Resonant frequency temperature coefficient regulating agent, dielectric ceramic material and preparation method and application of dielectric ceramic material

Abstract

The invention belongs to the technical field of electronic information functional ceramic materials, and particularly relates to a resonant frequency temperature coefficient regulating agent, a dielectric ceramic material and a preparation method and application of the dielectric ceramic material. The resonance temperature coefficient regulating agent is characterized in that the chemical formula of the resonance temperature coefficient regulating agent is CaY (2-x) SmxGe3O10, and x is more than or equal to 0 and less than or equal to 2. The regulating and controlling range of the temperature coefficient of resonance frequency of the regulating and controlling agent is-5 to-250 ppm / DEG C, the quality factor Q * f is greater than or equal to 40000 GHz, and the dielectric constant is less than or equal to 10.5. The microwave dielectric ceramic prepared by the method can well meet the increasingly stringent requirements of the current technical field of mobile communication on the temperature stability of materials, has a relatively high quality factor and a relatively low dielectric constant, has a large-range adjustable temperature coefficient of resonance frequency, can be used as a regulating agent of microwave dielectric ceramic with a positive temperature coefficient of resonance frequency, and has a wide application prospect. Therefore, the high-frequency, integrated and diversified application requirements of the device are met.

Description

Technical Field

[0001] The present invention belongs to the technical field of electronic information functional ceramic materials, and particularly relates to a resonance frequency temperature coefficient regulator, a dielectric ceramic material, a preparation method thereof, and an application thereof. Background Art

[0002] Microwave dielectric ceramics refer to ceramic materials used as dielectrics in microwave frequency band (300 MHz - 300 GHz) circuits. With the continuous development of communication technologies, the applied microwave frequency band is continuously increasing. The development of the Internet of Things requires higher signal transmission quality and faster signal transmission rate. Low relative permittivity dielectric materials can significantly improve the signal transmission rate and quality, and reduce the heat loss generated during the operation of devices in the high-frequency band.

[0003] To meet the increasing demands of various wireless communication devices for high-frequency, integration, and miniaturization, the resonance frequency temperature needs to be nearly zero. However, currently, some microwave dielectric ceramics have a positive resonance frequency temperature coefficient, and a regulator with a large negative resonance frequency temperature coefficient is required to regulate it to nearly zero. This regulator should simultaneously have the advantages of low permittivity, ultra-low loss, a large negative value of the resonance frequency temperature coefficient, and adjustable characteristics, so as to meet the requirement that the resonance frequency temperature coefficient of microwave dielectric ceramics with a positive resonance frequency temperature coefficient can be nearly zero after doping with a small amount of the regulator.

[0004] In summary, it is necessary to develop a low-permittivity dielectric ceramic material with an adjustable resonance frequency temperature coefficient, which has the excellent properties of low permittivity, ultra-low loss, and a wide range of adjustable resonance frequency temperature coefficients, so as to be used as a regulator for microwave dielectric ceramics with a positive resonance frequency temperature coefficient. Summary of the Invention

[0005] The purpose of the present invention is to provide a resonance frequency temperature coefficient regulator, a dielectric ceramic material, a preparation method thereof, and an application thereof. This regulator has the characteristics of low permittivity, high quality factor, and a wide range of adjustable resonance frequency temperature coefficients, providing a new regulator for microwave dielectric ceramics with a positive resonance frequency temperature coefficient, and has a wide application range.

[0006] To achieve the above purpose, the present invention provides a resonance temperature coefficient regulator, whose chemical formula is CaY 2-x Sm x Ge3O 10 , 0 ≤ x ≤ 2.

[0007] Furthermore, the regulation range of the resonance frequency temperature coefficient of the regulator is -5 to -250 ppm / °C, the quality factor Q×f ≥ 40000 GHz, and the permittivity ≤ 10.5.

[0008] A preparation method of the above-mentioned resonance temperature coefficient regulator, comprising the following steps:

[0009] S1. Weigh raw materials according to the stoichiometric ratio of the chemical formula CaY 2-x Sm x Ge3O 10 to prepare a mixed powder;

[0010] S2. Wet ball-mill the mixed powder, dry it and then carry out temperature-raising sintering to obtain a pre-sintered powder;

[0011] S3. Carry out secondary wet ball-milling on the pre-sintered powder, dry it and then carry out temperature-raising sintering again to obtain the regulator.

[0012] Further, in step S1, the raw material of Ca in CaY 2-x Sm x Ge3O 10 is CaCO3, the raw material of Y is Y2O3, the raw material of Sm is Sm2O3, and the raw material of Ge is GeO2.

[0013] Further, in step S2, the dispersant used for the wet ball-milling is anhydrous ethanol, and the ball-milling medium is zirconia;

[0014] and / or, the mass ratio of the mixed powder, the ball-milling medium and the dispersant is 1:(4 - 8):(1 - 3);

[0015] and / or, the time of the wet ball-milling is 4 - 7 h.

[0016] Further, in step S2, the sintering temperature is 1150 - 1250 °C, and the sintering time is 4 - 6 h; the sintering temperature in step S3 is 1200 - 1400 °C, and the sintering time is 3 - 4 h.

[0017] Further, in step S3, the dispersant used for the secondary wet ball-milling is anhydrous ethanol, and the ball-milling medium is zirconia;

[0018] and / or, the mass ratio of the mixed powder, the ball-milling medium and the dispersant is 1:(4 - 8):(1 - 3);

[0019] and / or, the time of the wet ball-milling is 6 - 10 h.

[0020] The present invention also provides an application of the above-mentioned resonance temperature coefficient regulator in a microwave dielectric ceramic material.

[0021] Further, the resonance temperature coefficient of the microwave dielectric ceramic material is -1 - 1 ppm / °C.

[0022] Further, the microwave dielectric ceramic material is obtained by mixing and sintering ceramic raw materials with a positive resonance temperature coefficient and the resonance temperature coefficient regulator.

[0023] Generally speaking, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:

[0024] 1. The resonance temperature coefficient regulator provided by the present invention, through specific element composition design, the obtained ceramic material has the characteristics of low dielectric constant, high quality factor, and wide range of adjustable resonance frequency temperature coefficient, etc., and can well meet the increasingly stringent requirements of the current mobile communication technology field for material temperature stability, providing a brand-new regulator for microwave dielectric ceramics with a positive resonance frequency temperature coefficient, with a wide application range, and can meet the high-frequency, integrated, and diversified application requirements of devices.

[0025] 2. The resonance temperature coefficient regulator provided by the present invention, through two wet ball milling and sintering, the obtained ceramic material has a single-phase structure, which can reduce the energy loss caused by interface polarization and defects, thereby helping to reduce dielectric loss.

[0026] 3. The resonance frequency temperature coefficient of the resonance temperature coefficient regulator provided by the present invention is adjustable in the range of -5 to -250 ppm / °C, and can be applied to a variety of microwave dielectric ceramic materials with a positive resonance frequency temperature coefficient, and a composite microwave dielectric ceramic with a resonance frequency temperature coefficient closer to zero can be obtained by compounding, which helps to expand the application of such materials. Description of the Drawings

[0027] Figure 1 is the XRD pattern of CaY 2-x Sm x Ge3O 10 ceramics prepared in Examples 1 - 6.

[0028] Figure 2 is the lattice parameter of CaY 2-x Sm x Ge3O 10 ceramics prepared in Examples 1 - 6. Detailed Embodiments

[0029] In order to make the objectives, technical solutions and advantages of the present invention clearer, the following examples are used to further elaborate on the present invention. It should be understood that the specific examples described herein are only for explaining the present invention and are not used to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0030] A resonance temperature coefficient regulator, its chemical formula is CaY 2-x Smx Ge3O 10 , which is prepared from raw materials according to the molar ratio of CaCO3:(Y2O3 and / or Sm2O3):GeO2 = 1:1:3. The main material uses CaCO3, (Y2O3 and / or Sm2O3) and GeO2 as raw materials, and is formulated according to the chemical formula CaY 2-x Sm x Ge3O 10 in the ratio of

[0031] A preparation method of a resonance temperature coefficient regulator includes the following steps:

[0032] Step 1: Using CaCO3, (Y2O3 and / or Sm2O3) and GeO2 as raw materials, and weighing according to the chemical formula CaY 2-x Sm x Ge3O 10 in the ratio to obtain a powder;

[0033] Step 2: Mix the powder obtained in Step 1 evenly. Using anhydrous ethanol as a dispersant and zirconia balls as a ball milling medium, where the diameter of the zirconia balls is 3 - 15 mm, carry out wet ball milling according to the mass ratio of powder:zirconia balls:anhydrous ethanol = 1:6:1.5. The ball milling time is 4 - 7 h, the rotation speed is 250 r / min - 360 r / min. After taking out, dry at 80 - 120 °C. The dried powder is passed through an 80-mesh sieve and then heated from room temperature to 1150 - 1250 °C at a heating rate of 5 °C / min and kept warm for 4 - 6 h, and then cooled naturally to room temperature in the furnace to obtain CaY 2-x Sm x Ge3O 10 powder;

[0034] Step 3: Ball mill the powder obtained in Step 2 sufficiently. Using anhydrous ethanol as a dispersant and zirconia balls as a ball milling medium, where the diameter of the zirconia balls is 3 - 15 mm, carry out ball milling according to the mass ratio of powder:zirconia balls:anhydrous ethanol = 1:6:1.5. The ball milling time is 6 - 10 h, the ball milling rotation speed is 250 r / min - 360 r / min. After taking out, dry at 80 - 120 °C. The dried powder is passed through an 80-mesh sieve, put into a sintering furnace, degummed at 550 - 600 °C for 2 - 3 h in an air atmosphere, and then sintered at 1200 - 1400 °C for 3 - 4 h, and cooled to room temperature in the furnace to obtain the regulator.

[0035] When preparing a ceramic with a near-zero resonance frequency temperature coefficient as a regulator, it can be obtained by composite sintering with a ceramic material having a positive resonance frequency temperature coefficient.

[0036] Further, the sieved powder can be directly mixed with a binder, granulated, pressed into a green body, and sintered into a ceramic body. Specifically, the powder is granulated by adding 6-10 wt% of an organic binder, sieved through a 80-mesh sieve, pressed into a green body, and then the green body is placed in a sintering furnace. Debinding is carried out at 550-600 °C for 2-3 h in an air atmosphere, and then sintering is carried out at a temperature of 1200-1400 °C for 3-4 h. Cooling with the furnace to room temperature gives a low dielectric constant dielectric ceramic material with an adjustable temperature coefficient of resonant frequency.

[0037] Example 1

[0038] A preparation method of a low dielectric constant dielectric ceramic material with an adjustable temperature coefficient of resonant frequency includes the following steps:

[0039] (1) Using CaCO3, Y2O3, and GeO2 as raw materials, weighing the materials according to the proportion of the chemical formula CaY2Ge3O 10 to prepare a powder.

[0040] (2) Mix the powder obtained in step 1 evenly. Using anhydrous ethanol as a dispersant and zirconia balls as a ball-milling medium, where the diameter of the zirconia balls is 3-15 mm, carry out ball milling according to the mass ratio of powder:zirconia balls:anhydrous ethanol = 1:6:1.5. The ball-milling time is 6 h. After taking out, dry at 100 °C. After drying, the obtained powder is sieved through an 80-mesh sieve, and then heated from room temperature to 1150 °C at a heating rate of 5 °C / min and held for 5 h. Cooling naturally with the furnace to room temperature gives CaY2Ge3O 10 , the pre-sintered powder.

[0041] (3) Carry out secondary ball milling on the CaY2Ge3O 10 powder obtained in step 2. Using anhydrous ethanol as a dispersant and zirconia balls as a ball-milling medium, carry out ball milling according to the mass ratio of powder:zirconia balls:anhydrous ethanol = 1:6:1.5. The ball-milling time is 6 h, and the ball-milling speed is 360 r / min. After taking out, dry at 100 °C. After drying, the obtained powder is sieved through an 80-mesh sieve, then add 7 wt% of PVA for granulation, sieve through a 120-mesh sieve, and press into a cylindrical plastic green body with a diameter of 10-12 mm and a height of 5-6 mm. Then place the green body in a muffle furnace, carry out debinding at 550 °C for 2 h in an air atmosphere, and then sinter at 1300 °C for 3 h. Cooling with the furnace to room temperature gives the low dielectric constant dielectric ceramic material.

[0042] Use an X-ray diffractometer to obtain the phase structure information of the material; use the dielectric resonator method proposed by Hakki and Coleman to test the dielectric constant and microwave dielectric properties at the resonant frequency of the cylinder, and obtain them through a network analyzer.

[0043] Example 2

[0044] A preparation method of a low dielectric constant dielectric ceramic material with adjustable temperature coefficient of resonant frequency, comprising the following steps:

[0045] (1) Using CaCO3, Y2O3, Sm2O3 and GeO2 as raw materials, weighing according to the chemical formula CaY 1.6 Sm 0.4 Ge3O 10 proportion to prepare a powder;

[0046] (2) Mix the powder obtained in step 1 evenly, use anhydrous ethanol as a dispersant and zirconia balls as a ball-milling medium, where the diameter of the zirconia balls is 3 - 15 mm, carry out wet ball-milling according to the mass ratio of powder: zirconia balls: anhydrous ethanol = 1:6:1.5, the ball-milling time is 6 h, take it out and dry it at 100 °C, after drying, the obtained powder passes through an 80-mesh sieve and is heated from room temperature to 1150 °C at a heating rate of 5 °C / min and kept warm for 5 h, and then naturally cooled to room temperature in the furnace to obtain CaY 1.6 Sm 0.4 Ge3O 10 pre-sintered powder;

[0047] (3) Carry out secondary ball-milling on the CaY 1.6 Sm 0.4 Ge3O 10 powder obtained in step 2, use anhydrous ethanol as a dispersant and zirconia balls as a ball-milling medium, carry out ball-milling according to the mass ratio of powder: zirconia balls: anhydrous ethanol = 1:6:1.5, the ball-milling time is 6 h, the ball-milling speed is 360 r / min, take it out and dry it at 100 °C, after drying, the obtained powder passes through an 80-mesh sieve, then add 7 wt% of PVA for granulation, pass through a 120-mesh sieve and press it into a cylindrical plastic blank with a diameter of 10 - 12 mm and a height of 5 - 6 mm, then put the blank into a muffle furnace, carry out debinding at 550 °C for 2 h in an air atmosphere, and then sinter at 1300 °C for 3 h, and cool to room temperature in the furnace to obtain the low dielectric constant dielectric ceramic material.

[0048] Use an X-ray diffractometer to obtain the phase structure information of the material; use the dielectric resonator method proposed by Hakki and Coleman to test the dielectric constant and microwave dielectric properties at the resonant frequency of the cylinder, and obtain it through a network analyzer.

[0049] Example 3

[0050] A preparation method of a low dielectric constant dielectric ceramic material with adjustable temperature coefficient of resonant frequency, comprising the following steps:

[0051] (1) Using CaCO3, Y2O3, Sm2O3 and GeO2 as raw materials, weigh the materials according to the chemical formula CaY 1.2 Sm 0.8 Ge3O 10 to prepare a powder;

[0052] (2) Mix the powder obtained in step (1) evenly. Using anhydrous ethanol as a dispersant and zirconia balls as a ball-milling medium, where the diameter of the zirconia balls is 3 - 15 mm, carry out wet ball-milling according to the mass ratio of powder:zirconia balls:anhydrous ethanol = 1:6:1.5. The ball-milling time is 6 h. After taking it out, dry it at 100 °C. After drying, the obtained powder is sieved through an 80-mesh sieve and then heated from room temperature to 1150 °C at a heating rate of 5 °C / min and held for 5 h, and then cooled naturally to room temperature in the furnace to obtain the CaY 1.2 Sm 0.8 Ge3O 10 pre-sintered powder;

[0053] (3) Carry out secondary ball-milling on the CaY 1.2 Sm 0.8 Ge3O 10 powder obtained in step (2). Using anhydrous ethanol as a dispersant and zirconia balls as a ball-milling medium, carry out ball-milling according to the mass ratio of powder:zirconia balls:anhydrous ethanol = 1:6:1.5. The ball-milling time is 6 h, and the ball-milling speed is 360 r / min. After taking it out, dry it at 100 °C. After drying, the obtained powder is sieved through an 80-mesh sieve, then add 7 wt% of PVA for granulation, sieve through a 120-mesh sieve and press it into a cylindrical green body with a diameter of 10 - 12 mm and a height of 5 - 6 mm. Then put the green body into a muffle furnace, degrease at 550 °C for 2 h in an air atmosphere, and then sinter at 1275 °C for 3 h, and cool to room temperature in the furnace to obtain the low dielectric constant dielectric ceramic material.

[0054] Obtain the phase structure information of the material using an X-ray diffractometer; use the dielectric resonator method proposed by Hakki and Coleman to test the dielectric constant and microwave dielectric properties at the resonant frequency of the cylinder, which is obtained by testing with a network analyzer.

[0055] Example 4

[0056] A preparation method of a low dielectric constant dielectric ceramic material with adjustable temperature coefficient of resonant frequency, comprising the following steps:

[0057] (1) Using CaCO3, Y2O3, Sm2O3 and GeO2 as raw materials, weigh the materials according to the chemical formula CaY 0.8 Sm 1.2 Ge3O 10 to prepare a powder;

[0058] (2) Mix the powder obtained in step (1) evenly. Using absolute ethanol as the dispersant and zirconia balls with a diameter of 3 - 15 mm as the ball-milling medium, perform wet ball-milling according to the ratio of powder : zirconia balls : absolute ethanol = 1:6:1.5 by mass. The ball-milling time is 6 h. After taking it out, dry it at 100 °C. After drying, sieve the obtained powder through a 80-mesh sieve and then heat it from room temperature to 1150 °C at a heating rate of 5 °C / min and hold for 5 h, and then cool it to room temperature naturally in the furnace to obtain CaY 0.8 Sm 1.2 Ge3O 10 Pre-sintered powder;

[0059] (3) Perform secondary ball-milling on the CaY 0.8 Sm 1.2 Ge3O 10 powder obtained in step (2). Using absolute ethanol as the dispersant and zirconia balls as the ball-milling medium, perform ball-milling according to the ratio of powder : zirconia balls : absolute ethanol = 1:6:1.5 by mass. The ball-milling time is 6 h and the ball-milling speed is 360 r / min. After taking it out, dry it at 100 °C. After drying, sieve the obtained powder through an 80-mesh sieve, then add 7 wt% of PVA for granulation, sieve it through a 120-mesh sieve, and press it into a cylindrical green compact with a diameter of 10 - 12 mm and a height of 5 - 6 mm. Then put the green compact into a muffle furnace, degrease it at 550 °C for 2 h in an air atmosphere, and then sinter it at 1275 °C for 3 h, and cool it to room temperature in the furnace to obtain the low-dielectric-constant dielectric ceramic material.

[0060] Obtain the phase structure information of the material using an X-ray diffractometer; use the dielectric resonator method proposed by Hakki and Coleman to measure the dielectric constant and microwave dielectric properties at the resonant frequency of the cylinder, which is obtained by testing with a network analyzer.

[0061] Example 5

[0062] A preparation method of a low-dielectric-constant dielectric ceramic material with adjustable resonant frequency temperature coefficient, comprising the following steps:

[0063] (1) Using CaCO3, Y2O3, Sm2O3, and GeO2 as raw materials, weigh them according to the chemical formula CaY 0.4 Sm 1.2 Ge3O 10 ratio to prepare the powder;

[0064] (2) Mix the powder obtained in step (1) evenly. Using absolute ethanol as the dispersant and zirconia balls as the ball-milling medium, where the diameter of the zirconia balls is 3 - 15 mm, carry out wet ball-milling according to the mass ratio of powder:zirconia balls:absolute ethanol = 1:6:1.5. The ball-milling time is 6 h. After taking out, dry it at 100 °C. After drying, sieve the obtained powder through an 80-mesh sieve and then heat it from room temperature to 1150 °C at a heating rate of 5 °C / min and hold for 5 h, and then cool it naturally to room temperature in the furnace to obtain CaY 0.4 Sm 1.2 Ge3O 10 Pre-sintered powder;

[0065] (3) Carry out secondary ball-milling on the CaY 0.4 Sm 1.2 Ge3O 10 powder obtained in step (2). Using absolute ethanol as the dispersant and zirconia balls as the ball-milling medium, carry out ball-milling according to the mass ratio of powder:zirconia balls:absolute ethanol = 1:6:1.5. The ball-milling time is 6 h and the ball-milling speed is 360 r / min. After taking out, dry it at 100 °C. After drying, sieve the obtained powder through an 80-mesh sieve, then add 7 wt% of PVA for granulation, sieve through a 120-mesh sieve and press it into a cylindrical plastic blank with a diameter of 10 - 12 mm and a height of 5 - 6 mm. Then put the blank into a muffle furnace, degrease at 550 °C for 2 h in an air atmosphere, then heat it to 1250 °C and sinter for 3 h, and cool it to room temperature in the furnace to obtain the low-dielectric-constant dielectric ceramic material.

[0066] Use an X-ray diffractometer to obtain the phase structure information of the material; use the dielectric resonator method proposed by Hakki and Coleman to test the dielectric constant and microwave dielectric properties at the resonant frequency of the cylinder, which is obtained by testing with a network analyzer.

[0067] Example 6

[0068] A preparation method of a low-dielectric-constant dielectric ceramic material with adjustable resonant frequency temperature coefficient, comprising the following steps:

[0069] (1) Using CaCO3, Sm2O3 and GeO2 as raw materials, weigh the materials according to the chemical formula CaSm2Ge3O 10 proportion to prepare the powder;

[0070] (2) Mix the powder obtained in step 1 evenly. Use absolute ethanol as the dispersant and zirconia balls as the ball-milling medium, where the diameter of the zirconia balls is 3 - 15 mm. Carry out wet ball-milling according to the mass ratio of powder:zirconia balls:absolute ethanol = 1:6:1.5. The ball-milling time is 6 h. After taking out, dry it at 100 °C. The dried powder is sieved through a 80-mesh sieve and then heated from room temperature to 1150 °C at a heating rate of 5 °C / min and held for 5 h, and then cooled to room temperature naturally with the furnace to obtain CaSm2Ge3O 10 Pre-sintered powder;

[0071] (3) Carry out secondary ball-milling on the CaSm2Ge3O 10 powder. Use absolute ethanol as the dispersant and zirconia balls as the ball-milling medium. Carry out ball-milling according to the mass ratio of powder:zirconia balls:absolute ethanol = 1:6:1.5. The ball-milling time is 6 h, and the ball-milling speed is 360 r / min. After taking out, dry it at 100 °C. The dried powder is sieved through a 80-mesh sieve, then add 7 wt% of PVA for granulation, and after sieving through a 120-mesh sieve, press it into a cylindrical plastic blank with a diameter of 10 - 12 mm and a height of 5 - 6 mm. Then put the blank into a muffle furnace, degrease at 550 °C for 2 h in an air atmosphere, and then sinter at 1250 °C for 3 h, and cool to room temperature with the furnace to obtain the low dielectric constant dielectric ceramic material.

[0072] Use an X-ray diffractometer to obtain the phase structure information of the material; adopt the dielectric resonator method proposed by Hakki and Coleman to test the dielectric constant and microwave dielectric properties at the resonant frequency of the cylinder, which is obtained by testing with a network analyzer.

[0073] Comparative Example 1

[0074] A preparation method of a low dielectric constant dielectric ceramic material, comprising the following steps:

[0075] (1) Use BaCO3, Er2O3 and GeO2 as raw materials, weigh them according to the proportion of the chemical formula BaEr2Ge3O 10 to prepare the powder;

[0076] (2) Mix the powder obtained in step 1 evenly. Use absolute ethanol as the dispersant and zirconia balls as the ball-milling medium, where the diameter of the zirconia balls is 3 - 15 mm. Carry out wet ball-milling according to the mass ratio of powder:zirconia balls:absolute ethanol = 1:6:1.5. The ball-milling time is 6 h. After taking out, dry it at 100 °C. The dried powder is sieved through a 80-mesh sieve and then heated from room temperature to 1250 °C at a heating rate of 5 °C / min and held for 5 h, and then cooled to room temperature naturally with the furnace to obtain BaEr2Ge3O 10 Pre-sintered powder;

[0077] (3) Subject the BaEr2Ge3O powder obtained in step 2 10 to secondary ball milling. Using absolute ethanol as the dispersant and zirconia balls as the ball milling medium, conduct ball milling according to the ratio of powder: zirconia balls: absolute ethanol = 1:6:1.5 by mass. The ball milling time is 6 h, the ball milling speed is 360 r / min. After taking out, dry it at 100 °C. Pass the dried powder through an 80-mesh sieve, then add 7 wt% of PVA for granulation. After passing through a 120-mesh sieve, press it into a cylindrical plastic blank with a diameter of 10 - 12 mm and a height of 5 - 6 mm. Then put the blank into a muffle furnace, degrease at 550 °C for 2 h in an air atmosphere, and then sinter at 1375 °C for 3 h. Cool it down to room temperature with the furnace to obtain the low dielectric constant dielectric ceramic material. The secondary heating temperatures in the above experimental examples are all the optimal sintering temperatures under this material condition.

[0078] Use an X-ray diffractometer to obtain the phase structure information of the material; adopt the dielectric resonator method proposed by Hakki and Coleman to test the dielectric constant and microwave dielectric properties at the resonant frequency of the cylinder, which is obtained by testing with a network analyzer.

[0079] Table 1 Performance test results of Examples 1 - 6 and Comparative Example 1

[0080]

[0081]

[0082] As can be seen from Table 1, under the element composition conditions defined in the present invention, the quality factor Q×f of the obtained ceramic materials is all above 40000 GHz, the dielectric constant is below 10.5, and by adjusting the content of each element, ceramic materials with different temperature coefficients of resonant frequency can be obtained, and the variation range is -5 to -250 ppm / °C. Therefore, it is convenient to be compounded with microwave dielectric ceramic materials with a positive temperature coefficient of resonant frequency to obtain microwave dielectric ceramics with a nearly zero temperature coefficient of resonant frequency. When the element composition of Comparative Example 1 changes, its quality factor decreases significantly and the dielectric loss increases, which is not conducive to the stable application of electronic communication devices.

[0083] From Figure 1 and 2 it can be seen that the dielectric ceramics prepared in the present invention are all single-phase structures, which can reduce the energy loss caused by interface polarization and defects, thereby reducing the dielectric loss.

[0084] It is easy for those skilled in the art to understand that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A resonant temperature coefficient regulator, characterized in that, Its chemical formula is CaY 2-x Sm x Ge3O 10 , 0 ≤ x ≤ 2 2. The resonance temperature coefficient regulator according to claim 1, wherein The regulation range of the temperature coefficient of the resonance frequency of the regulator is -5 to -250 ppm / °C, the quality factor Q×f ≥ 40000 GHz, and the dielectric constant ≤ 10.

5.

3. A preparation method of the resonance temperature coefficient regulator according to claim 1 or 2, characterized in that, It includes the following steps: S1. Weigh the raw materials according to the stoichiometric ratio of CaY 2-x Sm x Ge3O 10 to prepare a mixed powder S2. Wet ball-mill the mixed powder, dry it, and then sinter it by heating to obtain a pre-sintered powder. S3. Perform secondary wet ball-milling on the pre-sintered powder, dry it, and then sinter it by heating again to obtain the regulator.

4. The preparation method of the resonance temperature coefficient regulator according to claim 3, characterized in that, In step S1, the CaY 2-x Sm x Ge3O 10 The raw material of Ca is CaCO3, the raw material of Y is Y2O3, the raw material of Sm is Sm2O3, and the raw material of Ge is GeO2.

5. The preparation method of the resonance temperature coefficient regulator according to claim 3, characterized in that, In step S2, the dispersant used in the wet ball-milling is anhydrous ethanol, and the ball-milling medium is zirconia. And / or, the mass ratio of the mixed powder, the ball-milling medium, and the dispersant is 1:(4 - 8):(1 - 3). And / or, the time of the wet ball-milling is 4 to 7 h.

6. The preparation method of the resonant temperature coefficient regulator according to claim 3, wherein In step S2, the sintering temperature is 1150 to 1250 °C, and the sintering time is 4 to 6 h; in step S3, the sintering temperature is 1200 to 1400 °C, and the sintering time is 3 to 4 h.

7. The preparation method of the resonance temperature coefficient regulator according to claim 3, characterized in that, In step S3, the dispersant used in the secondary wet ball-milling is anhydrous ethanol, and the ball-milling medium is zirconia. And / or, the mass ratio of the mixed powder, the ball-milling medium, and the dispersant is 1:(4 - 8):(1 - 3). And / or, the time of the wet ball-milling is 6 to 10 h.

8. The application of a resonance temperature coefficient regulator as claimed in claim 1 or 2 in a microwave dielectric ceramic material.

9. The application according to claim 8, characterized in that, The resonance temperature coefficient of the microwave dielectric ceramic material is -1 to 1 ppm / °C.

10. The application according to claim 8, characterized in that The microwave dielectric ceramic material is obtained by mixing and sintering a ceramic raw material with a positive resonance temperature coefficient and the resonance temperature coefficient regulator.

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