CN106977203B - Zero-temperature-coefficient low-temperature sintering microwave medium and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field of electronic information materials and components, and provides a low-temperature sintering microwave medium with zero temperature coefficient and a preparation method thereof, which are used for solving the problem that the temperature coefficient of the existing microwave medium material limits the application; the chemical formula of the microwave medium is as follows: ca5+aCo4+bV6+cO24－yTiO2Wherein a is more than or equal to-0.05 and less than or equal to 0, b is more than or equal to-0.05 and less than or equal to 0, c is more than or equal to 0.05 and less than or equal to 0, and y is more than or equal to 0.07 and less than or equal to 0.19; the microwave medium can realize that the temperature coefficient of the resonance frequency is as follows: -10 ppm/DEG C to +10 ppm/DEG C, namely a zero temperature coefficient; meanwhile, the material has the characteristic of low sintering temperature, does not need to add any sintering aid, effectively prevents the dielectric property of the material from deteriorating due to the sintering aid, keeps higher density and ceramic strength, has simple preparation process, is environment-friendly and energy-saving, has good repeatability and low cost, and is easy to realize industrial production.
Description
Technical Field
The invention belongs to the technical field of electronic information materials and components, and particularly relates to a zero-temperature-coefficient low-temperature sintering microwave dielectric material and a preparation method thereof.
Background
The microwave medium is a novel electronic medium which is rapidly developed in the last 30 years and has the characteristics of low loss, small frequency temperature coefficient and the like. The microwave medium can be used for manufacturing microwave components such as a filter, a resonator, a medium guided wave loop and the like and a microwave circuit substrate, and is widely applied to the fields of satellites, televisions, radars, mobile communication, electronic computers and the like. The document of the outline of electronic information industry adjustment and joyful planning of the state institute as early as 2009 provides the importance of developing dielectric materials with serialized dielectric constants and excellent microwave properties. High quality factor, near zero frequency temperature coefficient and low sintering temperature are the key research and development directions of microwave media.
The interconnection conductor used in LTCC technology generally has silver metal with excellent conductivity, and its melting point is about 961 ℃, which requires that the ceramic material applied in LTCC technology must be sintered to be compact below 950 ℃, and in addition, the microwave ceramic material applied in LTCC technology should have the following characteristics: (1) a suitable dielectric constant to facilitate miniaturization of the device; (2) high quality factor to reduce losses, in generalQ x f is required to be more than or equal to 20000 GHz; (3) a near-zero temperature coefficient (10 to +10 ppm/. degree. C.) to facilitate temperature stability. However, in order to meet the temperature requirement of LTCC (sintering densification temperature is lower than 950 ℃), many high-temperature sintering microwave ceramics must be added with sintering aid (B)2O3Glass and V2O5Lower melting point oxides) such as those described in Oh satoH, Ohhashi T, Kato H, et al, microwave Dielectric Properties and Structure of the Ba6-3xSm8+2xTi18O54Solid Solutions[J]Ba is reported in Japanese Journal of Applied Physics,1995,34(1):187-1916-3xSm8+2xTi18O54By adding 0.5 wt% of B2O3Lowering the sintering temperature from 1733K to 1473K also lowers the quality factor and dielectric constant, which is typical of low temperature sintering in exchange for sacrificing microwave dielectric properties. Therefore, although the sintering aid can play a role in reducing sintering, the addition of the sintering aid can deteriorate the microwave dielectric property and reduce the density and the strength of the ceramic body; the structure formed by adding the sintering aid is difficult to control, the preparation process is relatively complex, the sintering aid generally needs to be prepared separately, such as through a glass melting process, the complexity of the process is increased, a large amount of energy is consumed, and the energy consumption is increased. Therefore, there has been a trend toward the development of low-temperature sintered microwave ceramics.
The vanadate system is a novel LTCC microwave dielectric material, has the advantages of low sintering temperature and high Q x f value, and is gradually concerned in recent years. For example, Journal of the American Ceramic Society,2013,96(6):1691-5A4(VO4)6(A2+ ═ Mg, Zn) reported that Ca5Zn4(VO4)6And Ca5Mg4(VO4)6Microwave dielectric property of microwave ceramic sintered at 725 ℃ and 800 ℃: dielectric constants 11.7 and 9.2, quality factor Q × f 49400GHz and 53300GHz, temperature coefficients-83 ppm/° c and-50 ppm/° c; journal of Materials Science: Materials in electronics 2016,27(7):7292-wave dielectric properties of lowtemperature sintering Ca5Mn4(VO4)6In the report of diabetes mellitus, Ca5Mn4(VO4)6The microwave medium is sintered at 875 ℃ and has good microwave dielectric property: the relative dielectric constant is 11.2, and the quality factor Q multiplied by f is 33800GHz, but the deficiency is that the temperature coefficient of the resonant frequency is-70 ppm/DEG C, which seriously limits the application of the microwave medium in electronic information materials and components.
Based on the method, the invention provides a low-temperature sintering microwave medium with zero temperature coefficient and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a low-temperature sintering microwave medium with zero temperature coefficient and a preparation method thereof, which are used for solving the problem that the temperature coefficient of the existing microwave medium material limits the application of the microwave medium material; the chemical formula of the material is as follows: ca5+aCo4+bV6+cO24－yTiO2Wherein a is more than or equal to-0.05 and less than or equal to 0, b is more than or equal to-0.05 and less than or equal to 0, c is more than or equal to 0.05 and less than or equal to 0, and y is more than or equal to 0.07 and less than or equal to 0.19; the microwave medium can realize that the temperature coefficient of the resonance frequency is as follows: the concentration of the active carbon is-10 ppm/DEG C to +10 ppm/DEG C, and the preparation process is simple, low in cost, good in repeatability and easy for industrial production.
In order to achieve the purpose, the invention adopts the technical scheme that:
a low-temperature sintering microwave medium with zero temperature coefficient is characterized in that the chemical expression of the microwave medium is as follows:
Ca5+aCo4+bV6+cO24－yTiO2wherein a + b + c is-0.05, -0.05-0.0, and 0.07-0.19.
Further, in the chemical expression of the microwave medium: y is more than or equal to 0.11 and less than or equal to 0.15; the main crystal phase of the microwave ceramic material is Ca5Co4(VO4)6The secondary crystal phase is TiO2。
Further, the resonant frequency temperature coefficient of the microwave medium is: -10ppm/° C to +10ppm/° C.
The preparation method of the low-temperature sintering microwave medium with the zero temperature coefficient comprises the following steps:
step 1: with CaO, Co2O3、V2O5And TiO2Raw materials are mixed according to a molar ratio of Ca: co: v: ti ═ 5+ a: 4+ b: 6+ c: y, blending and uniformly mixing to obtain a mixture; wherein a + b + c is-0.05 and-0.05 is less than or equal to a and is less than or equal to 0, -0.05 is less than or equal to b and is less than or equal to 0, -0.05 is less than or equal to c and is less than or equal to 0, and y is more than or equal to 0.07 is less than or equal to 0.19;
step 2: sequentially carrying out ball milling, drying and sieving on the mixture obtained in the step 1 to obtain dry powder;
and step 3: pre-sintering the powder obtained in the step 2 at the temperature of 750-850 ℃ for 2-4 hours to obtain a pre-sintered material;
and 4, step 4: performing ball milling, drying and sieving on the pre-sintered material obtained in the step 3 in sequence to obtain dry powder;
and 5: and (4) granulating the powder obtained in the step (4), carrying out dry pressing and forming and glue discharging treatment to obtain a green body, and sintering the green body at the temperature of 900-925 ℃ for 2-5 hours to obtain the microwave medium.
Further, the technological parameters of the step 2 and the step 4 are the same, and the ball milling time is as follows: 4-7 h, the drying temperature is as follows: 80-100 ℃.
The invention has the beneficial effects that:
the invention provides a low-temperature sintering microwave medium with zero temperature coefficient and a preparation method thereof, wherein the microwave medium can realize the following resonant frequency temperature coefficients: -10 ppm/DEG C to +10 ppm/DEG C, namely a zero temperature coefficient; the material has the characteristic of low sintering temperature (the sintering temperature is lower than 950 ℃), and no sintering aid is added, so that the dielectric property deterioration caused by the sintering aid is effectively prevented, and higher density and ceramic strength are kept; meanwhile, the problems that a complex phase structure formed by adding the sintering aid is difficult to control, the preparation process is complex (the sintering aid needs to be prepared separately, such as through a glass melting process) and the like are effectively avoided; in conclusion, the invention provides the low-temperature sintering microwave medium with the zero temperature coefficient, and meanwhile, the microwave medium has the advantages of simple preparation process, environmental protection, energy conservation, good repeatability, low cost and easy realization of industrial production.
Drawings
FIG. 1 shows Ca prepared in example 15+aCo4+bV6+cO24－yTiO2XRD diffraction analysis pattern of microwave medium.
FIG. 2 shows Ca prepared in example 15+aCo4+bV6+cO24－yTiO2Surface SEM images of microwave media.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Examples 1 to 5
The chemical expression of the microwave medium provided in the above embodiment is: ca5+aCo4+bV6+cO24－yTiO2Wherein a ═ b ═ 0, c ═ 0.05, and y ═ 0.13; the microwave medium comprises the following specific preparation steps:
step 1: with CaO, Co2O3、V2O5And TiO2Raw materials are mixed according to a molar ratio of Ca: co: v: ti ═ 5+ a: 4+ b: 6+ c: y, blending and uniformly mixing to obtain a mixture;
step 2: ball-milling the mixture obtained in the step 1 for 7 hours, drying at the temperature of 100 ℃, and sieving by a 40-mesh sieve to obtain dry powder;
and step 3: presintering the powder obtained in the step 2 at 775 ℃ for 3 hours to obtain a presintering material;
and 4, step 4: performing secondary ball milling on the obtained pre-sintering material for 7 hours, drying at the temperature of 100 ℃, and sieving by a 40-mesh sieve to obtain dry powder;
and 5: granulating the powder obtained in the step (4), performing dry pressing and glue discharging treatment to obtain a green body, and sintering the green body at the temperature of 900-925 ℃ for 2-5 hours to obtain a required microwave medium;
step 6: according to a Hakki-Coleman dielectric resonance method, testing the dielectric property and the frequency temperature coefficient of the sample at high frequency by using a network analyzer; the measured results include dielectric constant, quality factor and temperature coefficient of resonant frequency.
The specific composition, process parameters and microwave dielectric properties of examples 1-5 are shown in the following table:
in example 1, the XRD diffraction analysis pattern and the surface SEM pattern of the microwave medium are shown in fig. 1 and 2, respectively.
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 (6)
1. A low-temperature sintering microwave medium with zero temperature coefficient is characterized in that the chemical expression of the microwave medium is as follows:
Ca5+aCo4+bV6+cO24－yTiO2wherein a + b + c is-0.05, -0.05-0.0, and 0.07-0.19.
2. The zero temperature coefficient low temperature sintered microwave medium of claim 1 wherein the microwave medium has the chemical formula: y is more than or equal to 0.11 and less than or equal to 0.15.
3. The zero temperature coefficient low temperature sintering microwave medium of claim 1 wherein the microwave ceramic material has a main crystal phase of Ca5Co4(VO4)6The secondary crystal phase is TiO2。
4. The zero temperature coefficient low temperature sintered microwave medium of claim 1 wherein said microwave medium has a resonant frequency temperature coefficient of: -10ppm/° C to +10ppm/° C.
5. The method for preparing a zero temperature coefficient low temperature sintered microwave medium as claimed in claim 1, comprising the steps of:
step 1: with CaO, Co2O3、V2O5And TiO2Raw materials are mixed according to a molar ratio of Ca: co: v: ti ═ 5+ a: 4+ b: 6+ c: y, blending and uniformly mixing to obtain a mixture; wherein a + b + c is-0.05 and-0.05 is less than or equal to a and is less than or equal to 0, -0.05 is less than or equal to b and is less than or equal to 0, -0.05 is less than or equal to c and is less than or equal to 0, and y is more than or equal to 0.07 is less than or equal to 0.19;
step 2: sequentially carrying out ball milling, drying and sieving on the mixture obtained in the step 1 to obtain dry powder;
and step 3: pre-sintering the powder obtained in the step 2 at the temperature of 750-850 ℃ for 2-4 hours to obtain a pre-sintered material;
and 4, step 4: performing ball milling, drying and sieving on the pre-sintered material obtained in the step 3 in sequence to obtain dry powder;
and 5: and (4) granulating the powder obtained in the step (4), carrying out dry pressing and forming and glue discharging treatment to obtain a green body, and sintering the green body at the temperature of 900-925 ℃ for 2-5 hours to obtain the microwave medium.
6. The method for preparing the zero-temperature-coefficient low-temperature sintering microwave medium according to claim 5, wherein the process parameters of the step 2 and the step 4 are the same, and the ball milling time is as follows: 4-7 h, the drying temperature is as follows: 80-100 ℃.
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| "（1-x）ca5zn4（vo4）6-xca0.8sr0.2tio3陶瓷微波介电性能研究";层;《西安邮电大学学报》;20140910;第19卷(第5期);第91-95页 * |
| Low-temperature sintering and microwave dielectric properties of Ca5C4（VO4）6 ceramics;Guoguang Yao.etc;《Journal of the European Ceramic Society》;20140426;第2983-2987页 * |
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