CN102408202B - Microstrip antenna composite substrate material and preparation method thereof - Google Patents
Microstrip antenna composite substrate material and preparation method thereof Download PDFInfo
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- CN102408202B CN102408202B CN 201110235563 CN201110235563A CN102408202B CN 102408202 B CN102408202 B CN 102408202B CN 201110235563 CN201110235563 CN 201110235563 CN 201110235563 A CN201110235563 A CN 201110235563A CN 102408202 B CN102408202 B CN 102408202B
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Abstract
Belonging to the technical field of electronic materials, the invention relates to a microstrip antenna composite substrate material and its preparation method. The composite substrate material is formed by compounding 70-90 parts by mass of a main phase material and 10-30 parts by mass of an auxiliary phase material, wherein, the main phase material is a Co2Z hexagonal ferrite which has a molecular formula of Ba3-xSrxCo2Fe24O41 (with x located in the range of 0-1.5), and the auxiliary phase material is polypropylene resin. The preparation method consists of: 1) material weighing, mixing, first ball milling and drying; 2) presintering; 3) secondary ball milling and drying; 4) sintering; 5) tertiary ball milling and drying; 6) compounding and granulation; 7) thermoforming, etc. The composite substrate material has an isomagnetic dielectric property and low loss in a frequency scope of 300MHz-3GHz, and has certain flexibility at the same time. The preparation method in the invention is simple and easy to operate, and convenient for mastering and popularization. Employment of the composite substrate material as a microstrip antenna substrate is conducive to reduce microstrip antenna weight and volume, and is in favor of enhancing the bandwidth and radiation efficiency of microstrip antennas.
Description
Technical field
The invention belongs to technical field of electronic materials, relate to composite substrate material of a kind of 300MHz of being suitable for～3GHz microstrip antenna application and preparation method thereof.
Background technology
Microstrip antenna is a kind of new antenna that occurs earlier 1970s.It has, and volume is little, lightweight, section is low, easily and carrier conformal, compatible good with unicircuit realized the advantages such as two-band, dual polarization work easily.Conventional microstrip antenna applying frequency is all higher, in recent years, along with the development of mobile communication technology, also progressively is applied and develops than the microstrip antenna of low-frequency range (such as UHF, L, S-band).But according to the structure Design and Calculation formula of microstrip antenna, its substrate size size is directly proportional with the wavelength of electromagnetic field in medium substrate.Because electromagnetic wavelength is very long under low frequency, therefore adopt the low frequency microstrip aerial size of traditional sucrose substrate processing very large, and frequency is lower, size is larger.
In order to dwindle size, quality and the volume than the low-frequency range microstrip antenna, a kind of mode is to improve the effective dielectric constant ε of antenna substrate material
EffBut take this mode, not only evoke easily surface-duided wave, and the high-k substrate can fetter electric field, the radiation efficiency of antenna is reduced greatly.According to the antenna resonant frequency relational expression
As can be known, improve the Effective permeability μ of antenna medium substrates
Eff, equally also can reach the effect that reduces the antenna substrate size, and be difficult for the radiation that evokes surface-duided wave and be conducive to antenna energy.Simultaneously, if can make the Effective permeability of medium substrate and effective dielectric constant equate that the natural impedance of antenna medium substrates is
Namely equate with the natural impedance of vacuum, can make like this antenna energy reflection very little, also of great advantage to the radiation efficiency that improves antenna.In addition, because the bandwidth of microstrip antenna mainly is subjected to the impact of substrate dielectric constant size, and irrelevant with the magnetic permeability size, specific inductivity is more little more to be conducive to improve bandwidth of an antenna.Therefore, under comparable size, take the antenna of equimagnetic dielectric material preparation also to have wider bandwidth than the antenna that adopts pure dielectric materials preparation.Therefore, the equimagnetic dielectric material is applied on the antenna substrate is of great practical significance.But, in order to obtain to have at antenna substrate the equimagnetic dielectric material of practical value, except requiring its magnetic permeability and specific inductivity equate in the antenna applications frequency range as far as possible, in order to improve the gain of antenna, also require such material to have try one's best low dielectric and magnetic loss, and the magnetic permeability of material/specific inductivity limiting frequency all need to be higher than the applying frequency of antenna.Therefore, the research and development technology difficulty of the type material is larger.At present both at home and abroad for the report of this correlation type material, mainly contain the people such as the M.L.S.Teo of Singapore Hwa Chong Institution and L.B.Kong and adopt Li
0.50Fe
2.50O
4Ferrite and Mg
1-xCu
xFe
1.98O
4The mode that ferrite carries out suitable ion substitution or doping obtains the stupalith that equimagnetic is situated between.(M.L.S.Teo, L.B.Kong, et al. " Development of magneto-dielectric materials based on Li-ferrite ceramics:I; II, III ", J.Alloys.Comp., vol.559 (2008) 557-566,567-575,576-582; L.B.Kong, Z.W.Li, " Magneto-dielectric properties of Mg-Cu-Co Ferrite Ceramics:I; II ", J.Am.Ceram.Soc., vol.90 (2007) 3106-3112,2104-2112) and the people such as A.Thakur of French National Laboratory adopt the Ni of the nanometer scale of nanopowder manufacturing system technology preparation
0.5Zn
0.3Co
0.2Fe
2O
4Ferrite ceramics material (A.Thakur, A.Chevalier, et al. " Low-loss spinel nanoferrite with matching permeability and permittivity in the ultrahigh frequency range ", J.Appl.Phys., vol.108 (2010) 014301).In addition, the people such as the Su Hua of University of Electronic Science and Technology, Tang Xiaoli have proposed the compound equimagnetic dielectric material of a kind of ferrospinel and strontium bismuth titanate ceramics in the Chinese invention patent " a kind of low frequency microstrip aerial substrate material and preparation method thereof (application number 200910058207.3) " of application in 2009.But, all there are relatively distinct issues in these equimagnetic dielectric materials of reporting before this, be exactly that its magnetic permeability and specific inductivity are all higher, although can reduce largely antenna size, the Snooker law of following according to magneticsubstance, its magnetic permeability is higher, limiting frequency is just lower, and therefore, the equimagnetic dielectric material limiting frequency of report is all below 300MHz before this, that have even be only suitable for to be used for the above antenna substrate of 300MHz in using in the following frequency range of 100MHz.
Summary of the invention
The invention provides a kind of microstrip antenna composite substrate material and preparation method thereof.Described microstrip antenna composite substrate material is a kind of hexgonal screw pottery and the compound type material that forms of macromolecule organic material, in the range of frequency of 300MHz～3GHz, have equimagnetic Jie property and low-loss (its magnetic permeability and specific inductivity all about 3, and frequency range internal ratio magnetic loss coefficient and all be lower than 0.01 than dielectric loss coefficient); Simultaneously, this composite substrate material also has certain snappiness, and is better than the performance of the anti-mechanical shock of conventional ceramic substrate material.Adopt composite substrate material provided by the invention as microstrip aerial substrate, not only help to reduce the microstrip antenna weight and volume, and be conducive to improve bandwidth and the radiation efficiency of microstrip antenna.
Technical solution of the present invention is:
A kind of microstrip antenna composite substrate material is formed by the principal phase material of 70～90 mass fractions and the auxiliary phase Material cladding of 10～30 mass fractions.Described principal phase material is Co
2The Z-type hexad ferrite, its prescription molecular formula is Ba
3-xSr
xCo
2Fe
24O
41, wherein the span of x is 0～1.5; Described auxiliary phase material is acrylic resin.
Above-mentioned microstrip antenna composite substrate material, described Co
2The doping vario-property agent that can contain dopant dose in the Z-type hexad ferrite principal phase material (as is mixed a small amount of Nb
2O
5Improve ferrite sintered density, mix a small amount of Bi
2O
3Reduce ferrite sintered temperature etc.).
Need to prove: 1) principal phase material C o
2The Fe ion of the Co ion of divalence and trivalent also can be carried out a small amount of substituting by the metal ion of other divalence and trivalent in the Z-type hexad ferrite prescription molecular formula, thereby to ferritic magnetic property, consist of some impacts such as magnetic permeability, magnetic loss etc., enumerate no longer one by one at this, but these ion substitutions are optional; 2) principal phase material C o
2In the Z-type hexad ferrite prescription molecular formula, along with the value from 0 to 1.5 of x increases corresponding Co gradually
2The ferritic magnetic permeability of Z-type and specific inductivity increase to about 15 (specific inductivity is a little less than magnetic permeabilities) from about 10; Adopt acrylic resin (specific inductivity is about 2, and magnetic permeability is 1) and described Co
2The ferritic magnetic permeability of Z-type described compound in proportion after, the magnetic permeability of integral composite and specific inductivity can tune to about 3; 3) acrylic resin adopts conventional commercially available industrial injection moulding class acrylic resin get final product, and the injection moulding class acrylic resin of the different trades mark has slightly difference at specific inductivity, thus with Co
2The Z-iron oxysome carries out compound tense, can obtain by fine setting ferrite phase and the ratio of acrylic resin equimagnetic Jie's (magnetic permeability equates with specific inductivity or be substantially equal) parameter request.
The preparation method of above-mentioned microstrip antenna composite substrate material as shown in Figure 1, may further comprise the steps:
Step 1: with Fe
2O
3, BaCO
3, SrCO
3And Co
2O
3Be raw material, according to Co
2Z-iron oxysome prescription molecular formula Ba
3-xSr
xCo
2Fe
24O
41The ratio of middle metallic element is converted out Fe
2O
3, BaCO
3, SrCO
3And Co
2O
3Mass percent, carry out weighing, batch mixing, a ball milling post-drying; Wherein the span of x is 0～1.5.
Step 2: compacting punching in the sintering alms bowl after ball milling of step 1 gained oven dry material sieved, rise to calcined temperature by 3 ℃/minutes temperature rise rates and carry out pre-burning, furnace cooling obtains ferrite prefiring material.Described calcined temperature scope is 1150 ℃～1250 ℃, and soaking time is 2～3 hours.
Step 3: step 2 gained preburning powdered material is carried out secondary ball milling (also can in this process, add a small amount of doping vario-property agent, as mix a small amount of Nb
2O
5Improve ferrite sintered density, mix a small amount of Bi
2O
3Reduce ferrite sintered temperature etc., but it is optional to mix), the mean particle size of powder is controlled at below 1 micron behind the secondary ball milling, then the secondary ball abrasive material is dried.
Step 4: pour in the sintering alms bowl after step 3 gained secondary ball milling oven dry material sieved, rise to ferrite sintered temperature by 2～3 ℃/minutes temperature rise rates and carry out sintering, furnace cooling obtains Co
2The ferrite sintered powder of Z.Described ferrite sintered temperature range is 1200～1300 ℃, and soaking time is 3～4 hours.
Step 5: with the Co of step 4 gained
2The ferrite sintered powder of Z carries out ball milling three times, and the mean particle size of powder is controlled at below 1 micron behind three ball millings, then with three ball milling material oven dry.
Step 6: three ball milling oven dry of step 5 gained material is pressed b with acrylic resin: mass percent weighing (100-b), wherein the span of b is 70～90; Two kinds of material are mixed in parallel dual-screw extruding machine, and granulation obtains the granulation material of microstrip antenna composite substrate material.
Step 7: the pellet of step 6 granulation gained microstrip antenna composite substrate material is carried out hot-forming, obtain final microstrip antenna composite substrate material.Concrete hot pressing is: at first the granulation material of microstrip antenna composite substrate material is put into mould in 200 ℃ of lower preheatings 10～15 minutes, then hot pressing 5～8 minutes under 200 ℃, 10MPa pressure was colded pressing 5～8 minutes under normal temperature, lower 10MPa pressure at last.
Through above seven steps, just can obtain microstrip antenna composite substrate material of the present invention, after tested, this material is in the range of frequency of 300MHz～3GHz, magnetic permeability and specific inductivity all about 3, and frequency range internal ratio magnetic loss coefficient and all be lower than 0.01 than dielectric loss coefficient.
The major advantage of microstrip antenna composite substrate material provided by the invention is:
1, in the frequency range of 300M～3GHz, its magnetic permeability and specific inductivity are all about 3, and frequency range internal ratio magnetic loss coefficient and all be lower than 0.01 than dielectric loss coefficient, the limiting frequency of this matrix material reality can reach more than the 5GHz, may be used in principle on the frequency range near 5GHz, just surpass after the 3GHz, magnetic loss is relatively high, and the gain of antenna is had certain reduction.
2, adopt this material as microstrip aerial substrate, not only can dwindle size and the volume of microstrip antenna, expand bandwidth of an antenna, but also can guarantee that the impedance of antenna substrate properties of materials equates with the natural impedance of vacuum or approaching, thereby can promote significantly the radiation efficiency of antenna.
3, this baseplate material contains macromolecule organic material, and the snappiness of sheet material is higher than conventional ceramic substrate material.
4, this each step process of material preparation method is common process, and is simple to operation.
In sum, microstrip antenna composite substrate material provided by the invention, in the range of frequency of 300MHz～3GHz, have equimagnetic Jie property and low-loss (its magnetic permeability and specific inductivity all about 3, and frequency range internal ratio magnetic loss coefficient and all be lower than 0.01 than dielectric loss coefficient); Simultaneously, this composite substrate material also has certain snappiness, and is better than the performance of the anti-mechanical shock of conventional ceramic substrate material.Adopt composite substrate material provided by the invention as microstrip aerial substrate, not only help to reduce the microstrip antenna weight and volume, and be conducive to improve bandwidth and the radiation efficiency of microstrip antenna.This material preparation method that the present invention provides simultaneously is simple to operation, is convenient to grasp and promote.
Description of drawings
Fig. 1 is preparation method's schematic flow sheet of microstrip antenna composite substrate material provided by the invention.
Embodiment
A kind of microstrip antenna composite substrate material is formed by the principal phase material of 80 mass fractions and the auxiliary phase Material cladding of 20 mass fractions.Described principal phase material is Co
2The Z-type hexad ferrite, its prescription molecular formula is Ba
1.5Sr
1.5Co
2Fe
24O
41Described auxiliary phase material is acrylic resin (the commercially available trade mark: Dushanzi petrochemical industry EPS30R).
The concrete preparation method of above-mentioned microstrip antenna composite substrate material is as follows:
Step 1: with Fe
2O
3, BaCO
3, SrCO
3And Co
2O
3Be raw material, according to the mass percent that the ratio of metallic element in the above-mentioned ferrite formulations molecular formula is converted out various oxide compounds, carry out accurate weighing after, ball milling is 4 hours in planetary ball mill, material places baking oven in 100 ℃ of lower oven dry behind the ball milling.
Step 2: compacting punching in the sintering alms bowl after step 1 gained oven dry material sieved, rise to 1250 ℃ of pre-burnings by 3 ℃/minutes temperature rise rates, be incubated 2 hours, furnace cooling obtains ferrite prefiring material.
Step 3: step 2 gained ferrite prefiring powder was carried out secondary ball milling 6 hours, and then the mean particle size of powder dries the secondary ball abrasive material about 0.8 micron behind the secondary ball milling.
Step 4: pour in the sintering alms bowl after step 3 gained secondary ball milling oven dry material sieved, rise to 1230 ℃ by 2.5 ℃/minutes temperature rise rates and carry out sintering, be incubated 3 hours, furnace cooling obtains Co
2The ferrite sintered powder of Z.
Step 5: with step 4 gained Co
2The ferrite sintered powder of Z carried out three ball millings 6 hours again, then with three ball milling material oven dry.
Step 6: with three ball milling oven dry of step 5 gained material and the mass percent weighing of acrylic resin by 80: 20, two kinds of material are mixed in parallel dual-screw extruding machine, granulation obtains the granulation material of microstrip antenna composite substrate material.
Step 7: carry out the granulation material of step 6 gained microstrip antenna composite substrate material hot-forming.Concrete hot pressing is: at first the granulation material of microstrip antenna composite substrate material is put into mould in 200 ℃ of lower preheatings 10 minutes, then hot pressing 5 minutes under 200 ℃, 10MPa pressure was colded pressing 5 minutes under normal temperature, 10MPa pressure at last.
Through above-mentioned steps, obtain microstrip antenna composite substrate material of the present invention, after tested, this material is in the range of frequency of 300MHz～3GHz, magnetic permeability is stabilized between 2.95～3.05, is lower than 0.01 than magnetic loss coefficient always, part frequency even be in 10
-4Magnitude, specific inductivity are stabilized between 2.98～3.10, also are lower than 0.01 than dielectric loss coefficient always.
Adopt this composite substrate material to be used as working in the interior microstrip aerial substrate of 300MHz～3GHz band limits, not only be conducive to reduce the weight and volume of microstrip antenna, expand the bandwidth of antenna, and be very beneficial for the raising of microstrip antenna radiation efficiency.
Above-mentioned embodiment is not to be limitation of the invention further, and those skilled in the art should know according to of the present invention: by adjust principal phase Co in 0～1.5 scope
2Z-type hexad ferrite prescription molecular formula is Ba
3-xSr
xCo
2Fe
24O
41The span of middle x and in (70～90): adjust the quality proportioning between principal phase and the auxiliary phase in (10～30) scope, and suitably add the doping vario-property agent, all can obtain microstrip antenna composite substrate material of the present invention.
Claims (7)
1. a microstrip antenna composite substrate material is formed by the principal phase material of 70 ~ 90 mass fractions and the auxiliary phase Material cladding of 10 ~ 30 mass fractions; Described principal phase material is Co
2The Z-type hexad ferrite, its prescription molecular formula is Ba
3-xSr
xCo
2Fe
24O
41, wherein the span of x is 0 ~ 1.5; Described auxiliary phase material is acrylic resin.
2. a microstrip antenna composite substrate material is formed by the principal phase material of 70 ~ 90 mass fractions and the auxiliary phase Material cladding of 10 ~ 30 mass fractions; Described principal phase material is Co
2The Z-type hexad ferrite, its prescription molecular formula is Ba
3-xSr
xCo
2Fe
24O
41, wherein the span of x is 0 ~ 1.5, Co simultaneously
2Contain in the Z-type hexad ferrite principal phase material dopant dose, improve ferrite sintered density or reduce the doping vario-property agent of ferrite sintered temperature; Described auxiliary phase material is acrylic resin.
3. microstrip antenna composite substrate material according to claim 2 is characterized in that, the doping vario-property agent of the ferrite sintered density of described raising is Nb
2O
5The doping vario-property agent of the ferrite sintered temperature of described reduction is Bi
2O
3
4. the preparation method of a microstrip antenna composite substrate material may further comprise the steps:
Step 1: with Fe
2O
3, BaCO
3, SrCO
3And Co
2O
3Be raw material, according to Co
2Z-iron oxysome prescription molecular formula Ba
3-xSr
xCo
2Fe
24O
41The ratio of middle metallic element is converted out Fe
2O
3, BaCO
3, SrCO
3And Co
2O
3Mass percent, carry out weighing, batch mixing, a ball milling post-drying; Wherein the span of x is 0 ~ 1.5;
Step 2: compacting punching in the sintering alms bowl after ball milling of step 1 gained oven dry material sieved, rise to calcined temperature by 3 ℃/minutes temperature rise rates and carry out pre-burning, furnace cooling obtains ferrite prefiring material; Described calcined temperature scope is 1150 ℃ ~ 1250 ℃, and soaking time is 2～3 hours;
Step 3: step 2 gained preburning powdered material is carried out secondary ball milling, and the mean particle size of powder is controlled at below 1 micron behind the secondary ball milling, then the secondary ball abrasive material is dried;
Step 4: pour in the sintering alms bowl after step 3 gained secondary ball milling oven dry material sieved, rise to ferrite sintered temperature by 2 ~ 3 ℃/temperature rise rates that divide and carry out sintering, furnace cooling obtains Co
2The ferrite sintered powder of Z; Described ferrite sintered temperature range is 1200～1300 ℃, and soaking time is 3 ~ 4 hours;
Step 5: with the Co of step 4 gained
2The ferrite sintered powder of Z carries out ball milling three times, and the mean particle size of powder is controlled at below 1 micron behind three ball millings, then with three ball milling material oven dry;
Step 6: three ball milling oven dry of step 5 gained material is pressed b with acrylic resin: mass percent weighing (100-b), wherein the span of b is 70～90; Two kinds of material are mixed in parallel dual-screw extruding machine, and granulation obtains the granulation material of microstrip antenna composite substrate material;
Step 7: the pellet of step 6 granulation gained microstrip antenna composite substrate material is carried out hot-forming, obtain final microstrip antenna composite substrate material.
5. the preparation method of microstrip antenna composite substrate material according to claim 4, it is characterized in that, process described in the step 7 is: at first the granulation material of microstrip antenna composite substrate material is put into mould in 200 ℃ of lower preheatings 10 ~ 15 minutes, then hot pressing 5 ~ 8 minutes under 200 ℃, 10MPa pressure was colded pressing 5 ~ 8 minutes under normal temperature, 10MPa pressure at last.
6. according to claim 4 or the preparation method of 5 described microstrip antenna composite substrate materials, it is characterized in that, add in the secondary ball milling process in described step 3 dopant dose, improve ferrite sintered density or reduce the doping vario-property agent of ferrite sintered temperature.
7. the preparation method of microstrip antenna composite substrate material according to claim 6 is characterized in that, the doping vario-property agent of the ferrite sintered density of described raising is Nb
2O
5The doping vario-property agent of the ferrite sintered temperature of described reduction is Bi
2O
3
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| CN103242037B (en) * | 2013-05-13 | 2015-07-08 | 电子科技大学 | Hexagonal ferrite material with high magnetic loss in L wave band and preparation method thereof |
| CN104250094B (en) * | 2013-06-27 | 2017-03-22 | 江粉磁材（武汉）技术研发有限公司 | Nickel copper zinc ferrite used for preparation of noise inhibition sheet and preparation method of noise inhibition sheet |
| CN103304186B (en) * | 2013-07-03 | 2014-08-13 | 电子科技大学 | Ferrite-base composite magnetic dielectric antenna substrate material and preparation method thereof |
| CN103435337A (en) * | 2013-08-20 | 2013-12-11 | 韶关西格玛技术有限公司 | Method for improving property of dry pressing isotropic permanent magnetic ferrite |
| CN103482969A (en) * | 2013-09-12 | 2014-01-01 | 钢铁研究总院 | Ferrite wave-absorbing material and preparation method thereof |
| EP3180294B1 (en) * | 2014-07-31 | 2021-04-28 | Rogers Corporation | Co2 z-type ferrite composite material for use in ultra-high frequency antennas |
| CN104355608A (en) * | 2014-10-23 | 2015-02-18 | 苏州华冲精密机械有限公司 | High-performance ferrite core material and preparation method thereof |
| CN108475568B (en) * | 2016-01-18 | 2022-05-31 | 罗杰斯公司 | Magneto-dielectric material comprising hexaferrite fibres, method for preparing same and use thereof |
| KR102608246B1 (en) * | 2016-06-30 | 2023-11-29 | 삼성전자주식회사 | Magnetic sintered ceramic, method of making the same, and antenna device comprising the magnetic sintered ceramic |
| CN109111222B (en) * | 2018-09-30 | 2022-03-01 | 陕西科技大学 | Co-doped multiferroic ceramic with Olivies structure and preparation method thereof |
| CN110526617B (en) * | 2019-09-02 | 2022-01-25 | 深圳市信维通信股份有限公司 | Antenna substrate material |
| CN111639737A (en) * | 2019-09-27 | 2020-09-08 | 深圳锐驰物联科技有限公司 | Novel ultrahigh frequency anti-metal label production method |
| CN111302706B (en) * | 2020-03-12 | 2021-07-20 | 江西重恒工瓷科技有限公司 | High-flexibility magnetic dielectric composite substrate material and preparation method and application thereof |
| CN115677338B (en) * | 2022-11-21 | 2024-01-16 | 哈尔滨工业大学 | Z-type hexagonal ferrite magneto-electric coupling ceramic material and preparation method thereof |
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|---|---|---|---|---|
| CN101462872A (en) * | 2009-01-21 | 2009-06-24 | 电子科技大学 | Low frequency microstrip aerial substrate material and preparation thereof |
| CN101913850A (en) * | 2010-07-06 | 2010-12-15 | 电子科技大学 | Preparation method of high-magnetic-conductivity low-temperature-sintering Z-shaped hexagonal ferrite material |
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| CN101462872A (en) * | 2009-01-21 | 2009-06-24 | 电子科技大学 | Low frequency microstrip aerial substrate material and preparation thereof |
| CN101913850A (en) * | 2010-07-06 | 2010-12-15 | 电子科技大学 | Preparation method of high-magnetic-conductivity low-temperature-sintering Z-shaped hexagonal ferrite material |
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