CN108610047B - Ultralow temperature sintered microwave ceramic material and preparation method thereof - Google Patents

Ultralow temperature sintered microwave ceramic material and preparation method thereof Download PDF

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CN108610047B
CN108610047B CN201810507562.3A CN201810507562A CN108610047B CN 108610047 B CN108610047 B CN 108610047B CN 201810507562 A CN201810507562 A CN 201810507562A CN 108610047 B CN108610047 B CN 108610047B
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李波
田佳蔚
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University of Electronic Science and Technology of China
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Abstract

The invention belongs to the technical field of electronic ceramics and manufacturing thereof, and particularly provides an ultralow temperature sintering microwave ceramic material and a preparation method thereof, which are used for overcoming the defect that the sintering temperature of the existing microwave ceramic material is generally higher, and realizing ultralow temperature sintering at 700-750 ℃, wherein the optimal sintering temperature is 725 ℃. The ceramic material of the invention is single crystal phase Ca5Zn4V6O24Of the chemical formula Ca5+aZn4+bV6O24Wherein, 0<a<0.3，0<b<0.3; by adjusting the non-chemical dose ratio, the external loss such as pores and the internal loss such as vanadium vacancy caused by vanadium volatilization are controlled, excellent microwave dielectric property (dielectric constant is 12.0 under 9.9GHz frequency, Qxf value is 61974GHz, resonance frequency temperature coefficient is-91.2 ppm/° C) is obtained, and the microwave dielectric property is obviously superior to the chemical dose ratio Ca5Zn4V6O24. The ceramic material has rich raw materials and low cost, is beneficial to industrial production, and can be widely applied to the manufacture of microwave devices such as low-temperature co-fired ceramic systems, multilayer dielectric resonators, filters, microwave substrates and the like.

Description

Ultralow temperature sintered microwave ceramic material and preparation method thereof
Technical Field
The invention belongs to the technical field of electronic ceramics and manufacture thereof, and particularly relates to an ultralow temperature sintered microwave ceramic material and a preparation method thereof.
Background
With the rapid development of modern wireless communication industry, internet of things, wearable electronics and intelligent transportation systems, corresponding systems and devices are developing towards multifunction, miniaturization, flexibility, light weight, low cost and high frequency, further raising new requirements on the performance of dielectric materials, and increasing the demand on microwave dielectric ceramic materials with excellent performance. The low-temperature co-fired ceramic technology (L TCC) can realize high-density integrated circuits and hybrid integration of passive devices and active devices, thereby realizing miniaturization and multiple functions of the devices and systems.
The LTCC technology has main requirements for dielectric materials: (1) the low dielectric constant material can be used as a substrate material and the like, so that the delay of signal transmission is reduced; (2) the low dielectric loss is beneficial to reducing the loss of devices and improving the signal intensity; (3) the temperature coefficient of the frequency is near zero, so that the temperature stability of the dielectric constant and the resonant frequency is ensured; (4) below the sintering temperature of the electrode material; (5) good thermomechanical properties such as high thermal conductivity, linear expansion coefficient matching with the integrated material.
With the rapid development of flexible devices such as wearable electronics, ceramic materials are required to be integrated and co-fired with low-melting-point electrodes, semiconductor materials, polymer-based substrates and the like; although a large number of low loss microwave dielectric ceramic materials have been reported in the literature, most of them have high sintering temperatures. Therefore, one of the current research focuses is the development of ultra-low temperature sintered ceramic (ULTCC) materials below 750 ℃, which is beneficial to reduce energy consumption, prevent volatilization of volatile components and reaction with other materials. Most high quality factor (Q × f) dielectric materials have a high sintering temperature, and the addition of low melting point oxide is usually used to lower the sintering temperature, but tends to deteriorate the microwave dielectric properties and reduce the mechanical strength. A common low melting additive is TeO2、Bi2O3、B2O3、Li2O、V2O5And MoO3And the like. On the other hand, the microwave dielectric ceramic material with the intrinsic ultralow sintering temperature is designed and developed from the material science perspective, and not only has simple phase formation, but also has excellent performance.
The vanadate system microwave ceramic material is greatly concerned about due to the intrinsic low sintering temperature and excellent microwave dielectric property, and becomes an important research direction of the ultralow temperature microwave ceramic material. Ca is reported in the Ceramics International journal5N i4(VO4)6The ceramic is sintered at 875 ℃ to obtain excellent dielectric properties: epsilonr＝9.5GHz，Q×f＝54100GHz，τfAt-60 pp m/° c (at 10.5GHz), however, its elevated sintering temperature still limits its further development (43: 334-. Ca is reported in the journal of Ceramics International5Zn4(VO4)6The ceramic is sintered at 725 ℃, and the microwave dielectric property of the ceramic is as follows: epsilonr＝11.7，Q×f＝49400GHz，τf＝-81 ppm/. degree.C. (9.7GHz), although ultra-low temperature sintering is achieved, the Q x f value needs to be further improved (96[6 ] F]:1691-1693(2013)). In the actual production process, the vanadium element is a volatile element, so that uncontrollable loss can be generated in the pre-sintering and sintering processes, external loss such as air holes and internal loss such as vanadium vacancy and the like are caused, and the improvement of the Q x f value of the vanadate microwave ceramic is limited.
In summary, the invention provides an ultralow temperature sintered microwave ceramic material and a preparation method thereof.
Disclosure of Invention
The invention aims to provide an ultralow temperature sintering microwave ceramic material and a preparation method thereof, which are used for overcoming the defect that the sintering temperature of the existing microwave ceramic material is generally higher, and realizing ultralow temperature sintering at 700-750 ℃, wherein the optimal sintering temperature is 725 ℃. The ceramic material of the invention is single crystal phase Ca5Zn4V6O24Of the chemical formula Ca5+aZn4+bV6O24Wherein, 0<a<0.3，0<b<0.3; by adjusting the non-chemical dose ratio, the external loss such as pores and the internal loss such as vanadium vacancy caused by vanadium volatilization are controlled, excellent microwave dielectric property (dielectric constant is 12.0 under 9.9GHz frequency, Qxf value is 61974GHz, resonance frequency temperature coefficient is-91.2 ppm/° C) is obtained, and the microwave dielectric property is obviously superior to the chemical dose ratio Ca5Zn4V6O24. The ceramic material has rich raw materials and low cost, is beneficial to industrial production, and can be widely applied to the manufacture of microwave devices such as low-temperature co-fired ceramic systems, multilayer dielectric resonators, filters, microwave substrates and the like.
In order to achieve the purpose, the invention adopts the technical scheme that;
the ultralow temperature sintered microwave ceramic material is characterized by having a cubic garnet structure and a single crystal phase of Ca5Zn4V6O24The chemical formula is Ca5+aZn4+bV6O24Wherein, 0<a<0.3、0<b<0.3。
The preparation method of the ultralow temperature sintered microwave ceramic material is characterized by comprising the following steps:
step 1: using CaCO3、ZnO、V2O5As raw materials, according to Ca: zn: v ═ 5+ a: 4+ b: 6, mixing to obtain a mixture, wherein the molar ratio of 0<a<0.3、0<b<0.3；
Step 2: performing ball milling on the mixture obtained in the step 1 to obtain a ball grinding material;
and step 3: drying and sieving the ball-milled material obtained in the step 2 to obtain uniformly dispersed powder;
and 4, step 4: pre-burning the uniformly dispersed powder obtained in the step 3 at the temperature of 680-720 ℃ for 2-5 h to obtain pre-burned powder;
and 5: granulating the pre-sintered powder obtained in the step 4, and then performing dry pressing to obtain a green body;
step 6: and (4) sintering the green body obtained in the step (5) at the temperature of 700-750 ℃ for 3-5 h to obtain the ultralow-temperature sintering microwave ceramic material.
The invention has the beneficial effects that:
1. the microwave ceramic material provided by the invention can be sintered at an ultralow temperature of 700-750 ℃, belongs to an ultralow temperature sintering microwave ceramic material, and the ultralow sintering temperature not only can greatly reduce energy consumption and production cost, but also can prevent volatilization of volatile components and reaction with other materials;
2. the microwave ceramic material provided by the invention has ultralow intrinsic sintering temperature, and does not need to add any sintering aid, so that the dielectric property of the material is prevented from being deteriorated due to the sintering aid, and the density and the strength of the ceramic body are prevented from being reduced; the complicated preparation process of the sintering aid, such as glass melting and the like, is avoided;
3. the microwave ceramic material provided by the invention keeps single crystal phase Ca5Zn4V6O24The external loss such as air holes and the like and the internal loss such as vanadium vacancy and the like caused by vanadium volatilization are controlled by adjusting the non-chemical dose ratio, the dielectric property is greatly improved, the dielectric constant is about 12, the Qxf value is higher than 60000GHz, and the temperature coefficient of the resonance frequency is about-90 ppm/° C；
4. The ceramic material provided by the invention has the advantages of simple preparation process, rich raw materials and low cost, is beneficial to industrial production, and can be widely applied to the manufacture of microwave devices such as low-temperature co-fired ceramic systems, multilayer dielectric resonators, filters, microwave substrates and the like.
Drawings
FIG. 1 is an SEM image of an ultra-low temperature sintered microwave ceramic material prepared in example 1 of the present invention.
FIG. 2 is an XRD pattern of the ultra-low temperature sintered microwave ceramic material prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
The invention provides 5 embodiments which are numbered 1-5 respectively; each of the examples provides an ultra-low temperature sintered microwave ceramic material having a cubic garnet-type structure with Ca as a single crystal phase5Zn4V6O24The chemical formula is Ca5+aZn4+bV6O24Wherein, 0<a<0.3、0<b<0.3。
The preparation method of the ultralow temperature sintered microwave ceramic material comprises the following steps:
step 1: using CaCO3、ZnO、V2O5Is taken as a raw material, is mixed according to the chemical proportion of a chemical formula to obtain a mixture,
step 2: performing ball milling on the mixture obtained in the step 1 to obtain a ball grinding material;
and step 3: drying and sieving the ball-milled material obtained in the step 2 to obtain uniformly dispersed powder;
and 4, step 4: pre-burning the uniformly dispersed powder obtained in the step 3 at the temperature of 680-720 ℃ for 2-5 h to obtain pre-burned powder;
and 5: adding the pre-sintered powder obtained in the step 4 into a polyvinyl alcohol aqueous solution for granulation, and performing dry pressing forming under the pressure of 20Mpa to obtain a cylindrical green body with the diameter of 15mm and the thickness of 6-7 mm;
step 6: and (4) sintering the green body obtained in the step (5) at the temperature of 700-750 ℃ for 3-5 h to obtain the ultralow-temperature sintering microwave ceramic material.
The specific parameters disclosed in the above 5 examples and the microwave dielectric properties of the ultra-low temperature sintered microwave ceramic material are shown in the following table:
Figure BDA0001671625500000041
wherein, the SEM picture and XRD picture of the ultra-low temperature sintered microwave ceramic material prepared in example 1 are shown as figure 1 and figure 2 respectively, and it can be seen from the figure that the microwave ceramic material has a single crystal phase of Ca5Zn4V6O24And has a cubic garnet-type structure.
While the invention has been described with reference to specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise; all of the disclosed features, or all of the method or process steps, may be combined in any combination, except mutually exclusive features and/or steps.

Claims (2)

1. The ultralow temperature sintered microwave ceramic material is characterized by having a cubic garnet structure and a single crystal phase of Ca5Zn4V6O24The chemical formula is Ca5+aZn4+bV6O24Wherein, 0<a<0.3、0.1≤b<0.3; the Q multiplied by f value of the ultralow-temperature sintered microwave ceramic material is higher than 60000 GHz.
2. The method for preparing ultra-low temperature sintered microwave ceramic material as claimed in claim 1, which comprises the steps of:
step 1: using CaCO3、ZnO、V2O5As raw materials, according to Ca: zn: v =5+ a: 4+ b: 6, mixing to obtain a mixture, wherein the molar ratio of 0<a<0.3、0.1≤b<0.3；
Step 2: performing ball milling on the mixture obtained in the step 1 to obtain a ball grinding material;
and step 3: drying and sieving the ball-milled material obtained in the step 2 to obtain uniformly dispersed powder;
and 4, step 4: pre-burning the uniformly dispersed powder obtained in the step 3 at the temperature of 680-720 ℃ for 2-5 h to obtain pre-burned powder;
and 5: granulating the pre-sintered powder obtained in the step 4, and then performing dry pressing to obtain a green body;
step 6: and (4) sintering the green body obtained in the step (5) at the temperature of 700-750 ℃ for 3-5 h to obtain the ultralow-temperature sintering microwave ceramic material.
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CN110002874B (en) * 2019-04-30 2021-09-24 电子科技大学 Ultralow temperature sintered microwave dielectric ceramic material and preparation method thereof
CN110395984A (en) * 2019-08-01 2019-11-01 电子科技大学 A kind of low temperature sintering microwave ceramic material and preparation method thereof
CN110330334A (en) * 2019-08-01 2019-10-15 电子科技大学 Low-temperature sintering microwave medium material C a5Ni4-xZnxV6O24And preparation method thereof
CN111908920A (en) * 2020-07-31 2020-11-10 东莞市翔通光电技术有限公司 Barium-cobalt-zinc-niobium-based microwave dielectric ceramic and preparation method thereof
CN113582690B (en) * 2021-07-09 2022-10-14 电子科技大学 Ultralow temperature sintered microwave dielectric material Zn 2 V 2 O 7 And method for preparing the same
CN114550977B (en) * 2022-03-03 2024-01-30 太原理工大学 Low-temperature co-fired ceramic dielectric material and preparation method thereof
CN115872740B (en) * 2022-12-28 2023-10-27 北京工业大学 Ultralow-temperature sintered low-dielectric microwave dielectric ceramic and preparation method thereof

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WO2002080297A2 (en) * 2001-03-30 2002-10-10 Creavis Gesellschaft Für Technologie Und Innovation Mbh Electrolyte membrane, membrane electrode units comprising the same, method for the production thereof and specific uses therefor

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Novel series of low-firing microwave dielectric ceramic:Ca5A4(VO4)6（A2+=Mg,Zn）;Guo-Guang Yao et al.;《Journal of the American Ceramic Society》;20130630;第96卷(第6期);第1691-1693页 *

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