CN114477984B - Microwave dielectric ceramic material and preparation method thereof - Google Patents
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Abstract
The application provides a microwave dielectric ceramic material and a preparation method thereof, wherein the microwave dielectric ceramic material comprises the following components in percentage by mass: 33 to 38 percent of CaO,12 to 14 percent of MgO and 2 to 3%Z percentnO，24～43％SiO 2 And 3-28% GeO 2 . Zn for microwave dielectric ceramic material 2+ Partially replace CaMgSi 2 O 6 Mg of (B) 2+ Forming CaMg 1‑x Zn x Si 2 O 6 Solid solution, the microwave dielectric property of the ceramic material is improved; in addition to Ge 4+ Ion fraction replaces CaMg 1‑x Zn x Si 2 O 6 Si of (C) 4+ The total ion polarization rate of the ceramic system is increased, the intrinsic loss of the ceramic material is reduced, and the dielectric constant of the microwave dielectric ceramic is 7.8-8.2; q×f is 137000 ～ 200000GHz; the temperature coefficient of resonance frequency is-53 to-75 ppm/DEG C.
Description
Technical Field
The application relates to the field of electronic functional materials and devices, in particular to a microwave dielectric ceramic material and a preparation method thereof.
Background
Microwaves are electromagnetic waves with the frequency range of 300 MHz-300 GHz, and comprise decimeter waves, centimeter waves and millimeter wave bands. Microwaves have a very wide frequency band under a certain relative bandwidth, have a larger information capacity and a higher transmission rate, and are widely applied to mobile communication, satellite communication and radar systems. Microwave dielectric ceramics are key materials for human use in microwaves. The rapid development of modern mobile communication technology has put higher demands on communication equipment, miniaturization, high frequency and the like have become the development direction of the communication equipment, and the microwave dielectric ceramics are required to have the characteristics of low dielectric constant and low loss, and can have adjustability in a certain dielectric constant range.
CaMgSi 2 O 6 Is a common low-dielectric silicate ceramic system, has the advantages of lower sintering temperature and easy doping modification compared with other orthosilicate systems, and has the disadvantage of higher loss. How to reduce CaMgSi 2 O 6 Loss of ceramic systems is the target of many researchers, but none of the prior attempts have resulted in CaMgSi 2 O 6 The Q multiplied by f value of the ceramic system reachesTo 130000GHz or more.
Disclosure of Invention
The application provides a microwave dielectric ceramic material and a preparation method thereof, which aim to solve the problem of CaMgSi 2 O 6 The system microwave dielectric ceramic has high loss.
On one hand, the embodiment of the application provides a microwave dielectric ceramic material, which comprises the following components in percentage by mass: 33 to 38 percent of CaO,12 to 14 percent of MgO,2 to 3 percent of ZnO and 24 to 43 percent of SiO 2 And 3-28% GeO 2 The dielectric constant of the microwave dielectric ceramic is 7.8-8.2; q×f is 137000 ～ 200000GHz; the temperature coefficient of resonance frequency is-53 to-75 ppm/DEG C.
On the other hand, the embodiment of the application provides a preparation method of a microwave dielectric ceramic material, which comprises the following steps:
(1) Weighing raw material powder according to the proportion, and performing ball milling for the first time to obtain a mixture;
(2) Carrying out primary drying, sieving and presintering treatment on the mixture to obtain presintering material;
(3) Performing secondary ball milling, secondary drying, granulation and dry pressing forming treatment on the presintered material to obtain a green body;
(4) And sintering the green body to obtain the microwave dielectric ceramic material.
Preferably, the raw material powder in step (1) includes calcium carbonate, magnesium oxide, zinc oxide, silicon dioxide and germanium dioxide powder.
Preferably, the rotation speed of the first ball milling in the step (1) is 250-350 rpm, and the time is 4-8 hours.
Preferably, the ball milling medium for the first ball milling in the step (1) is alcohol, and the ball-to-material ratio is (8-12): 1.
Preferably, the temperature of the pre-sintering treatment in the step (2) is 1050-1150 ℃ and the time is 4-8 hours.
Preferably, the granulating in step (3) comprises adding an adhesive to the dried pre-sintered material after the second drying and mixing to form the dried pre-sintered material into granules having an average particle size of 0.1 to 0.5 mm.
Preferably, the dry-pressing in step (3) has a pressure of 100 to 200 mpa.
Preferably, the dry pressing molding treatment in the step (3) further comprises a glue discharging treatment, wherein the glue discharging temperature is 550-650 ℃ and the time is 4-8 hours.
Preferably, the sintering treatment temperature in the step (4) is 1150-1250 ℃ and the time is 4-8 hours.
The Zn for the microwave dielectric ceramic material provided by the invention 2+ Partially replace CaMgSi 2 O 6 Mg of (B) 2+ Forming CaMg 1-x Zn x Si 2 O 6 Solid solution with Zn 2+ The content is increased, the ceramic density is improved, and the porosity is reduced, so that the microwave dielectric property of the ceramic material is directly improved; in addition, ge is used 4+ Ion fraction replaces CaMg 1-x Zn x Si 2 O 6 Si of (C) 4+ The total ion polarization rate of the ceramic system is increased, the intrinsic loss of the ceramic material is reduced, the dielectric constant of the ceramic material is changed between 7.8 and 8.2, and the ceramic material has a higher Q multiplied by f value which can reach 200000GHz at maximum. The microwave dielectric ceramic material has simple preparation process and is expected to be applied to the manufacture of microwave devices such as microwave integrated circuit substrates, resonators, electronic product packages and the like.
Drawings
Features, advantages, and technical effects of exemplary embodiments of the present application will be described below with reference to the accompanying drawings.
FIG. 1 is a surface micrograph of a microwave dielectric ceramic material of example 1;
fig. 2 is an X-ray diffraction (XRD) pattern of the microwave dielectric ceramic material of example 1.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention clearer, the present invention will be further described in detail with reference to examples. It should be understood that the examples described in this specification are for the purpose of illustrating the invention only and are not intended to limit the invention.
For simplicity, only a few numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
In the description herein, unless otherwise indicated, "above" and "below" are intended to include the present number, "one or more" means two or more, and "one or more" means two or more.
The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. The following description more particularly exemplifies illustrative embodiments. Guidance is provided throughout this application by a series of embodiments, which may be used in various combinations. In various embodiments, the list is merely a representative group and should not be construed as exhaustive.
Microwave dielectric ceramic material
The embodiment of the first aspect of the invention provides a microwave dielectric ceramic material, which comprises the following components in percentage by mass: 33 to 38 percent of CaO,12 to 14 percent of MgO,2 to 3 percent of ZnO and 24 to 43 percent of SiO 2 And 3-28% GeO 2 The dielectric constant of the microwave dielectric ceramic is 7.8-8.2; q×f is 137000 ～ 200000GHz; the temperature coefficient of resonance frequency is-53 to-75 ppm/DEG C.
According to embodiments of the present application, in CaMgSi 2 O 6 2-3% ZnO is doped in the ceramic material to form solid solution, so that the sintering temperature of the ceramic material is reduced by 50-150 ℃, and the Q multiplied by f value of the ceramic material is improved; if more than 3% ZnO is doped, a second phase is generated, leadingThe Q x f value of the ceramic material is reduced, and the loss of the material is increased. In CaMgSi doped with 2-3% ZnO 2 O 6 GeO 3-28% doped in the ceramic 2 Solid solution can be formed, the intrinsic loss of the ceramic material is reduced, and the Q multiplied by f value of the ceramic material is further improved; if doped with more than 28% GeO 2 A second phase is generated, resulting in a decrease in the q×f value of the ceramic material, increasing the loss of the material.
To comprehensively improve CaMgSi 2 O 6 The Q multiplied by f value of the system microwave dielectric ceramic material is 33-38% of CaO, for example, 33%, 34%, 36%, 37% or 38% of CaO, etc.
To comprehensively improve CaMgSi 2 O 6 The Q multiplied by f value of the system microwave dielectric ceramic material is selected to be 12-14% by mass of MgO, for example, 12%, 13% or 14% by mass.
To comprehensively improve CaMgSi 2 O 6 Q×f value, siO of system microwave dielectric ceramic material 2 The mass percentage of (2) is selected to be 24-43%, for example, 24%, 25%, 28%, 30%, 32%, 35%, 38%, 40% or 43%.
To comprehensively improve CaMgSi 2 O 6 The Q multiplied by f value of the system microwave dielectric ceramic material is 2-3% by mass of ZnO, for example, 2%, 3% or 4% by mass.
To comprehensively improve CaMgSi 2 O 6 Q×f value, geO of system microwave dielectric ceramic material 2 The mass percentage of (3) to (28) is selected, for example, 3%, 5%, 10%, 15%, 20%, 25%, 26% or 28%.
The Zn for the microwave dielectric ceramic material provided by the invention 2+ Partially replace CaMgSi 2 O 6 Mg of (B) 2+ Forming CaMg 1-x Zn x Si 2 O 6 Solid solution with Zn 2+ The content is increased, the ceramic density is improved, and the porosity is reduced, so that the microwave dielectric property of the ceramic material is directly improved; in addition, in the case of the optical fiber,by Ge 4+ Ion fraction replaces CaMg 1-x Zn x Si 2 O 6 Si of (C) 4+ The total ion polarization rate of the ceramic system is increased, the intrinsic loss of the ceramic material is reduced, the dielectric constant of the ceramic material is changed to 7.8-8.2, and the Q multiplied by f value is 137000 ～ 200000GHz.
Preparation method of microwave dielectric ceramic material
An embodiment of the second aspect of the present invention provides a method for preparing a microwave dielectric ceramic material, including the steps of:
(1) Weighing raw material powder according to the proportion, and performing ball milling for the first time to obtain a mixture;
(2) Carrying out primary drying, sieving and presintering treatment on the mixture to obtain presintering material;
(3) Performing secondary ball milling, secondary drying, granulation and dry pressing forming treatment on the presintered material to obtain a green body;
(4) And sintering the green body to obtain the microwave dielectric ceramic material.
In an embodiment of the present application, the raw material powder in step (1) includes calcium carbonate, magnesium oxide, zinc oxide, silicon dioxide, and germanium dioxide powder. The raw material powder can be uniformly mixed by the first ball milling.
In the embodiment of the present application, the rotational speed of the first ball milling in the step (1) is 250 to 350 rpm, and the time is 4 to 8 hours. The first ball milling may be planetary ball milling, for example, the rotational speed may be 250 rpm, 280 rpm, 300 rpm, 320 rpm, or 350 rpm.
The ball milling medium for the first ball milling is alcohol, and the ball-material ratio is (8-12): 1. For example, the ball to material ratio may be 8:1, 9:1, 10:1, 11:1, or 12:1.
In the ball milling process, the impact force generated when the zirconium balls do centrifugal motion and the friction force between the zirconium balls and the inner wall of the ball milling tank are utilized to crush the raw materials to achieve the effect of refining the raw materials, alcohol is added as a ball milling medium, and the mixture is obtained after ball milling.
In some embodiments, the mixture is pre-fired after drying and sieving at 1050-1150 ℃ for 4-8 hours. For example, the burn-in temperature may be 1050 ℃, 1080 ℃, 1100 ℃, 1120 ℃, or 1150 ℃; the burn-in time may be 4 hours, 5 hours, 6 hours, 7 hours, or 8 hours.
A series of physicochemical reactions occur in the presintering process to synthesize the required crystal forms and phases, the presintering can also remove internal stress in the mixture to cause volume shrinkage, and part of impurities can be removed at high temperature, so that the purity of the mixture is improved.
According to the embodiment of the application, after the presintering, the presintering material is subjected to a second ball milling (which can be planetary ball milling), so that the particle size of the presintering material is further reduced, and the particle distribution is more uniform.
According to the embodiment of the application, the pre-sintered material after the second ball milling is dried and granulated, and the fluidity of the material can be improved after granulation, so that the subsequent dry pressing forming is facilitated.
In an embodiment of the present application, the granulating in step (3) includes adding an adhesive to the dried pre-sintered material after the second drying and mixing to form the dried pre-sintered material into particles having an average particle size of 0.1 to 0.5 mm.
In some embodiments, the adhesive may be selected from an aqueous solution of polyvinyl alcohol at a concentration of 5wt%.
In the embodiment of the present application, the dry-pressing molding pressure in the step (3) is 100 to 200 mpa, and the pressure applying manner is axial pressure. For example, the pressure may be 100 megapascals, 120 megapascals, 150 megapascals, 180 megapascals, or 200 megapascals. After the dry press molding under the above pressure, the pre-sintered particles become compact green bodies.
In some embodiments, the dry press forming process is followed by a de-sizing process for the purpose of removing the added binder during the granulation process. The glue discharging temperature is 550-650 ℃ and the time is 4-8 hours. For example, the temperature of the adhesive discharge is 550 ℃, 580 ℃, 600 ℃, 620 ℃ or 650 ℃; the glue discharge time can be 4 hours, 5 hours, 6 hours, 7 hours or 8 hours.
In the examples of the present application, the green body is sintered at 1150 to 1250 ℃ for 4 to 8 hours. For example, the temperature of the sintering process may be 1150 ℃, 1180 ℃, 1200 ℃, 1220 ℃, or 1250 ℃; the sintering treatment time may be 4 hours, 5 hours, 6 hours, 7 hours or 8 hours. In the sintering process, the grains fully grow, the size of the air holes is reduced, the porosity is reduced, the volume is shrunk, and the compactness is improved.
Examples
Example 1
(1) According to mass fraction of 37 percent CaO, 14 percent MgO, 3 percent ZnO and 42 percent SiO 2 And 3% GeO 2 Weighing calcium carbonate, magnesium oxide, zinc oxide, silicon dioxide and germanium dioxide, adding alcohol with proper content, and performing planetary ball milling for 4 hours;
(2) Drying the slurry, sieving, and presintering for 4 hours at 1100 ℃;
(3) The obtained powder is ball-milled for 4 hours, dried and sieved, added with a proper amount of polyvinyl alcohol aqueous solution (PVA), ground and granulated, and formed by dry pressing.
(4) Finally, the green body is subjected to glue discharging for 4 hours at 600 ℃, and then sintered for 4 hours at 1200 ℃ to obtain the ceramic material with the required chemical component proportion.
As shown in FIG. 1, the SEM surface morphology of the ceramic shows that the density of the ceramic is higher, the pores are fewer, and the volume density is 3.4g/cm 3 The average grain size was 1.5. Mu.m. The XRD spectrum of the ceramic is shown in FIG. 2, where the ceramic has no distinct second phase present. The dielectric constant was 7.8, Q.times.f. value was 200000GHz, and temperature coefficient of resonance frequency was-53 ppm/. Degree.C.
Example 2
(1) According to mass fraction of 37 percent CaO, 13 percent MgO, 3 percent ZnO and 39 percent SiO 2 And 8% GeO 2 Weighing calcium carbonate, magnesium oxide, zinc oxide, silicon dioxide and germanium dioxide, adding alcohol with proper content, and performing planetary ball milling for 4 hours;
(2) Drying the slurry, sieving, and presintering for 4 hours at 1100 ℃;
(3) The obtained powder is ball-milled for 4 hours, dried and sieved, added with a proper amount of polyvinyl alcohol aqueous solution (PVA), ground and granulated, and formed by dry pressing.
(4) Finally, the green body is subjected to glue discharging for 4 hours at 600 ℃, and then sintered for 4 hours at 1200 ℃ to obtain the ceramic material with the required chemical component proportion.
The bulk density of the ceramic was 3.4g/cm 3 . The dielectric constant was measured to be 7.9 by a network analyzer, the Q.times.f value was 167600GHz, and the temperature coefficient of the resonance frequency was-55 ppm/. Degree.C.
Example 3
(1) According to mass fraction of 36% CaO, 13% MgO, 2% ZnO and 36% SiO 2 And 13% GeO 2 Weighing calcium carbonate, magnesium oxide, zinc oxide, silicon dioxide and germanium dioxide, adding alcohol with proper content, and performing planetary ball milling for 4 hours;
(2) Drying the slurry, sieving, and presintering for 4 hours at 1100 ℃;
(3) The obtained powder is ball-milled for 4 hours, dried and sieved, added with a proper amount of polyvinyl alcohol aqueous solution (PVA), ground and granulated, and formed by dry pressing.
(4) Finally, the green body is subjected to glue discharging for 4 hours at 600 ℃, and then sintered for 4 hours at 1200 ℃ to obtain the ceramic material with the required chemical component proportion.
The bulk density of the ceramic was 3.5g/cm 3 . The dielectric constant was 8.0, Q.times.f.value was 137000GHz, and the temperature coefficient of resonance frequency was-58 ppm/. Degree.C.
Example 4
(1) According to mass fraction of 33% CaO, 12% MgO, 2% ZnO and 24% SiO 2 And 28% GeO 2 Weighing calcium carbonate, magnesium oxide, zinc oxide, silicon dioxide and germanium dioxide, adding alcohol with proper content, and performing planetary ball milling for 4 hours;
(2) Drying the slurry, sieving, and presintering for 4 hours at 1100 ℃;
(3) The obtained powder is ball-milled for 4 hours, dried and sieved, added with a proper amount of polyvinyl alcohol aqueous solution (PVA), ground and granulated, and formed by dry pressing.
(4) Finally, the green body is subjected to glue discharging for 4 hours at 600 ℃, and then sintered for 4 hours at 1200 ℃ to obtain the ceramic material with the required chemical component proportion.
The bulk density of the ceramic was 3.5g/cm 3 . The dielectric constant was measured by a network analyzer to be 8.2, Q.times.f.value was 173000GHz, and the temperature coefficient of resonance frequency was-75 ppm/. Degree.C.
Comparative example
Comparative example 1
(1) According to mass fraction of 38 percent CaO, 14 percent MgO, 3 percent ZnO and 45 percent SiO 2 Weighing calcium carbonate, magnesium oxide, zinc oxide and silicon dioxide, adding alcohol with proper content, and performing planetary ball milling for 4 hours;
(2) Drying the slurry, sieving, and presintering for 4 hours at 1100 ℃;
(3) The obtained powder is ball-milled for 4 hours, dried and sieved, added with a proper amount of polyvinyl alcohol aqueous solution (PVA), ground and granulated, and formed by dry pressing.
(4) Finally, the green body is subjected to glue discharging for 4 hours at 600 ℃, and then sintered for 4 hours at 1200 ℃ to obtain the ceramic material with the required chemical component proportion.
Comparative example 1 doped with ZnO alone and undoped GeO 2 The preparation procedure is exactly the same as in the examples. The bulk density of the ceramic in comparative example 1 was 3.3g/cm 3 . The dielectric constant was measured to be 7.8 by a network analyzer, the Q.times.f value was 117100GHz, and the temperature coefficient of the resonance frequency was-54 ppm/. Degree.C.
The results show that the Q×f value of comparative example 1 is significantly lower than that of the examples, and the dielectric constant is comparable to the resonance frequency of the examples. It can be seen that the Ge doping 4+ The Q multiplied by f value of the ceramic material can be obviously improved, namely the loss of the ceramic material is reduced, and the influence on the dielectric constant and the temperature coefficient of the resonant frequency is small.
While the invention has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions of equivalents may be made and equivalents will be apparent to those skilled in the art without departing from the scope of the invention. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. The microwave dielectric ceramic material is characterized by comprising the following components in percentage by mass: 33-38% of CaO, 12-14% of MgO, 2-3% of ZnO, 24-43% of SiO2 and 3-28% of GeO2, wherein the dielectric constant of the microwave dielectric ceramic is 7.8-8.2; q×f is 137000 ～ 200000GHz; the temperature coefficient of resonance frequency is-53 to-75 ppm/DEG C.
2. A method for preparing the microwave dielectric ceramic material according to claim 1, comprising the steps of:
(1) Weighing raw material powder according to the proportion, and performing ball milling for the first time to obtain a mixture;
(2) Carrying out primary drying, sieving and presintering treatment on the mixture to obtain presintering material;
(3) Performing secondary ball milling, secondary drying, granulation and dry pressing forming treatment on the presintered material to obtain a green body;
(4) And sintering the green body to obtain the microwave dielectric ceramic material.
3. The method of producing a microwave dielectric ceramic material according to claim 2, wherein the raw material powder in step (1) comprises calcium carbonate, magnesium oxide, zinc oxide, silica, and germanium dioxide powder.
4. The method for preparing a microwave dielectric ceramic material according to claim 2, wherein the rotational speed of the first ball milling in the step (1) is 250-350 rpm for 4-8 hours.
5. The method for preparing the microwave dielectric ceramic material according to claim 2, wherein the ball milling medium for the first ball milling in the step (1) is alcohol, and the ball-to-material ratio is (8-12): 1.
6. The method for preparing a microwave dielectric ceramic material according to claim 2, wherein the pre-sintering treatment in step (2) is performed at 1050-1150 ℃ for 4-8 hours.
7. The method of preparing a microwave dielectric ceramic material according to claim 2, wherein the granulating in step (3) comprises adding an adhesive to the dried pre-sintered material after the second drying and mixing to prepare the dried pre-sintered material into particles having an average particle size of 0.1 to 0.5 mm.
8. The method for preparing a microwave dielectric ceramic material according to claim 2, wherein the dry press molding pressure in the step (3) is 100 to 200 mpa.
9. The method for preparing a microwave dielectric ceramic material according to claim 2, wherein the dry pressing molding treatment in the step (3) further comprises a glue discharging treatment, wherein the glue discharging temperature is 550-650 ℃ and the time is 4-8 hours.
10. The method for preparing a microwave dielectric ceramic material according to claim 2, wherein the sintering treatment temperature in the step (4) is 1150-1250 ℃ for 4-8 hours.
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