of fifth embodiment of the invention.
The manufacture craft can make two panels Super-material antenna simultaneously, to save process and expand the scale of production, its specific system
It is as method：
PUR is coated on to the surface of metamaterial substrate, copper foil, and then shape are formed on PUR using process for copper is covered
Into base material；
Base material 404 and base material 406 are separated with steel plate 405, tool palette 401 and the inner side of tool palette 409 is placed in, and by base material
404 are separated with tool palette 401 with steel plate 403 and layers of kraft paper 402, by base material 406 and tool palette 409 steel plate 407 and ox-hide
Ply of paper 408 is separated, and forms structure as shown in Figure 4, is then carried out hot pressing using vacuum press, is obtained two panels copper-clad plate, wherein,
The thickness of steel plate 403,405,407 is 1 ~ 2mm, and layers of kraft paper 402,408 is made up of 10 ~ 20 thickness for 0.2mm brown paper,
Hot pressing temperature is 85 ~ 95 DEG C, and hot pressing pressure is 1 ~ 1.5MPa, and hot pressing time is 30 ~ 90min, and vacuum is less than 25mbar；
Working line is etched in two panels copper-clad plate using etch process, two panels Super-material antenna is formed.
In the present embodiment, the manufacture craft makes two panels Super-material antenna simultaneously.In other embodiments, the making work
Skill can also make the Super-material antenna of other numbers simultaneously according to actual needs.
It should be appreciated that the metamaterial substrate in above-described embodiment is not limited to make Super-material antenna, those skilled in the art
Metamaterial substrate easily can be applied to other circuits and electronic product by member according to the common knowledge of this area and the present invention
In, can for example it regard the present invention metamaterial substrate as encapsulating material, therefore, the related production of the metamaterial substrate comprising the present invention
Product are also included within protection scope of the present invention.
By the above-mentioned means, the preparation method and Super-material antenna of the metamaterial substrate of the present invention are by by modified zinc oxide
It is combined, can be prepared with anti-ultraviolet aging ability, antistatic effect, high plasticity and good power with high polymer
The metamaterial substrate for the advantages of learning performance.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright specification and accompanying drawing content are made, or directly or indirectly it is used in other related skills
Art field, is included within the scope of the present invention.
Claims (9)
1. a kind of preparation method of metamaterial substrate, it is characterised in that including：
Sediment will be obtained in the alkaline solution of the zinc salt place of being slowly added to stirring, the sediment is dried, cooled down
After obtain Zinc oxide powder, its step includes：The alkaline solution is stirred on magnetic stirring apparatus, will be analyzed more than pure
The zinc salt place of the being slowly added to alkaline solution with stirring in obtain white depositions, by the white depositions with 4~5
DEG C/min heating rate is warming up to 350~1200 DEG C and is dried, 2~5h is incubated, is obtained after naturally cooling to 18~25 DEG C
Zinc oxide powder；
The Zinc oxide powder is added in isopropanol, the first mixed solution is formed, coupling agent is added in acetone, stirred
After form the second mixed solution；
First mixed solution is slowly added in second mixed solution, is then filtered, is modified after drying
Zinc oxide；
Will the modified zinc oxide add organic solvent in carry out for the first time it is ultrasonically treated, make the modified zinc oxide dispersed
In the organic solvent, high polymer is then added, the 3rd mixed solution is obtained after stirring, wherein, the high polymer is
Bisphenol A epoxide resin, polyvinyl chloride, polystyrene, polyethylene or polypropylene；
3rd mixed solution is stirred and second ultrasonically treated, is dispersed in the modified zinc oxide described
In high polymer, then it is dried, obtains super material mixture；
The super material mixture is hot-forming, obtain metamaterial substrate.
2. the preparation method of metamaterial substrate according to claim 1, it is characterised in that the zinc salt and the alkalescence are molten
The mol ratio of liquid is 1:1.
3. the preparation method of metamaterial substrate according to claim 1, it is characterised in that the zinc salt is zinc nitrate or chlorine
Change zinc, the alkaline solution is sodium hydroxide or sodium carbonate liquor.
4. the preparation method of metamaterial substrate according to claim 1, it is characterised in that the quality of the Zinc oxide powder
Ratio with the volume of the isopropanol is 1g:80mL~2g:80mL, the coupling agent is titanate esters, its quality and described third
The ratio of the volume of ketone is 0.01g:80mL~0.05g:80mL.
5. the preparation method of metamaterial substrate according to claim 1, it is characterised in that it is described will be described modified oxidized
Progress is ultrasonically treated for the first time in zinc addition organic solvent, the modified zinc oxide is dispersed in the organic solvent,
Then add high polymer, in the step of obtaining three mixed solutions after stirring, the modified zinc oxide with it is described organic molten
The volume ratio of agent is 1:19~1:99, the mass ratio of the modified zinc oxide and the high polymer is 30%:70%~0.5%:
95.5%.
6. the preparation method of metamaterial substrate according to claim 5, it is characterised in that the organic solvent is methyl six
Hydrogen phthalic anhydride or tetrahydrofuran.
7. the preparation method of metamaterial substrate according to claim 1, it is characterised in that described that described 3rd mixing is molten
Liquid is stirred and second ultrasonically treated, the modified zinc oxide is dispersed in the high polymer, is then done
Dry, in the step of obtaining super material mixture, mixing time is 30~40min, second sonication treatment time be 30~
40min, drying temperature is 80~100 DEG C, the time is 5~5.5h.
8. the preparation method of metamaterial substrate according to claim 1, it is characterised in that described to mix the Meta Materials
Thing is hot-forming, and the step of obtaining metamaterial substrate includes：
The super material mixture is positioned over to hot-forming in mould, the metamaterial substrate of shape needed for obtaining, wherein, hot pressing
Temperature is the glass transition temperature of the high polymer, and its error is+5~+10 DEG C, and hot pressing pressure is 20~45MPa.
9. a kind of Super-material antenna, including copper foil and PUR, it is characterised in that the Super-material antenna also includes according to right
It is required that metamaterial substrate prepared by the method described in 1 to 8 any one, the copper foil is bonded in the super material by the PUR
Expect on substrate.
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| CN201210183314.0A CN103289316B (en) | 2012-03-02 | 2012-06-05 | The preparation method and Super-material antenna of a kind of metamaterial substrate |
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| CN101540435A (en) * | 2008-03-17 | 2009-09-23 | 西北工业大学 | S waveband arborization left-handed material microstrip antenna |
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| JPH09208927A (en) * | 1996-02-07 | 1997-08-12 | Sumitomo Osaka Cement Co Ltd | Ultraviolet-screening powder, ultraviolet-screening resin composition and ultraviolet-screening resin molding product |
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| CN101540435A (en) * | 2008-03-17 | 2009-09-23 | 西北工业大学 | S waveband arborization left-handed material microstrip antenna |
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