CN112608144A - Lithium-based microwave dielectric ceramic material, preparation method thereof and lithium-based microwave dielectric ceramic - Google Patents

Lithium-based microwave dielectric ceramic material, preparation method thereof and lithium-based microwave dielectric ceramic Download PDF

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CN112608144A
CN112608144A CN202011493263.2A CN202011493263A CN112608144A CN 112608144 A CN112608144 A CN 112608144A CN 202011493263 A CN202011493263 A CN 202011493263A CN 112608144 A CN112608144 A CN 112608144A
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lithium
sintering
microwave dielectric
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CN112608144B (en
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马丹丹
周世平
周纪平
温俊磊
李武
裴广斌
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Luoyang Zhongchao New Material Shares Co ltd
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Abstract

The invention provides a lithium-based microwave dielectric ceramic material, which comprises the following raw materials: a main powder and an auxiliary powder represented by formula (I); the auxiliary powder comprises glass powder accounting for 0.5-1.5 wt% of the main powder and rutile type TiO accounting for 5-10 wt% of the main powder2Micro-powder; li2(Zn(1‑x)Cux)(Ti(1‑y)(Mg1/3Nb2/3)y)3O8Formula (I). The specific glass powder of the invention reduces the sintering temperature of the system and introduces Mg2+、Nb5+Substituted Ti4+Improving the frequency temperature coefficient and introducing TiO2Can increase Li2CO3‑ZnO‑TiO2The sintering compactness of the system can be adjusted to be taufThe value is obtained. Cu2+The substitution and specification of glass frit successfully enabled Li2CO3‑ZnO‑TiO2The system is sintered at 850-890 ℃ and has excellent dielectric property, so that the material can be co-sintered with an Ag electrode.

Description

Lithium-based microwave dielectric ceramic material, preparation method thereof and lithium-based microwave dielectric ceramic
Technical Field
The invention relates to the technical field of materials, in particular to a lithium-based microwave dielectric ceramic material with a dielectric constant in low-temperature sintering, a preparation method thereof and a lithium-based microwave dielectric ceramic.
Background
With the development of electronic information technology towards high frequency and digitization, the requirements for integration and modularization of components and circuits are more and more urgent, and Low Temperature Co-fired ceramic LTCC (Low Temperature Co-fired ceramic) has become one of the hot spots for the modularization research of electronic devices due to its excellent electrical, mechanical, process characteristics and high reliability. With the progress of science and technology, the LTCC technology puts higher requirements on microwave dielectric ceramic materials: (1) excellent microwave dielectric property, proper dielectric constant, low loss and near-zero temperature coefficient of resonant frequency; (2) the sintering temperature is lower than 900 ℃, so that the sintering and the sintering of the Ag electrode material are realized; (3) the electrode material does not generate chemical reaction, the interface combination of the electrode material and the electrode material is firm, and the sintering shrinkage matching performance is good.
Most of the microwave dielectric ceramics such as MgTiO at present3、Nd(Zn0.5Ti0.5)O3、Ba(Mg1/3Ta2/3)O3And the like have excellent performance, but the sintering temperature is too high (not less than 1300 ℃) to be applied to the LTCC technology. Therefore, more and more researches are put on exploring a material system which has low sintering temperature and excellent performance and can realize co-firing compatibility with Ag electrodes. Li of spinel structure2ZnTi3O8Is a material with low inherent sintering temperature (1080 ℃) and excellent dielectric propertyMicrowave dielectric materials of properties, in addition Li2ZnTi3O8The ceramic has the advantages of low cost, good economy, easy realization of industrialization and the like, thereby having wide application prospect and attracting the wide attention of people. Researchers at home and abroad are mainly aimed at reducing Li2ZnTi3O8Some studies have been made on the sintering temperature and the improvement of the temperature coefficient of the resonance frequency. Wherein Lihua Kai, Lvwen, Leiwen, etc. are in "H3BO3Doping with Li2ZnTi3O8Microwave dielectric properties of ceramics "in the text (electronic components and materials, 2012,31(2):5-7.) Li was investigated2ZnTi3O8Doping with 2 wt% H3BO3The porcelain material system has better dielectric property, epsilon, after being sintered at 950 ℃ for 4 hoursr＝25.99、Q×f＝54926GHz、τf＝-12.17×10-6ppm/DEG C, but sintering temperature>The temperature is 900 ℃ and the heat preservation time is as long as 4 hours, so that the silver flying phenomenon is easy to occur; and a combustion assistant H3BO3Adverse effects can occur when preparing cast green tapes; ren H S, Hao L, Peng H Y et al in "Investigation on low-temperature configurable behavor and configurable dielectric properties of BLMT glass-Li2ZnTi3O8composition ceramics "in the Journal of the European Ceramic Society,2018,38(10):3498-2O3-La2O3-MgO-TiO2Glass pair Li2ZnTi3O8Influence of ceramic sintering characteristics and dielectric properties, doping with 20 wt% B2O3-La2O3-MgO-TiO2The sintering dielectric property is better when the temperature is kept at 900 ℃ for 2hr＝22.7、Q×f＝19900GHz、τf＝0.28×10-6ppm/DEG C, and glass addition levels up to 20 wt% were fired to lower the sintering temperature, resulting in Li2ZnTi3O8System epsilonrAnd the Qxf is low, the comprehensive performance is poor, and the application of the LTCC technology has certain limitation.
Invention patent "Li2ZnTi3O8Microwave dielectric material and low-temperature sintering method' CN101913859A discloses an additive sintered at 900 DEG CLi with addition of low-melting substances2ZnTi3O8Ceramic material (low melting point substance is H)3BO3、BaCu(B2O5)、V2O5And Bi2O3One of them). The material has a high temperature coefficient of resonance frequency (-47.2 to-20.7 ppm/DEG C), and the additive V2O5Has adverse effects in the production of cast green tapes. The invention discloses a low-temperature sintered lithium-based zinc-titanium microwave dielectric ceramic and a preparation method thereof, CN102617127A discloses that a sintering aid sintered at the temperature lower than 900 ℃ is H3BO3Or ZBS (60 wt% -ZnO, 30 wt% -B)2O3、10wt％-SiO2) Li of (2)2ZnTi3O8The ceramic material is added with a sintering aid, so that the dielectric property of a material system is deteriorated. The invention discloses a low-temperature co-fired microwave dielectric ceramic material and a preparation method thereof, CN102381874B discloses Li sintered at about 875 DEG C2ZnTi3O8A ceramic material, wherein the low-melting substance is Li2O-ZnO-B2O3Or Li2O-B2O3-SiO2The sintering heat preservation time of the glass in the material is 4 hours, the silver electrode is easy to ablate and erode after the heat preservation time is long, the Q x f integral of the material sintered at about 875 ℃ is slightly lower, the addition amount of different auxiliary components is different, the prepared material has poor comprehensive performance, the Q x f value and the taufCannot be considered well, such as: li2ZnTi3O8Adding LBS 1 wt% and TiO 5 wt%2Keeping the temperature at 875 ℃ for 4h for sintering, epsilonr＝26.0、Q×f＝24079GHz、τf＝1.6×10-6ppm/DEG C, again with Li addition2O-B2O3-SiO2Glass deteriorates Li2ZnTi3O8The dielectric properties of the system.
In conclusion, it is necessary to develop a lithium-based microwave dielectric ceramic material with medium dielectric constant in low-temperature sintering and a preparation method thereof, which can overcome the defects of the existing lithium-based microwave dielectric material, such as too high sintering temperature, too long heat preservation time, difficulty in matching and co-firing with a silver electrode, adverse effect of an additive on dielectric property, and the like.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a low-temperature sintered medium-dielectric-constant lithium-based microwave dielectric ceramic material, which has the advantages of low sintering temperature, short heat preservation time and good dielectric property.
The invention provides a lithium-based microwave dielectric ceramic material, which comprises the following raw materials:
a main powder and an auxiliary powder represented by formula (I); the auxiliary powder comprises glass powder accounting for 0.5-1.5 wt% of the main powder and rutile type TiO accounting for 5-10 wt% of the main powder2Micro-powder;
Li2(Zn(1-x)Cux)(Ti(1-y)(Mg1/3Nb2/3)y)3O8formula (I);
wherein x is more than or equal to 0 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.2.
Preferably, the glass powder is Li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3A glass system;
the glass powder D50 is 2-4 mu m;
the rutile type TiO2The particle size D50 of the micro powder is 0.5-1.0 μm;
preferably, the glass powder is prepared by performing wet ball milling, drying, smelting and crushing on the following raw materials in parts by weight:
Figure BDA0002841351830000031
preferably, the raw material of the glass frit further comprises a pretreatment comprising: pre-sintering ZnO at 600-700 ℃ and preserving heat for 4-5 h; na (Na)2CO3、K2CO3And B2O3Drying the mixture in an oven at 100-120 ℃ for 1-2 h respectively;
the smelting temperature is 1200-1350 ℃.
Preferably, the main powder represented by the formula (I) is Li2ZnTi3O8、Li2Zn(Ti0.95(Mg1/3Nb2/3)0.05)3O8、Li2Zn(Ti0.9(Mg1/3Nb2/3)0.1)3O8、Li2Zn(Ti0.8(Mg1/3Nb2/3)0.2)3O8、Li2(Zn0.975Cu0.025)Ti3O8、Li2(Zn0.95Cu0.05)Ti3O8、Li2(Zn0.95Cu0.05)(Ti0.9(Mg1/3Nb2/3)0.1)3O8Or Li2(Zn0.9Cu0.1)(Ti0.8(Mg1/ 3Nb2/3)0.2)3O8One or more of them.
The invention provides a preparation method of a lithium-based microwave dielectric ceramic material in any one of the technical schemes, which comprises the following steps:
a main powder body, glass powder and rutile type TiO shown in formula (I)2Mixing the micro powder, ball milling by a wet method, drying, mixing with a binder, granulating, pressing and sintering to obtain the nano-composite material.
Preferably, the preparation method of the main powder shown in the formula (I) specifically comprises the following steps:
Li2CO3、ZnO、TiO2CuO, MgO and Nb2O5Mixing according to a metering ratio, grinding by a wet method, drying, presintering and crushing to obtain the product.
Preferably, the preparation method of the main powder shown in the formula (I) further comprises pretreatment of ZnO and MgO, wherein the pretreatment specifically comprises: pre-sintering ZnO at 600-700 ℃ and preserving heat for 4-5 h; preserving the temperature of MgO at 700-800 ℃ for 4-5 h;
the particle size of the MgO is 40-80 nm;
the pre-sintering temperature is 800-900 ℃; the time is 2-6 h;
and crushing to obtain a main powder represented by the formula (I) with D50 being 1-3 μm.
Preferably, the wet ball milling time is 3-4 h; the drying temperature is 120-140 ℃; the binder is polyvinyl alcohol; the pressing pressure is 140-150 Mpa; the sintering temperature is 850-890 ℃; the sintering time is 0.5-1 h.
The invention provides lithium-based microwave dielectric ceramic which is prepared from the ceramic material or the ceramic material prepared by the preparation method.
The invention provides a microwave device, which is prepared from the ceramic material or the ceramic material prepared by the preparation method.
Compared with the prior art, the invention provides a lithium-based microwave dielectric ceramic material which comprises the following raw materials: a main powder and an auxiliary powder represented by formula (I); the auxiliary powder comprises glass powder accounting for 0.5-1.5 wt% of the main powder and rutile type TiO accounting for 5-10 wt% of the main powder2Micro-powder; li2(Zn(1-x)Cux)(Ti(1-y)(Mg1/3Nb2/3)y)3O8Formula (I); wherein x is more than or equal to 0 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.2. The invention is in Li2CO3-ZnO-TiO2By Cu on a system basis2+Substituted Zn2+To reduce Li2CO3-ZnO-TiO2Presintering temperature and sintering temperature, introducing the glass powder material of the invention to reduce the sintering temperature of the system, introducing Mg2+、Nb5+Substituted Ti4+Improving the frequency temperature coefficient and introducing TiO2On the one hand, Li can be increased2CO3-ZnO-TiO2The sintering compactness of the system can be adjusted on the other handfThe value is obtained. Cu2+The substitution and specification of glass frit successfully enabled Li2CO3-ZnO-TiO2The system can be sintered to be compact and obtain excellent dielectric property after being sintered for 1 hour at 850-890 ℃, so that the material can be co-sintered with an Ag electrode. The lithium-based microwave dielectric ceramic with the dielectric constant in low-temperature sintering has simple chemical composition and preparation process, and can be widely used for chip resonators, antennas, filters and the likeThe microwave device is an ideal low-temperature co-fired ceramic material for manufacturing.
Drawings
FIG. 1 is an XRD (X-ray diffraction pattern) of example 1 sintered at 890 ℃;
FIG. 2 is an XRD (X-ray diffraction pattern) of example 7 sintered at 875 ℃;
FIG. 3 is an SEM (scanning Electron micrograph) of example 1 sintered at 890 ℃;
FIG. 4 is an SEM (scanning Electron microscopy) image of example 7 sintered at 875 ℃.
Detailed Description
The invention provides a lithium-based microwave dielectric ceramic material with a dielectric constant in low-temperature sintering, a preparation method thereof and a lithium-based microwave dielectric ceramic. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention provides a lithium-based microwave dielectric ceramic material, which comprises the following raw materials:
a main powder and an auxiliary powder represented by formula (I); the auxiliary powder comprises glass powder accounting for 0.5-1.5 wt% of the main powder and rutile type TiO accounting for 5-10 wt% of the main powder2Micro-powder;
Li2(Zn(1-x)Cux)(Ti(1-y)(Mg1/3Nb2/3)y)3O8formula (I);
wherein x is more than or equal to 0 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.2.
The invention provides a lithium-based microwave dielectric ceramic material which comprises the following raw materials: a main powder represented by the formula (I).
Li2(Zn(1-x)Cux)(Ti(1-y)(Mg1/3Nb2/3)y)3O8Formula (I);
wherein x is more than or equal to 0 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.2.
The main powder represented by the formula (I) in the present invention is preferably Li2ZnTi3O8、Li2Zn(Ti0.95(Mg1/3Nb2/3)0.05)3O8、Li2Zn(Ti0.9(Mg1/3Nb2/3)0.1)3O8、Li2Zn(Ti0.8(Mg1/3Nb2/3)0.2)3O8、Li2(Zn0.975Cu0.025)Ti3O8、Li2(Zn0.95Cu0.05)Ti3O8、Li2(Zn0.95Cu0.05)(Ti0.9(Mg1/3Nb2/3)0.1)3O8Or Li2(Zn0.9Cu0.1)(Ti0.8(Mg1/3Nb2/3)0.2)3O8One or more of them.
The preparation method of the main powder shown in the formula (I) is preferably as follows:
Li2CO3、ZnO、TiO2CuO, MgO and Nb2O5Mixing according to a metering ratio, grinding by a wet method, drying, presintering and crushing to obtain the product.
Li according to the invention2CO3、ZnO、TiO2CuO, MgO and Nb2O5The purity is more than or equal to 99 percent, and the source of the product is not limited by the invention and can be sold in the market.
Firstly, pretreating raw materials, specifically pretreating ZnO and MgO.
The pretreatment specifically comprises the following steps: pre-sintering ZnO at 600-700 ℃ and preserving heat for 4-5 h; preferably presintering at 650-700 ℃ and preserving heat for 4-4.5 h; more preferably presintering at 700 ℃ and preserving heat for 4 hours;
preserving the temperature of MgO at 700-800 ℃ for 4-5 h; preferably, the temperature is kept at 750-800 ℃ for 4-4.5 h; more preferably, the temperature is kept for 4 hours at 800 ℃;
the particle size of the MgO is 40-80 nm.
Then to Li2CO3、ZnO、TiO2CuO, MgO and Nb2O5Mixing according to the metering ratio, and carrying out wet ball milling. The wet ball milling is carried out by taking water as grinding liquid, the ball-material ratio of the ball milling is 3:1, and the ball milling parameter is 300rpm/4 h.
And drying and presintering after wet grinding.
And drying the slurry obtained by ball milling, sieving by a 80-mesh sieve, and pressing into blocks. The drying temperature is 120 ℃ and the drying time is 4 h.
Then, pre-burning to prepare a pre-burning block.
The pre-sintering temperature is preferably 800-900 ℃; the time is preferably 2-6 h; more preferably 2-5 h; most preferably 2-4 h.
And crushing after pre-burning to obtain the product. The above-mentioned briquette was pulverized and ball-milled to obtain a main powder having a D50 of 1.15 μm.
The invention provides a low-temperature sintering medium dielectric constant lithium-based microwave dielectric ceramic material. The auxiliary powder comprises glass powder accounting for 0.5-1.5 wt% of the main powder; preferably, the glass powder accounts for 0.6-1.5 wt% of the main powder.
The glass powder is Li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3A glass system; the glass powder D50 is 2-4 mu m;
according to the invention, the glass powder is prepared by carrying out wet ball milling, drying, smelting and crushing on the following raw materials in parts by weight:
Figure BDA0002841351830000061
Figure BDA0002841351830000071
in a part of preferred embodiments of the present invention, the glass powder comprises the following raw materials in parts by weight:
Li2CO32.5 parts; al (Al)2O34.3 parts of a mixture; b is2O354.6 parts; 1.8 parts of ZnO; SiO 2232.7 parts of a mixture; na (Na)2CO31.2 parts; k2CO30.6 part; BaCO31.5 parts; la2O30.8 part.
In a part of preferred embodiments of the present invention, the glass powder comprises the following raw materials in parts by weight:
Li2CO32.5 parts; al (Al)2O34.3 parts of a mixture; b is2O352.2 parts of; 1.8 parts of ZnO; SiO 2233.6 parts; na (Na)2CO31.5 parts; k2CO31.8 parts; BaCO31.5 parts; la2O30.8 part.
In a part of preferred embodiments of the present invention, the glass powder comprises the following raw materials in parts by weight:
Li2CO34.5 parts; al (Al)2O34.2 parts of a mixture; b is2O351.9 parts; 1.8 parts of ZnO; SiO 2232.8 parts of; na (Na)2CO31.2 parts; k2CO31.3 parts; BaCO31.5 parts; la2O30.8 part.
In a part of preferred embodiments of the present invention, the glass powder comprises the following raw materials in parts by weight:
Li2CO33.5 parts; al (Al)2O34.1 parts; b is2O350.8 parts; 4.7 parts of ZnO; SiO 2231.6 parts; na (Na)2CO31.5 parts; k2CO31.2 parts; BaCO31.6 parts; la2O31.0 part.
In a part of preferred embodiments of the present invention, the glass powder comprises the following raw materials in parts by weight:
Li2CO33.5 parts; al (Al)2O37.6 parts; b is2O349.6 parts; 3.2 parts of ZnO; SiO 2230.6 parts; na (Na)2CO31.2 parts; k2CO31.5 parts; BaCO31.6 parts; la2O31.0 part.
In a part of preferred embodiments of the present invention, the glass powder comprises the following raw materials in parts by weight:
Li2CO33.2 parts of a mixture; al (Al)2O33.8 parts; b is2O353.6 parts; 3.6 parts of ZnO; SiO 2231.4 parts; na (Na)2CO31.4 parts; k2CO30.6 part; BaCO31.5 parts; la2O30.9 part.
In a part of preferred embodiments of the present invention, the glass powder comprises the following raw materials in parts by weight:
Li2CO34.5 parts; al (Al)2O34.2 parts of a mixture; b is2O345.5 parts; 5.2 parts of ZnO; SiO 2235.8 parts of; na (Na)2CO31.2 parts; k2CO30.8 part; BaCO31.6 parts; la2O31.2 parts.
In a part of preferred embodiments of the present invention, the glass powder comprises the following raw materials in parts by weight:
Li2CO32.6 parts; al (Al)2O34.3 parts of a mixture; b is2O355.2 parts; 2.1 parts of ZnO; SiO 2230.8 parts; na (Na)2CO31.2 parts; k2CO31.1 parts; BaCO31.5 parts; la2O31.2 parts.
The above parts by weight are equivalent to the weight percent when the weight is 100.
The preparation of the glass powder is preferably raw material pretreatment, and the pretreatment comprises the following steps: pre-sintering ZnO at 600-700 ℃ and preserving heat for 4-5 h; preferably presintering at 650-700 ℃ and preserving heat for 4-4.5 h; more preferably presintering at 700 ℃ and preserving heat for 4 hours;
Na2CO3、K2CO3and B2O3Drying the mixture in an oven at 100-120 ℃ for 1-2 h respectively; preferably, Na2CO3、K2CO3And B2O3Respectively in an ovenDrying for 1.5-2 h at 110-120 ℃; more preferably, Na2CO3、K2CO3And B2O3Drying in an oven at 120 ℃ for 2h respectively.
After pretreatment, the raw materials are proportioned according to the mass parts and are ball-milled by a wet method. Ball milling the obtained powder by using absolute ethyl alcohol as grinding fluid; the ball-milling ratio is 3:1, and the ball-milling parameter is 300rpm/4 h.
Drying and smelting after ball milling;
drying the slurry obtained by ball milling, sieving by a 80-mesh sieve, putting into a platinum crucible, smelting, and pouring the smelting liquid into pure water to quench glass; the smelting temperature is preferably 1200-1350 ℃.
And smelting and crushing to obtain the glass powder. And smelting the water-quenched glass, and performing ball milling to obtain glass powder with D50 being 2-4 mu m for later use.
The glass powder is Li obtained by smelting and grinding a mixture containing alkali metal and alkaline earth metal2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3A glass system.
The invention provides a low-temperature sintering medium dielectric constant lithium-based microwave dielectric ceramic material. The auxiliary powder comprises rutile TiO 5-10 wt% of the main powder2Micro-powder; preferably rutile type TiO 6-9 wt% of the main powder2And (5) micro-powder. The rutile type TiO of the invention2The particle diameter D50 of the fine powder is 0.5 to 1.0 μm.
The invention provides a preparation method of a low-temperature sintering medium dielectric constant lithium-based microwave dielectric ceramic material, which comprises the following steps:
a main powder body, glass powder and rutile type TiO shown in formula (I)2Mixing the micro powder, ball milling by a wet method, drying, mixing with a binder, granulating, pressing and sintering to obtain the nano-composite material.
The composition and specific preparation method of the main powder and the glass powder shown in the formula (I) are clearly described above, and are not repeated herein.
Firstly, main powder shown as formula (I), glass powder and rutile type TiO2Mixing micro powder, and performing wet ball milling, wherein the wet ball milling time is preferably 3-4 h; more preferably 4 h.
And drying the obtained slurry at 120-140 ℃ after wet ball milling. Adding a binder into the dried powder, and sieving the powder with a 80-mesh sieve for granulation. The binder is preferably polyvinyl alcohol; more preferably a 5% aqueous solution of polyvinyl alcohol.
Pressing the granulated powder under the pressure of 140-150 MPa to prepare a product; preferably, the granulated powder is pressed into a product with the diameter of 12mm multiplied by 5mm under the pressure of 150 MPa;
and sintering the product at 850-890 ℃ for 0.5-1 hour to obtain the microwave dielectric ceramic material.
The lithium-based microwave dielectric material with moderate dielectric constant (24.3-28.6), high Qxf value and nearly zero temperature coefficient of resonance frequency (tau f) can be obtained by mixing, molding and sintering the main powder and the auxiliary powder at 850-890 ℃, can be compatible with silver electrodes in co-firing, is used for microwave devices such as chip resonators, antennas, filters and the like, and is ideal low-temperature co-fired ceramic.
The invention provides lithium-based microwave dielectric ceramic which is prepared from the ceramic material or the ceramic material prepared by the preparation method.
The ceramic material and the preparation method thereof have been described clearly in the present invention, and are not described herein again.
The invention provides a microwave device, which is prepared from the ceramic material or the ceramic material prepared by the preparation method.
The microwave device of the present invention includes but is not limited to a chip resonator, an antenna, a filter, etc.
The invention provides a lithium-based microwave dielectric ceramic material, which comprises the following raw materials: a main powder and an auxiliary powder represented by formula (I); the auxiliary powder comprises glass powder accounting for 0.5-1.5 wt% of the main powder and main powder5-10 wt% rutile type TiO2Micro-powder; li2(Zn(1-x)Cux)(Ti(1-y)(Mg1/3Nb2/3)y)3O8Formula (I); wherein x is more than or equal to 0 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.2. The invention is in Li2CO3-ZnO-TiO2By Cu on a system basis2+Substituted Zn2+To reduce Li2CO3-ZnO-TiO2Presintering temperature and sintering temperature, introducing the glass powder material of the invention to reduce the sintering temperature of the system, introducing Mg2+、Nb5+Substituted Ti4+Improving the frequency temperature coefficient and introducing TiO2On the one hand, Li can be increased2CO3-ZnO-TiO2The sintering compactness of the system can be adjusted on the other handfThe value is obtained. Cu2+The substitution and specification of glass frit successfully enabled Li2CO3-ZnO-TiO2The system can be sintered to be compact and obtain excellent dielectric property after being sintered for 1 hour at 850-890 ℃, so that the material can be co-sintered with an Ag electrode. The lithium-based microwave dielectric ceramic with the dielectric constant in low-temperature sintering has simple chemical composition and preparation process, can be widely used for manufacturing microwave devices such as chip resonators, antennas, filters and the like, and is an ideal low-temperature co-fired ceramic material.
In order to further illustrate the present invention, the following will describe in detail a low-temperature sintering medium dielectric constant lithium-based microwave dielectric ceramic material, a preparation method thereof and a lithium-based microwave dielectric ceramic provided by the present invention with reference to the following examples.
Example 1
A low-temperature sintered medium-dielectric constant lithium-based microwave dielectric ceramic material and a preparation method thereof. The lithium-based microwave dielectric ceramic material comprises the following raw materials: a main powder and an auxiliary powder. The chemical formula of the main powder is as follows: li2(Zn(1-x)Cux)(Ti(1-y)(Mg1/3Nb2/3)y)3O8Wherein x is more than or equal to 0 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.2; the additional auxiliary powder comprises 0.5-1.5% of glass powder and 5-10% of rutile TiO relative to the main powder2And (5) micro-powder. WhereinThe glass powder is Li obtained by smelting and grinding a mixture containing alkali metal and alkaline earth metal2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3A glass system. The preparation method comprises the steps of mixing uniformly in a ball mill, drying, granulating, molding and sintering.
1) Synthesizing main powder: with purity of Li not less than 99%2CO3、ZnO、TiO2CuO, MgO and Nb2O5Is used as a main raw material and is carried out according to the following steps:
a. pretreatment of raw materials: presintering ZnO at 700 deg.C and holding for 4h, and presintering MgO with particle size of 40-80nm at 800 deg.C and holding for 4 h;
b. weighing the ingredients: according to Li2ZnTi3O8Metering and weighing;
c. wet ball milling: ball-milling the powder obtained in the step b by taking pure water as grinding fluid;
d. drying and pre-sintering: drying the slurry obtained in the step c, sieving by a 80-mesh sieve, pressing into blocks, and preserving heat at 900 ℃ for 4h for pre-sintering to prepare pre-sintered blocks;
e. crushing and pulverizing: the baked blocks are crushed and ball-milled to obtain D501.15 μm.
2) Preparing glass powder: li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3The system glass powder is Li with purity not less than 99%2CO3、Al2O3、B2O3、ZnO、SiO2、Na2CO3、K2CO3、BaCO3And La2O3Is taken as a main raw material and is carried out according to the following steps:
a. pretreatment of raw materials: presintering ZnO at 700 deg.C and holding for 4h, Na2CO3、K2CO3And B2O3Drying in a drying oven at 120 ℃ for 2h for later use;
b. weighing the ingredients: the weight percentages are as follows:
Figure BDA0002841351830000111
weighing;
c. wet ball milling: ball-milling the powder obtained in the step b by taking absolute ethyl alcohol as grinding fluid;
d. drying and smelting: drying the slurry obtained in the step c, sieving the dried slurry by a 80-mesh sieve, putting the dried slurry into a platinum crucible, smelting the platinum crucible at the temperature of 1350 ℃, and pouring the smelting liquid into pure water to quench glass;
e. crushing and pulverizing: ball milling the water quenched glass to obtain D502.16 μm glass frit.
3) Taking a certain amount of synthesized Li2ZnTi3O8Powder of Li in terms of glass powder2ZnTi3O81.5% of the powder, TiO2Occupy Li2ZnTi3O8And 5 percent of the powder is prepared. And drying the obtained slurry at 120 ℃ after wet ball milling for 4 hours. Adding 5% polyvinyl alcohol aqueous solution into the dried powder, and sieving with a 80-mesh sieve for granulation. The granulated powder is pressed into the powder under the pressure of 150MPa
Figure BDA0002841351830000112
The article of manufacture of (1). And sintering the product at 890 ℃ for 1 hour to obtain the microwave dielectric ceramic material. The microwave dielectric property of the material is as follows: epsilonr＝26.6、Q×f＝63621GHz、τf＝-8.66×10-6ppm/℃。
Example 2
A low-temperature sintered medium-dielectric constant lithium-based microwave dielectric ceramic and a preparation method thereof. The raw material of the lithium-based microwave dielectric ceramic is Li2(Zn(1-x)Cux)(Ti(1-y)(Mg1/3Nb2/3)y)3O8Main powder and auxiliary powder Li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3Bulk glass powder and TiO2And (4) forming.
1) Synthesizing main powder: with purity of Li not less than 99%2CO3、ZnO、TiO2CuO, MgO and Nb2O5Is used as a main raw material and is carried out according to the following steps:
a. pretreatment of raw materials: presintering ZnO at 700 deg.C and holding for 4h, and presintering MgO with particle size of 40-80nm at 800 deg.C and holding for 4 h;
b. weighing the ingredients: according to Li2Zn(Ti0.95(Mg1/3Nb2/3)0.05)3O8Metering and weighing;
c. wet ball milling: ball-milling the powder obtained in the step b for 4 hours by using pure water as grinding fluid;
d. drying and pre-sintering: drying the slurry obtained in the step c, sieving by a 80-mesh sieve, pressing into blocks, and preserving heat at 900 ℃ for 4h for pre-sintering to prepare pre-sintered blocks;
e. crushing and pulverizing: the baked blocks are crushed and ball-milled to obtain D502.18 μm.
2) Preparing glass powder: li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3The system glass powder is Li with purity not less than 99%2CO3、Al2O3、B2O3、ZnO、SiO2、Na2CO3、K2CO3、BaCO3And La2O3Is taken as a main raw material and is carried out according to the following steps:
a. pretreatment of raw materials: presintering ZnO at 700 deg.C and holding for 4h, Na2CO3、K2CO3And B2O3Drying in a drying oven at 120 ℃ for 2h for later use;
b. weighing the ingredients: the weight percentages are as follows:
Figure BDA0002841351830000121
weighing;
c. wet ball milling: ball-milling the powder obtained in the step b by taking absolute ethyl alcohol as grinding fluid;
d. drying and smelting: drying the slurry obtained in the step c, sieving the dried slurry by a 80-mesh sieve, putting the dried slurry into a platinum crucible, smelting the platinum crucible at the temperature of 1350 ℃, and pouring the smelting liquid into pure water to quench glass;
e. crushing and pulverizing: ball milling the water quenched glass to obtain D502.25 μm glass frit.
3) Taking a certain amount of synthesized Li2Zn(Ti0.95(Mg1/3Nb2/3)0.05)3O8Powder of Li in terms of glass powder2Zn(Ti0.95(Mg1/3Nb2/3)0.05)3O81.5% of the powder, TiO2Occupy Li2Zn(Ti0.95(Mg1/3Nb2/3)0.05)3O8And (5) mixing 8% of the powder. And drying the obtained slurry at 120 ℃ after wet ball milling for 4 hours. Adding 5% polyvinyl alcohol aqueous solution into the dried powder, and sieving with a 80-mesh sieve for granulation. The granulated powder is pressed into the powder under the pressure of 150MPa
Figure BDA0002841351830000132
The article of manufacture of (1). And sintering the product at 890 ℃ for 1 hour to obtain the microwave dielectric ceramic material. The microwave dielectric property of the material is as follows: epsilonr＝26.2、Q×f＝49128GHz、τf＝-5.6×10-6ppm/℃。
Example 3
A low-temperature sintered medium-dielectric constant lithium-based microwave dielectric ceramic and a preparation method thereof. The raw material of the lithium-based microwave dielectric ceramic is Li2(Zn(1-x)Cux)(Ti(1-y)(Mg1/3Nb2/3)y)3O8Main powder and auxiliary powder Li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3System glass powder and auxiliary powder TiO2And (4) forming.
1) Synthesizing main powder: with purity of Li not less than 99%2CO3、ZnO、TiO2CuO, MgO and Nb2O5Is used as a main raw material and is carried out according to the following steps:
a. pretreatment of raw materials: presintering ZnO at 700 deg.C and holding for 4h, and presintering MgO with particle size of 40-80nm at 800 deg.C and holding for 4 h;
b. weighing the ingredients: according to Li2Zn(Ti0.9(Mg1/3Nb2/3)0.1)3O8Metering and weighing;
c. wet ball milling: ball-milling the powder obtained in the step b by taking pure water as grinding fluid;
d. drying and pre-sintering: drying the slurry obtained in the step c, sieving by a 80-mesh sieve, pressing into blocks, and preserving heat at 900 ℃ for 4h for pre-sintering to prepare pre-sintered blocks;
e. crushing and pulverizing: the baked blocks are crushed and ball-milled to obtain D502.16 μm.
2) Preparing glass powder: li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3The system glass powder is Li with purity not less than 99%2CO3、Al2O3、B2O3、ZnO、SiO2、Na2CO3、K2CO3、BaCO3And La2O3Is taken as a main raw material and is carried out according to the following steps:
a. pretreatment of raw materials: presintering ZnO at 700 deg.C and holding for 4h, Na2CO3、K2CO3And B2O3Drying in a drying oven at 120 ℃ for 2h for later use;
b. weighing the ingredients: the weight percentages are as follows:
Figure BDA0002841351830000131
Figure BDA0002841351830000141
weighing;
c. wet ball milling: ball-milling the powder obtained in the step b by taking absolute ethyl alcohol as grinding fluid;
d. drying and smelting: drying the slurry obtained in the step c, sieving the dried slurry by a 80-mesh sieve, putting the dried slurry into a platinum crucible, smelting the platinum crucible at 1250 ℃, and pouring the smelting liquid into pure water to quench glass;
e. crushing and pulverizing: ball milling the water quenched glass to obtain D502.36 μm glass frit.
3) Taking a certain amount of synthesized Li2Zn(Ti0.9(Mg1/3Nb2/3)0.1)3O8Powder of Li in terms of glass powder2Zn(Ti0.9(Mg1/3Nb2/3)0.1)3O81.5% of the powder, TiO2Occupy Li2Zn(Ti0.9(Mg1/3Nb2/3)0.1)3O8And (5) mixing 8% of the powder. And drying the obtained slurry at 120 ℃ after wet ball milling for 4 hours. Adding 5% polyvinyl alcohol aqueous solution into the dried powder, and sieving with a 80-mesh sieve for granulation. Pressing the granulated powder under 150MPa to obtain
Figure BDA0002841351830000142
The article of manufacture of (1). And sintering the product at 880 ℃ for 1 hour to obtain the microwave dielectric ceramic material. The microwave dielectric property of the material is as follows: epsilonr＝26.8、Q×f＝50126GHz、τf＝-2.7×10-6ppm/℃。
Example 4
A low-temperature sintered medium-dielectric constant lithium-based microwave dielectric ceramic and a preparation method thereof. The raw material of the lithium-based microwave dielectric ceramic is Li2(Zn(1-x)Cux)(Ti(1-y)(Mg1/3Nb2/3)y)3O8Main powder and auxiliary powder Li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3System glass powder and auxiliary powder TiO2And (4) forming.
1) Synthesizing main powder: with purity of Li not less than 99%2CO3、ZnO、TiO2CuO, MgO and Nb2O5Is used as a main raw material and is carried out according to the following steps:
a. pretreatment of raw materials: presintering ZnO at 700 deg.C and holding for 4h, and presintering MgO with particle size of 40-80nm at 800 deg.C and holding for 4 h;
b. weighing the ingredients: according to Li2Zn(Ti0.8(Mg1/3Nb2/3)0.2)3O8Metering and weighing;
c. wet ball milling: ball-milling the powder obtained in the step b for 4 hours by using pure water as grinding fluid;
d. drying and pre-sintering: drying the slurry obtained in the step c, sieving by a 80-mesh sieve, pressing into blocks, and preserving heat at 900 ℃ for 4h for pre-sintering to prepare pre-sintered blocks;
e. crushing and pulverizing: the baked blocks are crushed and ball-milled to obtain D502.42 μm.
2) Preparing glass powder: li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3The system glass powder is Li with purity not less than 99%2CO3、Al2O3、B2O3、ZnO、SiO2、Na2CO3、K2CO3、BaCO3And La2O3Is taken as a main raw material and is carried out according to the following steps:
a. pretreatment of raw materials: presintering ZnO at 700 deg.C and holding for 4h, Na2CO3、K2CO3And B2O3Drying in a drying oven at 120 ℃ for 2h for later use;
b. weighing the ingredients: the weight percentages are as follows:
Figure BDA0002841351830000151
weighing;
c. wet ball milling: ball-milling the powder obtained in the step b by taking absolute ethyl alcohol as grinding fluid;
d. drying and smelting: drying the slurry obtained in the step c, sieving the dried slurry by a 80-mesh sieve, putting the dried slurry into a platinum crucible, smelting the platinum crucible at the temperature of 1350 ℃, and pouring the smelting liquid into pure water to quench glass;
e. crushing and pulverizing: ball milling the water quenched glass to obtain D502.86 μm glass frit.
3) Taking a certain amount of synthesized Li2Zn(Ti0.8(Mg1/3Nb2/3)0.2)3O8Powder of Li in terms of glass powder2Zn(Ti0.8(Mg1/3Nb2/3)0.2)3O81.5% of the powder, TiO2Occupy Li2Zn(Ti0.8(Mg1/3Nb2/3)0.2)3O8And 6 percent of the powder is prepared. And drying the obtained slurry at 120 ℃ after wet ball milling for 4 hours. Adding 5% polyvinyl alcohol aqueous solution into the dried powder, and sieving with a 80-mesh sieve for granulation. The granulated powder is pressed into the powder under the pressure of 150MPa
Figure BDA0002841351830000152
The article of manufacture of (1). And sintering the product at 880 ℃ for 1 hour to obtain the microwave dielectric ceramic material. The microwave dielectric property of the material is as follows: epsilonr＝28.2、Q×f＝57986GHz、τf＝1.8×10-6ppm/℃。
Example 5
A low-temperature sintered medium-dielectric constant lithium-based microwave dielectric ceramic and a preparation method thereof. The raw material of the lithium-based microwave dielectric ceramic is Li2(Zn(1-x)Cux)(Ti(1-y)(Mg1/3Nb2/3)y)3O8Main powder and auxiliary powder Li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3System glass powder and auxiliary powder TiO2And (4) forming.
1) Synthesizing main powder: with purity of Li not less than 99%2CO3、ZnO、TiO2CuO, MgO and Nb2O5Is used as a main raw material and is carried out according to the following steps:
a. pretreatment of raw materials: presintering ZnO at 700 deg.C and holding for 4h, and presintering MgO with particle size of 40-80nm at 800 deg.C and holding for 4 h;
b. weighing the ingredients: according to Li2(Zn0.975Cu0.025)Ti3O8Metering and weighing;
c. wet ball milling: ball-milling the powder obtained in the step b by taking pure water as grinding fluid;
d. drying and pre-sintering: drying the slurry obtained in the step c, sieving by a 80-mesh sieve, pressing into blocks, and pre-sintering at 850 ℃ for 4h to prepare pre-sintered blocks;
e. crushing and pulverizing: the baked blocks are crushed and ball-milled to obtain D502.36 μm.
2) Preparing glass powder: li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3The system glass powder is Li with purity not less than 99%2CO3、Al2O3、B2O3、ZnO、SiO2、Na2CO3、K2CO3、BaCO3And La2O3Is taken as a main raw material and is carried out according to the following steps:
a. pretreatment of raw materials: presintering ZnO at 700 deg.C and holding for 4h, Na2CO3、K2CO3And B2O3Drying in a drying oven at 120 ℃ for 2h for later use;
b. weighing the ingredients: the weight percentages are as follows:
Figure BDA0002841351830000161
weighing;
c. wet ball milling: ball-milling the powder obtained in the step b by taking absolute ethyl alcohol as grinding fluid;
d. drying and smelting: drying the slurry obtained in the step c, sieving the dried slurry by a 80-mesh sieve, putting the dried slurry into a platinum crucible, smelting the platinum crucible at the temperature of 1350 ℃, and pouring the smelting liquid into pure water to quench glass;
e. crushing and pulverizing: ball milling the water quenched glass to obtain D503.12 μm glass frit.
3) Taking a certain amount of synthesized Li2(Zn0.975Cu0.025)Ti3O8Powder of Li in terms of glass powder2(Zn0.975Cu0.025)Ti3O81.5% of the powder, TiO2Occupy Li2(Zn0.975Cu0.025)Ti3O8And (5) mixing 8% of the powder. And drying the obtained slurry at 120 ℃ after wet ball milling for 4 hours. Adding 5% polyvinyl alcohol aqueous solution into the dried powder, and sieving with a 80-mesh sieve for granulation. The granulated powder is pressed into the powder under the pressure of 150MPa
Figure BDA0002841351830000171
The article of manufacture of (1). And sintering the product at 875 ℃ for 1 hour to obtain the microwave dielectric ceramic material. The microwave dielectric property of the material is as follows: epsilonr＝26.5、Q×f＝59176GHz、τf＝-3.6×10-6ppm/℃。
Example 6
A low-temperature sintered medium-dielectric constant lithium-based microwave dielectric ceramic and a preparation method thereof. The raw material of the lithium-based microwave dielectric ceramic is Li2(Zn(1-x)Cux)(Ti(1-y)(Mg1/3Nb2/3)y)3O8Main powder and auxiliary powder Li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3System glass powder and auxiliary powder TiO2And (4) forming.
1) Synthesizing main powder: with purity of Li not less than 99%2CO3、ZnO、TiO2CuO, MgO and Nb2O5Is used as a main raw material and is carried out according to the following steps:
a. pretreatment of raw materials: presintering ZnO at 700 deg.C and holding for 4h, and presintering MgO with particle size of 40-80nm at 800 deg.C and holding for 4 h;
b. weighing the ingredients: according to Li2(Zn0.95Cu0.05)Ti3O8Metering and weighing;
c. wet ball milling: ball-milling the powder obtained in the step b by taking pure water as grinding fluid;
d. drying and pre-sintering: drying the slurry obtained in the step c, sieving by a 80-mesh sieve, pressing into blocks, and pre-sintering at 840 ℃ for 4h to prepare pre-sintered blocks;
e. crushing and pulverizing: the baked blocks are crushed and ball-milled to obtain D502.65 μm.
2) Preparing glass powder: li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3The system glass powder is Li with purity not less than 99%2CO3、Al2O3、B2O3、ZnO、SiO2、Na2CO3、K2CO3、BaCO3And La2O3Is taken as a main raw material and is carried out according to the following steps:
a. pretreatment of raw materials: presintering ZnO at 700 deg.C and holding for 4h, Na2CO3、K2CO3And B2O3Drying in a drying oven at 120 ℃ for 2h for later use;
b. weighing the ingredients: the weight percentages are as follows:
Figure BDA0002841351830000181
weighing;
c. wet ball milling: ball-milling the powder obtained in the step b by taking absolute ethyl alcohol as grinding fluid;
d. drying and smelting: drying the slurry obtained in the step c, sieving the dried slurry by a 80-mesh sieve, putting the dried slurry into a platinum crucible, smelting the platinum crucible at 1300 ℃, and pouring the smelting liquid into pure water to quench glass;
e. crushing and pulverizing: on the upper partBall milling the water quenched glass to obtain D503.12 μm glass frit.
3) Taking a certain amount of synthesized Li2(Zn0.95Cu0.05)Ti3O8Powder of Li in terms of glass powder2(Zn0.95Cu0.05)Ti3O81.5% of the powder, TiO2Occupy Li2(Zn0.95Cu0.05)Ti3O8And (5) mixing 8% of the powder. And drying the obtained slurry at 120 ℃ after wet ball milling for 4 hours. Adding 5% polyvinyl alcohol aqueous solution into the dried powder, and sieving with a 80-mesh sieve for granulation. The granulated powder is pressed into the powder under the pressure of 150MPa
Figure BDA0002841351830000182
The article of manufacture of (1). And sintering the product at 875 ℃ for 1 hour to obtain the microwave dielectric ceramic material. The microwave dielectric property of the material is as follows: epsilonr＝26.3、Q×f＝56319GHz、τf＝-4.5×10-6ppm/℃。
Example 7
A low-temperature sintered medium-dielectric constant lithium-based microwave dielectric ceramic and a preparation method thereof. The raw material of the lithium-based microwave dielectric ceramic is Li2(Zn(1-x)Cux)(Ti(1-y)(Mg1/3Nb2/3)y)3O8Main powder and auxiliary powder Li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3System glass powder and TiO2And (4) forming.
1) Synthesizing main powder: with purity of Li not less than 99%2CO3、ZnO、TiO2CuO, MgO and Nb2O5Is used as a main raw material and is carried out according to the following steps:
a. pretreatment of raw materials: presintering ZnO at 700 deg.C and holding for 4h, and presintering MgO with particle size of 40-80nm at 800 deg.C and holding for 4 h;
b. weighing the ingredients: according to Li2(Zn0.95Cu0.05)(Ti0.9(Mg1/3Nb2/3)0.1)3O8Metering and weighing;
c. wet ball milling: ball-milling the powder obtained in the step b by taking pure water as grinding fluid;
d. drying and pre-sintering: drying the slurry obtained in the step c, sieving by a 80-mesh sieve, pressing into blocks, and pre-sintering at 850 ℃ for 4h to prepare pre-sintered blocks;
e. crushing and pulverizing: the baked blocks are crushed and ball-milled to obtain D502.51 μm.
2) Preparing glass powder: li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3The system glass powder is Li with purity not less than 99%2CO3、Al2O3、B2O3、ZnO、SiO2、Na2CO3、K2CO3、BaCO3And La2O3Is taken as a main raw material and is carried out according to the following steps:
a. pretreatment of raw materials: presintering ZnO at 700 deg.C and holding for 4h, Na2CO3、K2CO3And B2O3Drying in a drying oven at 120 ℃ for 2h for later use;
b. weighing the ingredients: the weight percentages are as follows:
Figure BDA0002841351830000191
weighing;
c. wet ball milling: ball-milling the powder obtained in the step b by taking absolute ethyl alcohol as grinding fluid;
d. drying and smelting: drying the slurry obtained in the step c, sieving the dried slurry by a 80-mesh sieve, putting the dried slurry into a platinum crucible, smelting the platinum crucible at the temperature of 1350 ℃, and pouring the smelting liquid into pure water to quench glass;
e. crushing and pulverizing: ball milling the water quenched glass to obtain D503.28 μm glass frit.
3) Taking a certain amount of synthesized Li2(Zn0.95Cu0.05)(Ti0.9(Mg1/3Nb2/3)0.1)3O8Powder of Li in terms of glass powder2(Zn0.95Cu0.05)(Ti0.9(Mg1/3Nb2/3)0.1)3O81% of powder, TiO2Occupy Li2(Zn0.95Cu0.05)(Ti0.9(Mg1/ 3Nb2/3)0.1)3O8And (5) mixing 8% of the powder. And drying the obtained slurry at 120 ℃ after wet ball milling for 4 hours. Adding 5% polyvinyl alcohol aqueous solution into the dried powder, and sieving with a 80-mesh sieve for granulation. The granulated powder is pressed into the powder under the pressure of 150MPa
Figure BDA0002841351830000202
The article of manufacture of (1). And sintering the product at 875 ℃ for 1 hour to obtain the microwave dielectric ceramic material. The microwave dielectric property of the material is as follows: epsilonr＝26.2、Q×f＝58863GHz、τf＝-1.3×10-6ppm/℃。
Example 8
A low-temperature sintered medium-dielectric constant lithium-based microwave dielectric ceramic and a preparation method thereof. The raw material of the lithium-based microwave dielectric ceramic is Li2(Zn(1-x)Cux)(Ti(1-y)(Mg1/3Nb2/3)y)3O8Main powder and auxiliary powder Li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3System glass powder and auxiliary powder TiO2And (4) forming.
1) Synthesizing main powder: with purity of Li not less than 99%2CO3、ZnO、TiO2CuO, MgO and Nb2O5Is used as a main raw material and is carried out according to the following steps:
a. pretreatment of raw materials: presintering ZnO at 700 deg.C and holding for 4h, and presintering MgO with particle size of 40-80nm at 800 deg.C and holding for 4 h;
b. weighing the ingredients: according to Li2(Zn0.9Cu0.1)(Ti0.8(Mg1/3Nb2/3)0.2)3O8Metering and weighing;
c. wet ball milling: ball-milling the powder obtained in the step b by taking pure water as grinding fluid;
d. drying and pre-sintering: drying the slurry obtained in the step c, sieving by a 80-mesh sieve, pressing into blocks, and pre-sintering at 840 ℃ for 4h to prepare pre-sintered blocks;
e. crushing and pulverizing: the baked blocks are crushed and ball-milled to obtain D502.21 μm.
2) Preparing glass powder: li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3The system glass powder is Li with purity not less than 99%2CO3、Al2O3、B2O3、ZnO、SiO2、Na2CO3、K2CO3、BaCO3And La2O3Is taken as a main raw material and is carried out according to the following steps:
a. pretreatment of raw materials: presintering ZnO at 700 deg.C and holding for 4h, Na2CO3、K2CO3And B2O3Drying in a drying oven at 120 ℃ for 2h for later use;
b. weighing the ingredients: the weight percentages are as follows:
Figure BDA0002841351830000201
Figure BDA0002841351830000211
weighing;
c. wet ball milling: ball-milling the powder obtained in the step b by taking absolute ethyl alcohol as grinding fluid;
d. drying and smelting: drying the slurry obtained in the step c, sieving the dried slurry by a 80-mesh sieve, putting the sieved slurry into a platinum crucible, smelting the platinum crucible at the temperature of 1200 ℃, and pouring the smelting liquid into pure water to quench glass;
e. crushing and pulverizing: ball milling the water quenched glass to obtain D503.12 μm glass frit.
3) Taking a certain amount of synthesized Li2(Zn0.9Cu0.1)(Ti0.8(Mg1/3Nb2/3)0.2)3O8Powder of Li in terms of glass powder2(Zn0.9Cu0.1)(Ti0.8(Mg1/3Nb2/3)0.2)3O81% of powder, TiO2Occupy Li2(Zn0.9Cu0.1)(Ti0.8(Mg1/3Nb2/3)0.2)3O8And (5) mixing 8% of the powder. And drying the obtained slurry at 120 ℃ after wet ball milling for 4 hours. Adding 5% polyvinyl alcohol aqueous solution into the dried powder, and sieving with a 80-mesh sieve for granulation. The granulated powder is pressed into the powder under the pressure of 150MPa
Figure BDA0002841351830000212
The article of manufacture of (1). And sintering the product at 850 ℃ for 1 hour to obtain the microwave dielectric ceramic material. The microwave dielectric property of the material is as follows: epsilonr＝25.9、Q×f＝45386GHz、τf＝-4.3×10-6ppm/℃。
FIG. 1 shows the XRD (X-ray diffraction pattern) of example 1 sintered at 890 deg.C, FIG. 2 shows the XRD (X-ray diffraction pattern) of example 7 sintered at 875 deg.C, from which it can be seen that no significant second phase is formed after the addition of the sintering aid and the substitution at the B-position; FIG. 3 is SEM (scanning electron microscope image) of example 1 sintered at 890 ℃, FIG. 4 is SEM (scanning electron microscope image) of example 7 sintered at 875 ℃, and it can be seen that doping with sintering aid and substitution at B site promotes sintering densification, thereby improving Li2CO3-ZnO-TiO2Microwave properties of the system ceramic.
Comparative example 1
Preparing materials: to analyze pure Li2CO3ZnO and TiO2Powder as main raw material, according to Li2ZnTi3O8Proportioning according to a stoichiometric ratio;
ball milling: placing the prepared mixed powder into a resin ball milling tank, taking absolute ethyl alcohol as a dispersing agent and zirconia balls as a grinding medium, and carrying out ball milling for 24 hours at a ball milling rotating speed of 300rpm for 30 min;
drying: putting the tray containing the slurry into a drying oven with the temperature of 75 ℃ for drying;
pre-burning: pre-burning at 900 deg.C for 4 hr to obtain pre-burnt block, and crushing;
taking a certain amount of synthesized Li2ZnTi3O8Powder according to ZnO-La2O3-B2O3Glass powder of Li2ZnTi3O81.0 percent of the powder is mixed. And drying the obtained slurry at 75 ℃ after ball milling. Adding a polyvinyl alcohol water-alcohol solution accounting for 5 percent of the weight of the powder into the dried powder, and granulating by a double-layer screen of 40-60 meshes. And pressing the granulation powder into a green body with the height-diameter ratio of 0.4-0.6. Sintering the product at 925 ℃ for 4 hours to obtain Li2ZnTi3O8+1.0％ZnO-La2O3-B2O3Microwave dielectric ceramic material. The microwave dielectric property of the material is as follows: epsilonr＝24.34、Q×f＝41360GHz、τf＝-13.4×10-6ppm/℃。
Comparative example 2
Preparing materials: to analyze pure Li2CO3、ZnO、TiO2And Al2O3LiF and CaF2The powder as starting powder, according to Li2.1Zn0.8Al0.1Ti3O8The stoichiometric ratio of the raw materials is weighed and mixed;
ball milling: placing the prepared mixed powder into a resin ball milling tank, and carrying out ball milling for 24 hours by using absolute ethyl alcohol as a dispersing agent and zirconia balls as a grinding medium;
drying: putting the ground slurry after ball milling into a drying oven with the temperature of 75 ℃ for drying;
pre-burning: putting the dried powder into an alumina crucible, preserving heat at 900 ℃ for 4h for pre-sintering, preparing into pre-sintered blocks, and crushing;
secondary ball milling: performing secondary ball milling on the pre-sintered powder according to the ratio of ball materials to alcohol in the primary ball milling;
the resulting slurry was dried at 75 ℃. Taking a certain amount of synthesized Li2.1Zn0.8Al0.1Ti3O8Powder according to (LiF/CaF)2) Occupy Li2.1Zn0.8Al0.1Ti3O82.0 wt% of the powder was dosed. And drying the obtained slurry at 75 ℃ after ball milling. Adding a polyvinyl alcohol water-alcohol solution accounting for 5 percent of the weight of the powder into the dried powder, and granulating by a double-layer screen of 40-60 meshes. And pressing the granulation powder into a green body with the height-diameter ratio of 0.4-0.6. Sintering the green body at 900 ℃ for 4 hours to obtain 0.98Li2Zn0.4Co0.6Ti3O8-0.02(LiF/CaF2) Microwave dielectric ceramic material. The microwave dielectric property of the material is as follows: epsilonr＝25.77、Q×f＝34547GHz、τf＝-8.89×10-6ppm/℃。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (11)

1. A lithium-based microwave dielectric ceramic material is characterized in that the raw materials comprise:
a main powder and an auxiliary powder represented by formula (I); the auxiliary powder comprises glass powder accounting for 0.5-1.5 wt% of the main powder and rutile type TiO accounting for 5-10 wt% of the main powder2Micro-powder;
Li2(Zn(1-x)Cux)(Ti(1-y)(Mg1/3Nb2/3)y)3O8formula (I);
wherein x is more than or equal to 0 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.2.
2. The lithium-based microwave dielectric ceramic material as claimed in claim 1, wherein the glass frit is Li2O-Al2O3-B2O3-ZnO-SiO2-Na2O-K2O-BaO-La2O3A glass system;
the glass powder D50 is 2-4 mu m;
the rutile type TiO2The particle diameter D50 of the fine powder is 0.5 to 1.0 μm.
3. The lithium-based microwave dielectric ceramic material as claimed in claim 2, wherein the glass powder is prepared by performing wet ball milling, drying, smelting and crushing on the following raw materials in parts by weight:
Figure FDA0002841351820000011
4. the lithium-based microwave dielectric ceramic material of claim 3 wherein the raw material of the glass frit further comprises a pretreatment comprising: pre-sintering ZnO at 600-700 ℃ and preserving heat for 4-5 h; na (Na)2CO3、K2CO3And B2O3Drying the mixture in an oven at 100-120 ℃ for 1-2 h respectively;
the smelting temperature is 1200-1350 ℃.
5. The lithium-based microwave dielectric ceramic material as claimed in claim 1, wherein the main powder represented by formula (I) is Li2ZnTi3O8、Li2Zn(Ti0.95(Mg1/3Nb2/3)0.05)3O8、Li2Zn(Ti0.9(Mg1/3Nb2/3)0.1)3O8、Li2Zn(Ti0.8(Mg1/3Nb2/3)0.2)3O8、Li2(Zn0.975Cu0.025)Ti3O8、Li2(Zn0.95Cu0.05)Ti3O8、Li2(Zn0.95Cu0.05)(Ti0.9(Mg1/3Nb2/3)0.1)3O8Or Li2(Zn0.9Cu0.1)(Ti0.8(Mg1/3Nb2/3)0.2)3O8One or more of them.
6. The preparation method of the lithium-based microwave dielectric ceramic material as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
a main powder body, glass powder and rutile type TiO shown in formula (I)2Mixing the micro powder, ball milling by a wet method, drying, mixing with a binder, granulating, pressing and sintering to obtain the nano-composite material.
7. The preparation method according to claim 6, wherein the preparation method of the main powder represented by the formula (I) specifically comprises:
Li2CO3、ZnO、TiO2CuO, MgO and Nb2O5Mixing according to a metering ratio, grinding by a wet method, drying, presintering and crushing to obtain the product.
8. The preparation method according to claim 7, wherein the preparation method of the main powder represented by the formula (I) further comprises pretreatment of ZnO and MgO, and the pretreatment specifically comprises: pre-sintering ZnO at 600-700 ℃ and preserving heat for 4-5 h; preserving the temperature of MgO at 700-800 ℃ for 4-5 h;
the particle size of the MgO is 40-80 nm;
the pre-sintering temperature is 800-900 ℃; the time is 2-6 h;
and crushing to obtain a main powder represented by the formula (I) with D50 being 1-3 μm.
9. The preparation method of claim 6, wherein the wet ball milling time is 3-4 h; the drying temperature is 120-140 ℃; the binder is polyvinyl alcohol; the pressing pressure is 140-150 Mpa; the sintering temperature is 850-890 ℃; the sintering time is 0.5-1 h.
10. A lithium-based microwave dielectric ceramic prepared from the ceramic material according to any one of claims 1 to 5 or the ceramic material prepared by the preparation method according to any one of claims 6 to 9.
11. A microwave device prepared from the ceramic material of any one of claims 1 to 5 or the ceramic material prepared by the preparation method of any one of claims 6 to 9.
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