CN110357607B - MAS-LT composite microwave dielectric ceramic and preparation method thereof - Google Patents
MAS-LT composite microwave dielectric ceramic and preparation method thereof Download PDFInfo
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- CN110357607B CN110357607B CN201910827080.0A CN201910827080A CN110357607B CN 110357607 B CN110357607 B CN 110357607B CN 201910827080 A CN201910827080 A CN 201910827080A CN 110357607 B CN110357607 B CN 110357607B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 94
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims description 20
- 238000005245 sintering Methods 0.000 claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 74
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 15
- 229910007848 Li2TiO3 Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 82
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 66
- 239000000843 powder Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 44
- 238000000227 grinding Methods 0.000 claims description 43
- 238000000498 ball milling Methods 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000000654 additive Substances 0.000 claims description 29
- 230000000996 additive effect Effects 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 229910052681 coesite Inorganic materials 0.000 claims description 24
- 229910052906 cristobalite Inorganic materials 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- 229910052682 stishovite Inorganic materials 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052905 tridymite Inorganic materials 0.000 claims description 24
- 238000007873 sieving Methods 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 15
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 14
- 238000003825 pressing Methods 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 abstract description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 49
- 238000001816 cooling Methods 0.000 description 30
- 238000004321 preservation Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 9
- 239000007767 bonding agent Substances 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 229910052573 porcelain Inorganic materials 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 231100000956 nontoxicity Toxicity 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000010295 mobile communication Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052844 willemite Inorganic materials 0.000 description 1
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Abstract
The invention provides a MAS-LT composite microwave dielectric ceramic, which has a general formula shown as the following formula: mg (magnesium)2‑xBaxAl4Si5O18‑Li2TiO3(ii) a Wherein x is 0 to 0.16; li in MAS-LT composite microwave dielectric ceramic2TiO3The mass percentage of the component (A) is 6-24%. Compared with the prior art, the MAS-LT composite microwave dielectric ceramic provided by the invention takes the composite oxide with the specific general formula as a main material, and Li is adjusted2TiO3The content of (A) can realize that the dielectric constant is between 4 and 6, and the frequency temperature coefficient is continuously adjustable; moreover, the MAS-LT composite microwave dielectric ceramic has a stable structure, a specific dielectric constant and a high Q multiplied by f value, and the temperature coefficient of the resonant frequency is continuously adjustable. Experimental results show that the dielectric constant of the MAS-LT composite microwave dielectric ceramic is 4-5.8, the Qxf is not less than 35800GHz and can reach 87600GHz, and compared with other microwave dielectric ceramics with the same dielectric constant, the system has high Qxf value and low dielectric loss; meanwhile, the temperature coefficient of the resonance frequency is continuously adjustable between-12 ppm/DEG C and +13 ppm/DEG C, the sintering temperature is as low as 950 ℃, and the formula can be flexibly adjusted.
Description
Technical Field
The invention relates to the technical field of microwave dielectric ceramics, in particular to MAS-LT composite microwave dielectric ceramics and a preparation method thereof.
Background
In the future, mobile communication technology and industry will step into the development stage of the fifth generation mobile communication (5G). The 5G can meet the requirements of people on ultrahigh flow density, ultrahigh connection number density and ultrahigh mobility, can permeate into the fields of Internet of things and the like, is deeply integrated with industrial facilities, medical instruments, vehicles and the like, comprehensively realizes the 'everything interconnection' and effectively meets the information service requirements of vertical industries such as industry, medical treatment, traffic and the like. The frequency band of 5G deployment in the global scope mainly comprises Sub-6 and millimeter wave. Millimeter waves with shorter wavelengths provide better resolution and security for data transmission due to narrower beams, and are favored because of high speed, large data volume and small time delay. The frequency is inversely proportional to the square root of the dielectric constant under the same size, so that the millimeter wave application needs a microwave dielectric material with the dielectric constant of 4-6. At present, cordierite systems, forsterite systems and willemite systems which are researched more frequently have the defects of overlarge frequency temperature coefficient and high sintering temperature, and the large-scale use is limited.
Disclosure of Invention
In view of the above, the present invention provides a MAS-LT composite microwave dielectric ceramic and a preparation method thereof, wherein the MAS-LT composite microwave dielectric ceramic has a dielectric constant of 4 to 6, a high Q × f value, a low dielectric loss, and a continuously adjustable temperature coefficient of resonance frequency.
The invention provides a MAS-LT composite microwave dielectric ceramic, which has a general formula shown in a formula (I):
Mg2-xBaxAl4Si5O18-Li2TiO3formula (I);
in the formula (I), x is 0-0.16; li in MAS-LT composite microwave dielectric ceramic2TiO3The mass percentage of the component (A) is 6-24%.
Preferably, the method further comprises the following steps:
an additive;
the additive is prepared from the following components in percentage by mass (1-10): (10-30): (15-40): (12-40): (1-10) SiO2、B2O3、ZnO、Bi2O3And MgO.
Preferably, the preparation method of the additive specifically comprises the following steps:
mixing SiO2、B2O3、ZnO、Bi2O3Mixing with MgO, ball milling, melting at 900-1200 deg.c for 10-30 min, separating, crushing and sieving to obtain the additive.
The invention also provides a preparation method of the MAS-LT composite microwave dielectric ceramic, which comprises the following steps:
a) MgCO is mixed with3、BaCO3、Al2O3And SiO2After mixing, carrying out primary grinding treatment, and then carrying out primary presintering to obtain a MAS presintering material;
b) mixing Li2CO3And TiO2After mixing, carrying out secondary grinding treatment, and then carrying out secondary pre-sintering to obtain an LT pre-sintering material;
c) mixing the MAS pre-sintering material and the LT pre-sintering material, and then carrying out third grinding treatment to obtain MAS-LT powder;
d) adding a binder into the MAS-LT powder for granulation molding to obtain a ceramic green body; sintering the obtained ceramic green body to obtain MAS-LT composite microwave dielectric ceramic;
the step a) and the step b) are not limited in order.
Preferably, the first grinding treatment in step a) specifically comprises the following steps:
mixing the mixed raw materials, agate balls and water in a ratio of 1: (1-4): (2-3), ball-milling for 6-10 h at the rotating speed of 200-300 r/min, and drying at 80-150 ℃ to obtain the mixed material after the first grinding treatment.
Preferably, the temperature of the first presintering in the step a) is 800-1100 ℃, the heating rate is 2-4 ℃/min, and the heat preservation time is 2-3 h.
Preferably, the adhesive in the step b) is a polyvinyl alcohol aqueous solution with the mass percentage of 6-8%;
the MASs ratio of the MAS-LT powder to the adhesive is 100: (7-10).
Preferably, the granulation molding process in the step b) specifically comprises the following steps:
adding an adhesive into the MAS-LT powder, granulating and grinding for 0.5-1.5 h, sieving with a 30-50-mesh sieve, and pressing and molding the obtained powder under the pressure of 80-120 MPa to obtain a ceramic green body.
Preferably, the sintering temperature in the step b) is 950-1330 ℃, the heating rate is 2-4 ℃/min, and the heat preservation time is 2-4 h.
Preferably, the step c) further comprises:
and mixing the MAS pre-sintering material, the LT pre-sintering material and the additive, and then carrying out third grinding treatment to obtain MAS-LT powder.
The invention provides a MAS-LT composite microwave dielectric ceramic, which has a general formula shown as the following formula: mg (magnesium)2- xBaxAl4Si5O18-Li2TiO3(ii) a Wherein x is 0 to 0.16; li in MAS-LT composite microwave dielectric ceramic2TiO3The mass percentage of the component (A) is 6-24%. Compared with the prior art, the MAS-LT composite microwave dielectric ceramic provided by the invention takes the composite oxide with the specific general formula as a main material, and Li is adjusted2TiO3The content of (A) can realize that the dielectric constant is between 4 and 6, and the frequency temperature coefficient is continuously adjustable; moreover, the MAS-LT composite microwave dielectric ceramic has a stable structure, a specific dielectric constant and a high Q multiplied by f value, and the temperature coefficient of the resonant frequency is continuously adjustable. Experimental results show that the dielectric constant of the MAS-LT composite microwave dielectric ceramic is 4-5.8, the Qxf is not less than 35800GHz and can reach 87600GHz, and compared with other microwave dielectric ceramics with the same dielectric constant, the system has high Qxf value and low dielectric loss; meanwhile, the temperature coefficient of the resonance frequency is continuously adjustable between-12 ppm/DEG C to +13 ppm/DEG C, and the formula can be flexibly adjusted.
In addition, the preparation method provided by the invention has the advantages of simple process, low sintering temperature of 950 ℃, environmental protection, no toxicity, no environmental pollution, suitability for large-scale industrialization and very wide development prospect, and meets the requirement of environmental protection.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a MAS-LT composite microwave dielectric ceramic, which has a general formula shown in a formula (I):
Mg2-xBaxAl4Si5O18-Li2TiO3formula (I);
in the formula (I), x is 0-0.16; li in MAS-LT composite microwave dielectric ceramic2TiO3The mass percentage of the component (A) is 6-24%.
In the invention, the MAS-LT composite microwave dielectric ceramic is made of MAS (Mg)2-xBaxAl4Si5O18) And LT (Li)2TiO3) Compounding; wherein MAS is composed of MgO and BaCO3、Al2O3And SiO2Based on a composite of LT and LiCO3And TiO2Is compounded on the basis. In the invention, Li in MAS-LT composite microwave dielectric ceramic2TiO3The mass percentage content of the compound is 6 to 24 percent; in the preferred embodiment of the invention, Li in MAS-LT composite microwave dielectric ceramic2TiO3The mass percentage of the components is respectively 6%, 12%, 18% and 24%. In the present invention, the Li2TiO3The addition of (A) is mainly to improve the dielectric constant and adjust the temperature coefficient of the resonant frequency to approach zero; if Li is present2TiO3Less than 6%, the dielectric constant is large, and Li2TiO3When the amount of (2) is more than 24%, the Q.times.f. value is drastically decreased.
In the invention, x is 0-0.16, preferably 0.08; in a preferred embodiment of the present invention, the value of x is 0, 0.08, and 0.16, respectively.
The MAS-LT composite microwave dielectric ceramic provided by the invention takes the composite oxide with the specific general formula as a main body material, can realize the dielectric constant of 4-6, and simultaneously leads Mg with a negative resonance frequency temperature coefficient2-xBaxAl4Si5O18(x-0 to 0.16) ceramic and Li having positive temperature coefficient of resonance frequency2TiO3Ceramic phaseCompounding provides a composition comprising Mg2- xBaxAl4Si5O18(x is 0 to 0.16) and Li2TiO3The composite microwave dielectric ceramic with two crystal phase structures not only leads the resonant frequency temperature coefficient of the composite microwave dielectric ceramic to approach zero, but also improves the Q multiplied by f value of the ceramic; moreover, the MAS-LT composite microwave dielectric ceramic has a stable structure, and meanwhile, the temperature coefficient of the resonant frequency is continuously adjustable, and the formula can be flexibly adjusted.
In the present invention, the MAS-LT composite microwave dielectric ceramic preferably further comprises:
and (3) an additive.
In the invention, the additive is preferably prepared from the following components in a mass ratio of (1-10): (10-30): (15-40): (12-40): (1-10) SiO2、B2O3、ZnO、Bi2O3And MgO, more preferably 8: 27: 30: 25: 10 SiO2、B2O3、ZnO、Bi2O3And MgO.
In the present invention, the preparation method of the additive is preferably specifically:
mixing SiO2、B2O3、ZnO、Bi2O3Mixing with MgO, ball milling, melting at 900-1200 deg.c for 10-30 min, separating, crushing and sieving to obtain additive;
more preferably:
mixing SiO2、B2O3、ZnO、Bi2O3Mixing with MgO, ball milling, drying, sieving, melting at 1000 deg.C for 20min, separating, crushing, and sieving to obtain the additive.
The ball milling equipment is not particularly limited in the present invention, and a ball mill known to those skilled in the art may be used. In the present invention, the time for the ball milling is preferably 20 to 30 hours, and more preferably 24 hours. In the present invention, the separation is preferably performed by extraction with water, and the present invention is not particularly limited thereto. The process of the present invention is not particularly limited, and the crushing method known to those skilled in the art may be used. In the present invention, the size of the mesh of the screen is preferably 150 to 250 mesh, and more preferably 200 mesh. By adopting the preparation method, the refined additive can be obtained, and the subsequent use is convenient.
In the present invention, the amount of the additive is preferably not more than 3% by MASs, more preferably 1.5% to 3% by MASs of the MAS-LT composite microwave dielectric ceramic.
In the invention, the additive can reduce the sintering temperature, inhibit titanium reduction and improve the Q multiplied by f value.
The invention also provides a preparation method of the MAS-LT composite microwave dielectric ceramic, which comprises the following steps:
a) MgCO is mixed with3、BaCO3、Al2O3And SiO2After mixing, carrying out primary grinding treatment, and then carrying out primary presintering to obtain a MAS presintering material;
b) mixing Li2CO3And TiO2After mixing, carrying out secondary grinding treatment, and then carrying out secondary pre-sintering to obtain an LT pre-sintering material;
c) mixing the MAS pre-sintering material and the LT pre-sintering material, and then carrying out third grinding treatment to obtain MAS-LT powder;
d) adding a binder into the MAS-LT powder for granulation molding to obtain a ceramic green body; sintering the obtained ceramic green body to obtain MAS-LT composite microwave dielectric ceramic;
the step a) and the step b) are not limited in order.
Firstly, MgCO is mixed with3、BaCO3、Al2O3And SiO2After mixing, grinding for the first time, and then pre-sintering for the first time to obtain the MAS pre-sintering material. The invention is directed to the MgCO3、BaCO3、Al2O3And SiO2The source of (A) is not particularly limited, and commercially available products known to those skilled in the art may be used. In the present invention, the MgCO is3、BaCO3、Al2O3And SiO2In an amount corresponding to Mg in the general formula shown in formula (I)2-xBaxAl4Si5O18The stoichiometric ratio of (c) was calculated.
In the present invention, the first grinding process preferably includes:
mixing the mixed raw materials, agate balls and water in a ratio of 1: (1-4): (2-3), ball-milling for 6-10 h at the rotating speed of 200-300 r/min, and drying at 80-150 ℃ to obtain a mixed material after primary grinding treatment;
more preferably:
mixing the mixed raw materials, agate balls and water in a ratio of 1: 2: 2, ball-milling for 6 hours at the rotating speed of 250r/min, and then drying at 150 ℃ to obtain a mixed material after the first grinding treatment.
The ball milling equipment is not particularly limited in the present invention, and a planetary ball mill well known to those skilled in the art may be used.
After the mixed material after the first grinding treatment is obtained, the mixed material obtained after the first grinding treatment is subjected to first presintering to obtain a MAS presintering material. In the invention, the temperature of the first presintering is preferably 800-1100 ℃, and more preferably 1000 ℃; the heating rate of the first presintering is preferably 2-4 ℃/min, more preferably 3 ℃/min; the heat preservation time of the first pre-sintering is preferably 2h to 3h, and more preferably 3 h.
Before obtaining the MAS pre-sintering material, the invention preferably also comprises the steps of cooling the product after the first pre-sintering; the furnace cooling solution known to those skilled in the art may be used, and the present invention is not limited thereto.
Meanwhile, the invention uses Li2CO3And TiO2And after mixing, carrying out secondary grinding treatment, and then carrying out secondary pre-sintering to obtain the LT pre-sintering material. The invention is directed to said Li2CO3And TiO2The source of (A) is not particularly limited, and commercially available products known to those skilled in the art may be used. In the present invention, the Li2CO3And TiO2In an amount corresponding to Li in the general formula shown in formula (I)2TiO3Stoichiometric calculation of (i.e. Li)2CO3：TiO21: 1, calculated as a molar ratio.
In the present invention, the second grinding process is the same as the first grinding process, and preferably specifically includes:
mixing the mixed raw materials, agate balls and water in a ratio of 1: (1-4): (2-3), ball-milling for 6-10 h at the rotating speed of 200-300 r/min, and drying at 80-150 ℃ to obtain a mixed material after the second grinding treatment;
more preferably:
mixing the mixed raw materials, agate balls and water in a ratio of 1: 2: 2, ball-milling for 6 hours at the rotating speed of 250r/min, and then drying at 150 ℃ to obtain a mixed material after the second grinding treatment.
The ball milling equipment is not particularly limited in the present invention, and a planetary ball mill well known to those skilled in the art may be used.
After the mixed material after the second grinding treatment is obtained, the mixed material obtained after the second grinding treatment is subjected to second pre-sintering to obtain an LT pre-sintering material. In the invention, the temperature of the second pre-sintering is preferably 800-1100 ℃, and more preferably 1000 ℃; the heating rate of the second pre-sintering is preferably 2-4 ℃/min, and more preferably 3 ℃/min; the heat preservation time of the second pre-sintering is preferably 2h to 3h, and more preferably 2 h.
Before obtaining the LT pre-sintering material, the method preferably further comprises the steps of cooling a product after the second pre-sintering; the furnace cooling solution known to those skilled in the art may be used, and the present invention is not limited thereto.
After the MAS pre-sintering material and the LT pre-sintering material are obtained, the MAS pre-sintering material and the LT pre-sintering material are mixed and then are ground for the third time to obtain MAS-LT powder. The present invention preferably further comprises:
and mixing the MAS pre-sintering material, the LT pre-sintering material and the additive, and then carrying out third grinding treatment to obtain MAS-LT powder. In the present invention, the additive is the same as that described in the above technical solution, and is not described herein again. In the present invention, the amount of the additive is preferably not more than 3%, more preferably 1.5% to 3%, of the total MASs of the MAS pre-firing material and the LT pre-firing material.
In the present invention, the third grinding process is the same as the first grinding process, and preferably specifically includes:
mixing the mixed raw materials, agate balls and water in a ratio of 1: (1-4): (2-3), ball-milling for 6-10 h at the rotating speed of 200-300 r/min, and drying at 80-150 ℃ to obtain MAS-LT powder;
more preferably:
mixing the mixed raw materials, agate balls and water in a ratio of 1: 2: 2, ball milling for 10 hours at the rotating speed of 250r/min, and then drying at the temperature of 80 ℃ to obtain MAS-LT powder.
The ball milling equipment is not particularly limited in the present invention, and a planetary ball mill well known to those skilled in the art may be used.
After the MAS-LT powder is obtained, adding a binder into the MAS-LT powder for granulation molding to obtain a ceramic green body; and sintering the obtained ceramic green body to obtain the MAS-LT composite microwave dielectric ceramic. In the invention, the adhesive has enough viscosity, can ensure good formability and mechanical strength of the green body, and can be completely volatilized after high-temperature calcination, so that residual impurities of the adhesive are not left in the green body. In the present invention, the binder is preferably a polyvinyl alcohol aqueous solution with a mass percentage of 6% to 8%, and more preferably a polyvinyl alcohol aqueous solution with a mass percentage of 7%. In the present invention, the polyvinyl alcohol is converted into CO after high-temperature calcination (subsequent sintering process)2And H2O, can be completely volatilized.
In the present invention, the MASs ratio of the MAS-LT powder to the binder is preferably 100: (7-10), more preferably 100: 7.
in the present invention, the granulation molding process preferably includes:
adding an adhesive into the MAS-LT powder, granulating and grinding for 0.5-1.5 h, sieving with a 30-50-mesh sieve, and pressing and molding the obtained powder under the pressure of 80-120 MPa to obtain a ceramic green body;
more preferably:
and adding a binder into the MAS-LT powder, granulating and grinding for 1h, sieving by a 40-mesh sieve, and pressing and molding the obtained powder under the pressure of 100MPa to obtain a ceramic green body. In the present invention, the granulating and grinding process enables the MAS-LT powder to be uniformly mixed with a binder and granulated.
In the present invention, the ceramic green body is preferably a thin cylindrical green body having a thickness of 4mm to 10mm and a diameter of 8mm to 20mm, and more preferably a thin cylindrical green body having a thickness of 6mm and a diameter of 13mm (a cylinder having a diameter to height ratio of about 2.0).
In the invention, the sintering temperature is preferably 950-1330 ℃, and more preferably 950-1120 ℃; the heating rate of the sintering is preferably 2-4 ℃/min, and more preferably 3 ℃/min; the heat preservation time for sintering is preferably 2h to 4h, and more preferably 2 h.
After sintering, the invention preferably also comprises the steps of cooling the sintered product to obtain MAS-LT composite microwave dielectric ceramic; the furnace cooling solution known to those skilled in the art may be used, and the present invention is not limited thereto.
The preparation method provided by the invention has the advantages of simple process, low sintering temperature of 950 ℃, environmental protection, no toxicity, no pollution to the environment, suitability for large-scale industrialization and very wide development prospect, and meets the requirement of environmental protection.
The invention provides a MAS-LT composite microwave dielectric ceramic, which has a general formula shown as the following formula: mg (magnesium)2- xBaxAl4Si5O18-Li2TiO3(ii) a Wherein x is 0 to 0.16; li in MAS-LT composite microwave dielectric ceramic2TiO3The mass percentage of the component (A) is 6-24%. Compared with the prior art, the MAS-LT composite microwave dielectric ceramic provided by the invention takes the composite oxide with the specific general formula as a main material, and Li is adjusted2TiO3The content of (A) can realize that the dielectric constant is between 4 and 6 and the temperature coefficient of frequencyIs continuously adjustable; moreover, the MAS-LT composite microwave dielectric ceramic has a stable structure, a specific dielectric constant and a high Q multiplied by f value, and the temperature coefficient of the resonant frequency is continuously adjustable. Experimental results show that the dielectric constant of the MAS-LT composite microwave dielectric ceramic is 4-5.8, the Qxf is not less than 35800GHz and can reach 87600GHz, and compared with other microwave dielectric ceramics with the same dielectric constant, the system has high Qxf value and low dielectric loss; meanwhile, the temperature coefficient of the resonance frequency is continuously adjustable between-12 ppm/DEG C to +13 ppm/DEG C, and the formula can be flexibly adjusted.
In addition, the preparation method provided by the invention has the advantages of simple process, low sintering temperature of 950 ℃, environmental protection, no toxicity, no environmental pollution, suitability for large-scale industrialization and very wide development prospect, and meets the requirement of environmental protection.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials of the medicines used in the following examples of the present invention are all commercially available products; wherein the adhesive is 7% polyvinyl alcohol aqueous solution by mass percent; the additive is a composite oxide and is prepared from the following components in a mass ratio of 8: 27: 30: 25: 10 SiO2、B2O3、ZnO、Bi2O3And MgO, and the preparation method specifically comprises the following steps:
mixing SiO2、B2O3、ZnO、Bi2O3Mixing with MgO, ball milling for 24 hr, drying, sieving, melting at 1000 deg.C for 20min, extracting with deionized water, pulverizing, and sieving with 200 mesh sieve to obtain the additive.
Example 1
(1) According to the formula Mg2Al4Si5O1850.11g MgCO were weighed3、60.6g Al2O3And 89.28gSiO2Mixing to obtain a first mixture; mixing the first mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 6h by using a planetary mill wet method, drying at 150 ℃, presintering at 1000 ℃ (in atmospheric atmosphere) for 3h with the heating rate of 3 ℃/min, and cooling along with the furnace to obtain the MAS presintering material.
(2) According to Li2CO3：TiO21: molar ratio of 1 96.09g Li were weighed2CO3And 103.91g TiO2Mixing to obtain a second mixture; mixing the second mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 6h by using a planetary mill wet method, drying at 150 ℃, presintering at 1000 ℃ (in atmospheric atmosphere) for 2h with the heating rate of 3 ℃/min, and cooling along with a furnace to obtain the LT presintering material.
(3) Weighing 88g of MAS pre-sintering material and 12g of LT pre-sintering material, and mixing to obtain a third mixture; mixing the third mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 10 hours by a planet wet method, and drying at 80 ℃ to obtain MAS-LT powder.
(4) Adding a bonding agent accounting for 7% of the MASs of the MAS-LT powder, granulating and grinding for 1h, sieving with a 40-mesh sieve, and pressing the powder into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, wherein the pressure is 100 MPa; sintering the blank body into porcelain at 1330 ℃, wherein the heating rate is 3 ℃/min, the heat preservation time is 2h, and then cooling along with a furnace to obtain MAS-LT composite microwave dielectric ceramic; wherein the MASs of LT accounts for 12 percent of the total MASs of the MAS-LT composite microwave dielectric ceramic.
The MAS-LT composite microwave dielectric ceramic provided by the embodiment 1 of the invention is tested for various performances, and specifically comprises the following steps:
polishing the surface of the prepared ceramic sample, and determining the dielectric constant epsilon according to a Hakki-Coleman method by using an Agilient 8722ET network analyzerrAnd a quality factor Qxf; in addition, the measurement of the temperature coefficient of the resonant frequency is to directly connect a network analyzer with a constant temperature box, test the change value of the resonant frequency in the temperature range of 20-85 ℃, and then calculate tau according to the formula shown in formula (II)fA value;
the test results of various performances of the MAS-LT composite microwave dielectric ceramic provided by the embodiment 1 of the invention are as follows: epsilonr＝5，Q×f＝35800GHz(14GHz)，τf＝0ppm/℃。
Example 2
(1) According to the formula Mg1.92Ba0.08Al4Si5O1847.47g of MgCO were weighed3、4.63g BaCO3、59.8g Al2O3And 88.1g SiO2Mixing to obtain a first mixture; mixing the first mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 6h by using a planetary mill wet method, drying at 150 ℃, presintering at 1000 ℃ (in atmospheric atmosphere) for 3h with the heating rate of 3 ℃/min, and cooling along with the furnace to obtain the MAS presintering material.
(2) According to Li2CO3：TiO21: molar ratio of 1 96.09g Li were weighed2CO3And 103.91g TiO2Mixing to obtain a second mixture; mixing the second mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 6h by using a planetary mill wet method, drying at 150 ℃, presintering at 1000 ℃ (in atmospheric atmosphere) for 2h with the heating rate of 3 ℃/min, and cooling along with a furnace to obtain the LT presintering material.
(3) Weighing 88g of MAS pre-sintering material and 12g of LT pre-sintering material, and mixing to obtain a third mixture; mixing the third mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 10 hours by a planet wet method, and drying at 80 ℃ to obtain MAS-LT powder.
(4) Adding a bonding agent accounting for 7% of the MASs of the MAS-LT powder, granulating and grinding for 1h, sieving with a 40-mesh sieve, and pressing the powder into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, wherein the pressure is 100 MPa; sintering the blank body into porcelain at 1330 ℃, wherein the heating rate is 3 ℃/min, the heat preservation time is 2h, and then cooling along with a furnace to obtain MAS-LT composite microwave dielectric ceramic; wherein the MASs of LT accounts for 12 percent of the total MASs of the MAS-LT composite microwave dielectric ceramic.
The various performances of the microwave dielectric ceramic provided in embodiment 2 of the present invention are tested according to the test method provided in embodiment 1, and the test results are as follows: epsilonr＝5.2，Q×f＝54700GHz(14GHz)，τf＝0.1ppm/℃。
Example 3
(1) According to the formula Mg1.84Ba0.16Al4Si5O1844.9g MgCO were weighed3、9.13g BaCO3、59.02g Al2O3And 86.95g SiO2Mixing to obtain a first mixture; mixing the first mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 6h by using a planetary mill wet method, drying at 150 ℃, presintering at 1000 ℃ (in atmospheric atmosphere) for 3h with the heating rate of 3 ℃/min, and cooling along with the furnace to obtain the MAS presintering material.
(2) According to Li2CO3：TiO21: molar ratio of 1 96.09g Li were weighed2CO3And 103.91g TiO2Mixing to obtain a second mixture; mixing the second mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 6h by using a planetary mill wet method, drying at 150 ℃, presintering at 1000 ℃ (in atmospheric atmosphere) for 2h with the heating rate of 3 ℃/min, and cooling along with a furnace to obtain the LT presintering material.
(3) Weighing 88g of MAS pre-sintering material and 12g of LT pre-sintering material, and mixing to obtain a third mixture; mixing the third mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 10 hours by a planet wet method, and drying at 80 ℃ to obtain MAS-LT powder.
(4) Adding a bonding agent accounting for 7% of the MASs of the MAS-LT powder, granulating and grinding for 1h, sieving with a 40-mesh sieve, and pressing the powder into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, wherein the pressure is 100 MPa; sintering the blank body into porcelain at 1330 ℃, wherein the heating rate is 3 ℃/min, the heat preservation time is 2h, and then cooling along with a furnace to obtain MAS-LT composite microwave dielectric ceramic; wherein the MASs of LT accounts for 12 percent of the total MASs of the MAS-LT composite microwave dielectric ceramic.
The various performances of the microwave dielectric ceramic provided in embodiment 3 of the present invention are tested according to the test method provided in embodiment 1, and the test results are as follows: epsilonr＝5.1，Q×f＝43600GHz(14GHz)，τf＝0.3ppm/℃。
Example 4
(1) According to the formula Mg1.92Ba0.08Al4Si5O1847.47g of MgCO were weighed3、4.63g BaCO3、59.8g Al2O3And 88.1g SiO2Mixing to obtain a first mixture; mixing the first mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 6h by using a planetary mill wet method, drying at 150 ℃, presintering at 1000 ℃ (in atmospheric atmosphere) for 3h with the heating rate of 3 ℃/min, and cooling along with the furnace to obtain the MAS presintering material.
(2) According to Li2CO3：TiO21: molar ratio of 1 96.09g Li were weighed2CO3And 103.91g TiO2Mixing to obtain a second mixture; mixing the second mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 6h by using a planetary mill wet method, drying at 150 ℃, presintering at 1000 ℃ (in atmospheric atmosphere) for 2h with the heating rate of 3 ℃/min, and cooling along with a furnace to obtain the LT presintering material.
(3) Weighing 88g of MAS pre-sintering material, 12g of LT pre-sintering material and 1.5g of additive, and mixing to obtain a third mixture; mixing the third mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 10 hours by a planet wet method, and drying at 80 ℃ to obtain MAS-LT powder.
(4) Adding a bonding agent accounting for 7% of the MASs of the MAS-LT powder, granulating and grinding for 1h, sieving with a 40-mesh sieve, and pressing the powder into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, wherein the pressure is 100 MPa; sintering the blank body into porcelain at 1120 ℃, wherein the heating rate is 3 ℃/min, the heat preservation time is 2h, and then cooling along with a furnace to obtain MAS-LT composite microwave dielectric ceramic; wherein the MASs of LT accounts for 12 percent of the total MASs of the MAS-LT composite microwave dielectric ceramic.
The various performances of the microwave dielectric ceramic provided in embodiment 4 of the present invention are tested according to the test method provided in embodiment 1, and the test results are as follows: epsilonr＝5.4，Q×f＝75000GHz(14GHz)，τf＝0.2ppm/℃。
Example 5
(1) According to the formula Mg1.92Ba0.08Al4Si5O1847.47g of MgCO were weighed3、4.63g BaCO3、59.8g Al2O3And 88.1g SiO2Mixing to obtain a first mixture; mixing the first mixture, agate balls and deionizingWater in a ratio of 1: 2: 2, ball milling for 6h by using a planetary mill wet method, drying at 150 ℃, presintering at 1000 ℃ (in atmospheric atmosphere) for 3h with the heating rate of 3 ℃/min, and cooling along with the furnace to obtain the MAS presintering material.
(2) According to Li2CO3：TiO21: molar ratio of 1 96.09g Li were weighed2CO3And 103.91g TiO2Mixing to obtain a second mixture; mixing the second mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 6h by using a planetary mill wet method, drying at 150 ℃, presintering at 1000 ℃ (in atmospheric atmosphere) for 2h with the heating rate of 3 ℃/min, and cooling along with a furnace to obtain the LT presintering material.
(3) Weighing 88g of MAS pre-sintering material, 12g of LT pre-sintering material and 3g of additive, and mixing to obtain a third mixture; mixing the third mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 10 hours by a planet wet method, and drying at 80 ℃ to obtain MAS-LT powder.
(4) Adding a bonding agent accounting for 7% of the MASs of the MAS-LT powder, granulating and grinding for 1h, sieving with a 40-mesh sieve, and pressing the powder into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, wherein the pressure is 100 MPa; sintering the blank at 950 ℃ to form ceramic, wherein the heating rate is 3 ℃/min, the heat preservation time is 2h, and then cooling along with a furnace to obtain MAS-LT composite microwave dielectric ceramic; wherein the MASs of LT accounts for 12 percent of the total MASs of the MAS-LT composite microwave dielectric ceramic.
The various performances of the microwave dielectric ceramic provided in embodiment 5 of the present invention are tested according to the test method provided in embodiment 1, and the test results are as follows: epsilonr＝4.7，Q×f＝43000GHz(14GHz)，τf＝0.3ppm/℃。
Example 6
(1) According to the formula Mg1.92Ba0.08Al4Si5O1847.47g of MgCO were weighed3、4.63g BaCO3、59.8g Al2O3And 88.1g SiO2Mixing to obtain a first mixture; mixing the first mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 6 hours by a planetary mill wet method, drying at 150 ℃, and presintering at 1000 ℃ (in largeIn gas atmosphere) for 3h, the heating rate is 3 ℃/min, and the MAS pre-sintering material is obtained after furnace cooling.
(2) According to Li2CO3：TiO21: molar ratio of 1 96.09g Li were weighed2CO3And 103.91g TiO2Mixing to obtain a second mixture; mixing the second mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 6h by using a planetary mill wet method, drying at 150 ℃, presintering at 1000 ℃ (in atmospheric atmosphere) for 2h with the heating rate of 3 ℃/min, and cooling along with a furnace to obtain the LT presintering material.
(3) Weighing 94g of MAS pre-sintering material, 6g of LT pre-sintering material and 1.5g of additive, and mixing to obtain a third mixture; mixing the third mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 10 hours by a planet wet method, and drying at 80 ℃ to obtain MAS-LT powder.
(4) Adding a bonding agent accounting for 7% of the MASs of the MAS-LT powder, granulating and grinding for 1h, sieving with a 40-mesh sieve, and pressing the powder into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, wherein the pressure is 100 MPa; sintering the blank body into porcelain at 1120 ℃, wherein the heating rate is 3 ℃/min, the heat preservation time is 2h, and then cooling along with a furnace to obtain MAS-LT composite microwave dielectric ceramic; wherein the MASs of LT accounts for 6 percent of the total MASs of the MAS-LT composite microwave dielectric ceramic.
The various performances of the microwave dielectric ceramic provided in embodiment 6 of the present invention are tested according to the test method provided in embodiment 1, and the test results are as follows: epsilonr＝5.8，Q×f＝87600GHz(14GHz)，τf＝-12ppm/℃。
Example 7
(1) According to the formula Mg1.92Ba0.08Al4Si5O1847.47g of MgCO were weighed3、4.63g BaCO3、59.8g Al2O3And 88.1g SiO2Mixing to obtain a first mixture; mixing the first mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 6h by using a planetary mill wet method, drying at 150 ℃, presintering at 1000 ℃ (in atmospheric atmosphere) for 3h with the heating rate of 3 ℃/min, and cooling along with the furnace to obtain the MAS presintering material.
(2) According to Li2CO3：TiO21: molar ratio of 1 96.09g Li were weighed2CO3And 103.91g TiO2Mixing to obtain a second mixture; mixing the second mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 6h by using a planetary mill wet method, drying at 150 ℃, presintering at 1000 ℃ (in atmospheric atmosphere) for 2h with the heating rate of 3 ℃/min, and cooling along with a furnace to obtain the LT presintering material.
(3) Weighing 82g of MAS pre-sintering material, 18g of LT pre-sintering material and 1.5g of additive, and mixing to obtain a third mixture; mixing the third mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 10 hours by a planet wet method, and drying at 80 ℃ to obtain MAS-LT powder.
(4) Adding a bonding agent accounting for 7% of the MASs of the MAS-LT powder, granulating and grinding for 1h, sieving with a 40-mesh sieve, and pressing the powder into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, wherein the pressure is 100 MPa; sintering the blank body into porcelain at 1120 ℃, wherein the heating rate is 3 ℃/min, the heat preservation time is 2h, and then cooling along with a furnace to obtain MAS-LT composite microwave dielectric ceramic; wherein the MASs of LT accounts for 18 percent of the total MASs of the MAS-LT composite microwave dielectric ceramic.
The various performances of the microwave dielectric ceramic provided in embodiment 7 of the present invention are tested according to the test method provided in embodiment 1, and the test results are as follows: epsilonr＝4.6，Q×f＝63700GHz(14GHz)，τf＝6ppm/℃。
Example 8
(1) According to the formula Mg1.92Ba0.08Al4Si5O1847.47g of MgCO were weighed3、4.63g BaCO3、59.8g Al2O3And 88.1g SiO2Mixing to obtain a first mixture; mixing the first mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 6h by using a planetary mill wet method, drying at 150 ℃, presintering at 1000 ℃ (in atmospheric atmosphere) for 3h with the heating rate of 3 ℃/min, and cooling along with the furnace to obtain the MAS presintering material.
(2) According to Li2CO3：TiO21: 1 molar ratio of 96.09g Li2CO3And 103.91g TiO2Mixing to obtain a second mixture; mixing the second mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 6h by using a planetary mill wet method, drying at 150 ℃, presintering at 1000 ℃ (in atmospheric atmosphere) for 2h with the heating rate of 3 ℃/min, and cooling along with a furnace to obtain the LT presintering material.
(3) Weighing 76g of MAS pre-sintering material, 24g of LT pre-sintering material and 1.5g of additive, and mixing to obtain a third mixture; mixing the third mixture, agate balls and deionized water in a ratio of 1: 2: 2, ball milling for 10 hours by a planet wet method, and drying at 80 ℃ to obtain MAS-LT powder.
(4) Adding a bonding agent accounting for 7% of the MASs of the MAS-LT powder, granulating and grinding for 1h, sieving with a 40-mesh sieve, and pressing the powder into a thin cylindrical blank with the thickness of 6mm and the diameter of 13mm, wherein the pressure is 100 MPa; sintering the blank body into porcelain at 1120 ℃, wherein the heating rate is 3 ℃/min, the heat preservation time is 2h, and then cooling along with a furnace to obtain MAS-LT composite microwave dielectric ceramic; wherein the MASs of LT accounts for 24 percent of the total MASs of the MAS-LT composite microwave dielectric ceramic.
The various performances of the microwave dielectric ceramic provided in embodiment 8 of the present invention are tested according to the test method provided in embodiment 1, and the test results are as follows: epsilonr＝4，Q×f＝45100GHz(14GHz)，τf＝13ppm/℃。
Experimental results show that the dielectric constant of the MAS-LT composite microwave dielectric ceramic is 4-5.8, the Qxf is not less than 35800GHz and can reach 87600GHz, and compared with other microwave dielectric ceramics with the same dielectric constant, the system has high Qxf value and low dielectric loss; meanwhile, the temperature coefficient of the resonance frequency is continuously adjustable between-12 ppm/DEG C to +13 ppm/DEG C, and the formula can be flexibly adjusted.
In addition, the preparation method provided by the invention has the advantages of simple process, low sintering temperature of 950 ℃, environmental protection, no toxicity, no environmental pollution, suitability for large-scale industrialization and very wide development prospect, and meets the requirement of environmental protection.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A MAS-LT composite microwave dielectric ceramic has a general formula shown in a formula (I):
Mg2-xBaxAl4Si5O18-Li2TiO3formula (I);
in formula (I), x is 0.08; li in MAS-LT composite microwave dielectric ceramic2TiO3The mass percentage content of the compound is 6 to 24 percent;
the MAS-LT composite microwave dielectric ceramic also comprises:
an additive;
the additive is prepared from the following components in percentage by mass of 8: 27: 30: 25: 10 SiO2、B2O3、ZnO、Bi2O3And MgO; the preparation method of the additive specifically comprises the following steps:
mixing SiO2、B2O3、ZnO、Bi2O3Mixing with MgO, ball-milling for 24h, drying, sieving, melting at 1000 deg.C for 20min, extracting with deionized water, pulverizing, and sieving with 200 mesh sieve to obtain additive;
the amount of the additive is 1.5 percent of the MASs of the MAS-LT composite microwave dielectric ceramic.
2. A method for preparing MAS-LT composite microwave dielectric ceramic as claimed in claim 1, comprising the steps of:
a) MgCO is mixed with3、BaCO3、Al2O3And SiO2After mixing, carrying out primary grinding treatment, and then carrying out primary presintering to obtain a MAS presintering material;
b) mixing Li2CO3And TiO2After mixing, carrying out secondary grinding treatment, and then carrying out secondary pre-sintering to obtain an LT pre-sintering material;
c) mixing the MAS pre-sintering material, the LT pre-sintering material and an additive, and then carrying out third grinding treatment to obtain MAS-LT powder;
d) adding a binder into the MAS-LT powder for granulation molding to obtain a ceramic green body; sintering the obtained ceramic green body to obtain MAS-LT composite microwave dielectric ceramic;
the step a) and the step b) are not limited in order.
3. The preparation method according to claim 2, wherein the first grinding treatment in step a) is specifically performed by:
mixing the mixed raw materials, agate balls and water in a ratio of 1: (1-4): (2-3), ball-milling for 6-10 h at the rotating speed of 200-300 r/min, and drying at 80-150 ℃ to obtain the mixed material after the first grinding treatment.
4. The preparation method according to claim 2, wherein the temperature of the first presintering in the step a) is 800-1100 ℃, the heating rate is 2-4 ℃/min, and the holding time is 2-3 h.
5. The preparation method according to claim 2, wherein the adhesive in the step b) is a polyvinyl alcohol aqueous solution with the mass percentage of 6-8%;
the MASs ratio of the MAS-LT powder to the adhesive is 100: (7-10).
6. The preparation method according to claim 2, wherein the granulating and forming process in the step b) is specifically as follows:
adding an adhesive into the MAS-LT powder, granulating and grinding for 0.5-1.5 h, sieving with a 30-50-mesh sieve, and pressing and molding the obtained powder under the pressure of 80-120 MPa to obtain a ceramic green body.
7. The preparation method according to claim 2, wherein the sintering temperature in step b) is 950 ℃ to 1330 ℃, the heating rate is 2 ℃/min to 4 ℃/min, and the holding time is 2h to 4 h.
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