CN114804867B - Ceramic dielectric material suitable for hot-pressing sintering, ceramic device and preparation method thereof - Google Patents
Ceramic dielectric material suitable for hot-pressing sintering, ceramic device and preparation method thereof Download PDFInfo
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Abstract
The invention provides a ceramic dielectric material suitable for hot-pressing sintering and a preparation method thereof, and relates to the technical field of ceramic materials. The ceramic material comprises 98.5-99.5% of main material and 0.5-1.5% of modified additive, wherein the main material comprises 90-93% of material A and 7-10% of material B by mass ratio, and the chemical formula of A is Ba 3 Mg x Co 1‑x Nb 2 O 9 ，0.4<x<0.75, B has the formula Zn 0.8 Mg 0.2 Nb 2 O 6 . In the preparation method of the material, the material A and the material B which are synthesized in advance are ground and mixed, and the obtained main material is presintered again, so that the original structure of the material can be effectively ensured, the two materials are presintered again at a relatively low temperature and are presintered in advance, and the generation of impurities and increase of cavities caused by high temperature can be avoided. The ceramic dielectric material provided by the invention can be sintered into ceramic at 1450-1550 ℃ under the pressure environment of 1-3Mpa, the dielectric constant of the ceramic dielectric material at room temperature is 32-36, the Qf value is more than or equal to 100000, and the temperature coefficient tau f (-40-110 ℃) of: +/-5 ppm/DEG C, excellent performance and capability of meeting the performance requirement of a microwave device.
Description
Technical Field
The invention relates to the field of ceramic materials, in particular to a microwave dielectric ceramic material with a medium dielectric constant and a high Qf and a preparation method thereof.
Background
The microwave dielectric ceramic material is a novel functional ceramic material which is rapidly developed in recent years and has low microwave loss, high dielectric constant and dielectric constant temperature coefficient tau f Stable and the like. The dielectric material is used as a dielectric material in a microwave frequency band circuit, is a core basic material of a novel microwave circuit and a device including a dielectric resonator, a filter, an oscillator, a duplexer, an antenna, a dielectric substrate and the like, and is widely applied to modern microwave communication and satellite navigation systems and equipment.
The dielectric resonator has resonance property when working in narrow frequency band, is an electromagnetic element, generally consists of ceramic cylinders with proper dielectric constant and low loss, and has the advantages of small size, low loss, stable device and the like compared with the traditional metal waveguide resonator. Existing dielectricsMedium constant dielectric ceramic material, mainly Sr/CaTiO 3 -La/Sm/NdAlO 3 The system is mainly characterized in that the sintering temperature is too high or the Q value is not high, so that the application of the system is limited, the quality factor Qf can only reach about 80000GHz usually, and the requirement of a high frequency band on the Q value is difficult to meet.
Disclosure of Invention
The invention aims to provide a high-quality-factor ceramic dielectric material suitable for hot-pressing sintering, which has the advantages of low dielectric loss, high quality factor and temperature coefficient approaching zero.
The invention also aims to provide a preparation method of the high-quality-factor ceramic dielectric material suitable for hot-pressing sintering, which is simple, easy to operate and suitable for stable production.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
A ceramic dielectric material suitable for hot-pressing sintering comprises a main material with the mass fraction of 98.5-99.5% and a modified additive with the mass fraction of 0.5-1.5%; the main material consists of a material A accounting for 90-93% by mass and a material B accounting for 7-10% by mass, wherein the chemical formula of A is Ba 3 Mg x Co 1-x Nb 2 O 9 ，0.4<x<0.75, B has the formula Zn 0.8 Mg 0.2 Nb 2 O 6 。
As an improvement of the ceramic dielectric material suitable for hot-pressing sintering, the modifying additive is selected from SnO 2 、SrCO 3 、MnCO 3 、Y 2 O 3 、CeO 2 And ZrO 2 One or more of (a).
As an improvement of the ceramic dielectric material suitable for hot-press sintering, in terms of mass fraction, the mass fraction of each component in the microwave dielectric ceramic material in the modified additive is as follows: snO 2 0～1％、SrCO 3 0～1％、MnCO 3 0～1％、Y 2 O 3 0～0.2％、CeO 2 0～0.3％，ZrO 2 0～0.3％。
The invention also provides a preparation method of the ceramic dielectric material suitable for hot-pressing sintering, which comprises the following steps: and mixing the main material and the modified additive, adding water, and performing wet ball milling to obtain the ceramic dielectric material in a powder state.
As an improvement of the preparation method of the ceramic dielectric material suitable for hot press sintering, the main material comprises the material A and the material B; the material A is BaCO 3 、MgO、Co 2 O 3 And Nb 2 O 5 Mixing, ball milling, drying, and presintering at 1050-1150 deg.c for 2-4 hr.
As an improvement of the preparation method of the ceramic dielectric material suitable for hot-pressing sintering, the material B is prepared by mixing ZnO, mgO and Nb 2 O 5 Weighing according to a molar ratio of 0.8.
As an improvement of the preparation method of the ceramic dielectric material suitable for hot-pressing sintering, the main material is obtained by mixing and grinding 90-93% of material A and 7-10% of material B by mass ratio, drying and then pre-sintering at 950-1050 ℃ for 0.5-3 h.
The invention also provides a preparation method of the ceramic device, which is to further carry out hot-pressing sintering on the ceramic dielectric material prepared by the preparation method of the ceramic dielectric material, and specifically comprises the following steps:
adding an auxiliary preparation into the ceramic dielectric material, wherein the auxiliary preparation can comprise an adhesive, a plasticizer and a dispersing agent, the adhesive can be modified polyvinyl alcohol, the plasticizer can be phthalic diester, and the dispersing agent can be a mixture of hard amide and higher alcohol; adding an auxiliary agent, performing ball milling and drying to obtain particles, performing compression molding on the particles, performing heat preservation at 500-700 ℃ for 24h for binder removal, then performing heat preservation at 1450-1550 ℃ under the atmosphere pressure of 1-3Mpa for 1-3 h for sintering, and annealing at 1150 ℃ to obtain the ceramic device.
As an improvement of the manufacturing method of the ceramic device, the sintering gas pressure is preferably 2MPa.
The invention finally provides a ceramic device which is prepared according to the preparation method of the ceramic device.
The ceramic dielectric material suitable for hot-pressing sintering, the ceramic device and the preparation method thereof have the beneficial effects that:
material Ba 3 Mg x Co 1-x Nb 2 O 9 ，0.4<x<0.75, a high dielectric constant of 37-41, and a positive temperature coefficient, but a low Qf value, material Zn 0.8 Mg 0.2 Nb 2 O 6 The dielectric constant of the material is about 20, the temperature coefficient is-60 ppm/DEG C, and the two materials with opposite temperature coefficients of resonance frequency are combined together to form a solid solution, so that the temperature coefficient close to zero can be obtained, and the required dielectric constant can be obtained. In the preparation method of the material, the material A and the material B which are synthesized in advance are ground and mixed, and the obtained main material is presintered again, so that the original structure of the material can be effectively ensured, the problem of abnormal shape of the material structure caused by segregation components is solved, the material A and the material B are presintered again at a relatively low temperature and are presintered in advance, the generation of impurities and increase of holes caused by high temperature can be avoided, the uniformity of the main material can be effectively ensured by mixing and grinding again, and the obtained main material has the advantages of low dielectric loss and continuously adjustable dielectric constant. The properties of the microwave dielectric ceramic material can be further improved by optimizing the selection and the proportion of the modified additives, including the Qf value of the microwave dielectric material. In the preparation method of the ceramic device, 1-3Mpa hot pressing condition sintering is adopted to ensure the uniformity of the environmental atmosphere and ensure the high Qf value and the low temperature coefficient which are more than 100000 GHz. The invention successfully uses a solid-phase synthesis mechanism of two-phase pre-compounding and oriented post-doping modes to prepare the ceramic dielectric material with good uniformity and meets the requirement of high-performance ceramic dielectric materials.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The embodiment of the invention provides a ceramic dielectric material with high quality factor suitable for hot pressing sintering and a preparation method thereof.
A ceramic dielectric material suitable for hot-pressing sintering comprises 98.5-99.5% of main material and 0.5-1.5% of modified additive by mass fraction; the main material consists of a material A accounting for 90-93% by mass and a material B accounting for 7-10% by mass, wherein the chemical formula of A is Ba 3 Mg x Co 1-x Nb 2 O 9 ，0.4<x<0.75, B has the formula Zn 0.8 Mg 0.2 Nb 2 O 6 。
Material Ba 3 Mg x Co 1-x Nb 2 O 9 ，0.4<x<0.75, a high dielectric constant of 37-41 and a positive temperature coefficient, but a low Qf value, and Zn as a material 0.8 Mg 0.2 Nb 2 O 6 The dielectric constant of the material is about 20, the temperature coefficient is-60 ppm/DEG C, and the two materials with opposite temperature coefficients of resonance frequency are combined together to form a solid solution, so that the temperature coefficient close to zero can be obtained, and the required dielectric constant can be obtained. Under the condition of the proportion of the main material and the modifying additive, the microwave dielectric ceramic material can be effectively modified, the obtained microwave dielectric ceramic material can be sintered into porcelain under the environment of 1450-1550 ℃ and 1-3Mpa pressure, and a microwave ceramic body with the dielectric constant of 32-36 and the quality factor Qf value of more than or equal to 100000GHz is obtained.
In a preferred embodiment, the modifying additive is selected from SnO 2 、SrCO 3 、MnCO 3 、Y 2 O 3 、CeO 2 And ZrO 2 One or more of (a).
In a preferred embodiment, the mass fractions of the components in the microwave dielectric ceramic material in the modifying additives are as follows: snO 2 0～1％、SrCO 3 0～1％、MnCO 3 0～1％、Y 2 O 3 0～0.2％、CeO 2 0～0.3％，ZrO 2 0 to 0.3 percent. The properties of the microwave dielectric ceramic material can be further improved by optimizing the selection and the proportion of the modifying additive, such as the Qf value of the microwave dielectric ceramic material.
The invention also provides a preparation method of the ceramic dielectric material suitable for hot-pressing sintering, which comprises the following steps:
s1, mixing compounds according to the molar ratio of each element in the material A, adding water, carrying out ball milling, drying, and calcining in an air atmosphere to obtain the material A. For example, the material A can be BaCO 3 、MgO、Co 2 O 3 And Nb 2 O 5 Mixing, ball milling, drying, and presintering at 1050-1150 deg.c for 2-4 hr.
And S2, mixing the compounds according to the molar ratio of each element in the material B, adding water, performing ball milling, drying, and calcining in an air atmosphere to obtain the material B. For example, znO, mgO, and Nb can be used as the material B 2 O 5 Weighing according to a molar ratio of 0.8.
S3, mixing the synthesized material A and B according to a mass ratio of 90-93%: 7 to 10 percent of the mixture is ground, dried and presintered for 0.5 to 3 hours at 950 to 1050 ℃ to obtain the main material. Further, in the step, after the components are mixed, water is added according to the mass ratio of the mixture to water of 1.2-1.5 for wet ball milling.
And S4, mixing the main material and the modified additive according to the mass ratio of 98.5-99.5 to 0.5, adding water according to the mass ratio of the material to the water of 1.5-1, carrying out wet ball milling, and optionally adding a modified polyvinyl alcohol binder and the like, and carrying out spray drying to obtain the powdery ceramic dielectric material.
In the preparation method of the material, the pre-synthesized material A and the pre-synthesized material B are ground and mixed, and the obtained main material is pre-sintered again, so that the original structure of the material can be effectively ensured, the problem of abnormal shape of the material structure caused by segregation components is solved, the pre-sintering and the pre-compounding are carried out again at a relatively low temperature in advance, the generation of impurities and the increase of holes caused by high temperature can be avoided, the uniformity of the main material can be effectively ensured by mixing and grinding again, and the obtained main material has the advantages of low dielectric loss and continuously adjustable dielectric constant.
The invention also provides a preparation method of the ceramic device, which is to further perform hot-pressing sintering on the powdery ceramic dielectric material prepared by the preparation method of the ceramic dielectric material, and specifically comprises the following steps:
s5, adding an auxiliary agent into the powdery ceramic dielectric material, and performing ball milling to obtain slurry, wherein: the auxiliary agent comprises a binder, a plasticizer and a dispersant. The binder may be, for example, polyvinyl alcohol, the plasticizer may be, for example, polyethylene glycol, and the dispersant may be, for example, ammonium carboxylate-based dispersant.
And S6, drying the slurry to obtain spherical particles, and pressing the spherical particles into a green body.
And S7, performing glue discharging, hot-pressing sintering and annealing treatment on the green body to obtain the product.
Further, in step S7, the conditions for discharging the adhesive are as follows: and (3) preserving the heat for 24h at the temperature of 500-700 ℃, removing organic matters in the green body, wherein the temperature rise speed in the whole glue removing process is required to be less than 10 ℃/h.
Further, in this step S7, the hot press sintering conditions: keeping the temperature for 1 to 3 hours at 1450 to 1550 ℃ under the environment of 1 to 3 Mpa. In the preparation method of the ceramic device, 1-3Mpa hot pressing condition sintering is adopted to ensure the uniformity of the environmental atmosphere and ensure the high Qf value and the low temperature coefficient which are more than 100000 GHz. Among them, the sintering pressure is more preferably 2MPa.
Further, in step S7, the conditions of the annealing treatment: and preserving the heat for 0.5 to 1.5 hours at the temperature of 1100 to 1250 ℃ to obtain the ceramic device.
The invention successfully uses a solid-phase synthesis mechanism of two-phase pre-compounding and oriented post-doping modes to prepare the ceramic dielectric material with good uniformity, thereby meeting the requirements of high-performance ceramic dielectric materials.
The features and properties of the present invention are described in further detail below with reference to examples.
Examples
The ceramic dielectric material suitable for hot-pressing sintering and having a high quality factor is prepared according to the following steps:
(1) According to material A being Ba 3 Mg x Co 1-x Nb 2 O 9 ，0.4<x<0.75 stoichiometric ratio. Mixing BaCO 3 、MgO、Co 2 O 3 And Nb 2 O 5 The raw materials are uniformly mixed according to the mixture ratio shown in the following table 1, the mixture is placed in a ball mill, deionized water is added according to the mass ratio of 1.5 of the solid mixture to the deionized water for wet ball milling, spray drying is carried out after ball milling, and finally, the dried products of the three groups of formulas are calcined for 3 hours at temperatures of 1060 ℃, 1080 ℃ and 1120 ℃ respectively. Wherein in formulation A1, x =0.45, baCO is added 3 、MgO、Co 2 O 3 And Nb 2 O 5 3; in formulation A2, x =0.53, baCO added 3 、MgO、Co 2 O 3 And Nb 2 O 5 In a molar ratio of 3: 1; in formulation A3, x =0.72, baCO added 3 、MgO、Co 2 O 3 And Nb 2 O 5 3: 1.
TABLE 1 proportioning table of materials A
(2) According to the material B being Zn 0.8 Mg 0.2 Nb 2 O 6 The stoichiometric ratio of (A) to (B) of ZnO, mgO, nb 2 O 5 Accurately weighing according to a molar ratio of 0.8Spray drying, and calcining at 1210 deg.C for 2.5 hr in air furnace to obtain Zn as material B 0.8 Mg 0.2 Nb 2 O 6 。
(3) The material A and the material B are weighed according to the table 2, and are placed in a ball mill according to the mass ratio of the mixture (A + B) to the deionized water of 1.5 to be subjected to water-adding wet ball milling, the ball milling is uniform, the drying is carried out, and the calcining is carried out in an air furnace at the temperature of 1000 ℃ for 0.75 hour to obtain the main material.
TABLE 2 Main Material proportioning Table
(4) According to the composition proportion of the following table 3, a modification additive is added into the main material, and deionized water is added into the main material according to the mass ratio of the material to the deionized water of 1. Ball-milling until the average particle size of the powder reaches 300-600 nm to obtain the ceramic dielectric material in a powder state.
TABLE 3 ceramic dielectric material proportioning table
(5) And (4) adding a proper amount of adhesive, plasticizer and dispersant into the powder in the step (4), and carrying out ball milling for 2h in a ball milling tank by using alumina balls as ball milling media to obtain slurry. The slurry was subjected to centrifugal spray drying to obtain spherical particles having good fluidity.
(6) And (4) pressing the spherical particles obtained in the step (5) under the pressure of 5-10 MPa to form cylindrical green sheets with the size of 15 x 8mm.
(7) And (3) placing the green sheet at 600 ℃, preserving heat for 24h, removing organic matters in the green sheet, and requiring the temperature rise speed in the whole glue removing process to be less than 10 ℃/h.
(8) And (3) carrying out annealing treatment on the No. 1-9 blank subjected to glue discharging in the table 3 for 1-3 h at a heating rate of 150-300 ℃/h and under a hot-pressing environment of 1450-1550 ℃ and 2MPa for 1-3 h. And (3) keeping the temperature of the No. 10 blank after the glue discharging for 1 to 3 hours at 1450 to 1550 ℃ and normal pressure (about 0.1 MPa) at the heating rate of 150 to 300 ℃/h, and annealing for 1 hour at 1150 ℃.
For the samples obtained in the examples, an agilent network analyzer was used to test the performance by the parallel plate resonance method. The test results are shown in table 4. Samples 1 to 10 in Table 4 correspond one-to-one to samples No. 1 to 10 in Table 3.
Table 4 table of performance test results
As shown in Table 4, the microwave dielectric ceramic material obtained by the preparation method has the advantages that samples No. 1-9 are sintered at 1450-1550 ℃ and 2MPa to form microwave dielectric ceramic devices, the room temperature dielectric constant is 32-36, and the temperature coefficient tau is formed by adjusting the material synthesis ratio f (-40-110 ℃) of: the Q value of the ceramic resonator made of the material can reach more than 13000 (applied to the communication field with the frequency f being more than or equal to 8 GHz), and the loss energy is small. The No. 10 sample is sintered at 1530 ℃ under the normal pressure condition without pressurization to form a microwave dielectric ceramic device, and compared with the No. 1-9 samples, the temperature coefficient tau f The temperature (-40-110 ℃) is obviously increased, the Qf value is obviously reduced, and the loss energy of the microwave dielectric ceramic device is increased.
Comparative example: the experimental procedure of this comparative example is substantially the same as that of the example, and there are two differences, one of which is that the material A is changed to Ba 3 (Mg 0.1 Co 0.9 )Nb 2 O 9 According to a molar ratio of 3:0.1:0.45:1 accurately weighing BaCO 3 、MgO、Co 2 O 3 And Nb 2 O 5 Preparing three groups of samples with the same molar ratio, carrying out wet mixing ball milling, and carrying out other steps and material mixingThe same example includes ball milling, spray drying, calcining at 1060 deg.C, 1080 deg.C, 1120 deg.C for 3 hours, recording sample numbers D1, D2, D3, replacing A1 with D1, A2 with D2, A3 with D3, adding Zn as material B according to the mass ratio in Table 2 0.8 Mg 0.2 Nb 2 O 6 Carrying out wet ball milling, carrying out uniform ball milling, drying, and calcining for 0.75 hour at the temperature of 1000 ℃ in an air furnace to obtain three groups of main materials.
And then according to the formula of table 3, and the steps (4) - (8) of the embodiment are executed, and the two differences between the comparative example and the embodiment are that in the step (8), the green body after rubber discharge, the samples with the sample numbers D1 and D2 are heated to 1540 ℃ rapidly under the hot-pressing condition of 2Mpa, the sample with the sample number D3 is heated to 1150 ℃ for 3h rapidly at the heating rate of 150-300 ℃/h under the non-pressurization condition, and the performances of the obtained three groups of samples are shown in table 5.
TABLE 5 comparative example sample Performance test results Table
As is clear from a comparison of the results in tables 5 and 4, ba was used in the comparative example 3 (Mg 0.1 Co 0.9 )Nb 2 O 9 Alternative to Ba of the examples 3 Mg x Co 1-x Nb 2 O 9 ，0.4<x<0.75, the material B is still Zn 0.8 Mg 0.2 Nb 2 O 6 The Qf value is significantly reduced to 57000GHz or less, and the loss energy is increased if the ceramic resonator made of the material of the comparative example is used.
After 2PMa is adopted for hot pressing, the quality factor of the material is remarkably improved, the temperature coefficient is reduced, and mainly because the material contains compounds of Co and Zn, the volatilization temperature is lower than 1300 ℃, and the material is easy to volatilize in the high-temperature sintering process (above 1450 ℃), so that the component deviation is caused; the hot-pressing sintering can effectively ensure the uniformity of the environmental atmosphere, and is suitable for materials which contain volatile substances and have high requirements on performance.
The embodiments described above are some, not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (8)
1. A method for manufacturing a ceramic device, comprising: carrying out hot-pressing sintering on the ceramic dielectric material, and specifically comprising the following steps of:
adding an auxiliary preparation into the ceramic dielectric material, carrying out ball milling and drying to obtain particles, carrying out compression molding on the particles, carrying out heat preservation at 500 to 700 ℃ for 24 hours to carry out binder removal, then carrying out heat preservation at 1450 to 1550 ℃ in an air pressure environment of 1-3Mpa for 1 to 3 hours to carry out sintering, and carrying out annealing at 1150 ℃ to obtain the ceramic device;
wherein the ceramic dielectric material comprises a main material with the mass fraction of 98.5 to 99.5 percent and a modified additive with the mass fraction of 0.5 to 1.5 percent; the main material consists of 90-93% by mass of a material A and 7-10% by mass of a material B, wherein the chemical formula of A is Ba 3 Mg x Co 1-x Nb 2 O 9 ，0.4<x<0.75, B has the formula Zn 0.8 Mg 0.2 Nb 2 O 6 The preparation method of the ceramic dielectric material comprises the following steps: and mixing the main material and the modified additive, adding water, and performing wet ball milling to obtain the ceramic dielectric material in a powder state.
2. The method for producing a ceramic device according to claim 1, characterized in that: the modifying additive is selected from SnO 2 、SrCO 3 、MnCO 3 、Y 2 O 3 、CeO 2 And ZrO 2 One or more of (a).
3. The method of claim 2The method for manufacturing a ceramic device is characterized in that: in the modified additive, the mass fractions of the components in the ceramic dielectric material are as follows: snO 2 0~1%、SrCO 3 0~1%、MnCO 3 0~1%、Y 2 O 3 0~0.2%、CeO 2 0~0.3%，ZrO 2 0~0.3%。
4. The method for manufacturing a ceramic device according to any one of claims 1 to 3, wherein: the main material comprises the material A and the material B; the material A is BaCO 3 、MgO、Co 2 O 3 And Nb 2 O 5 Mixing, ball-milling, drying, and presintering at 1050-1150 ℃ for 2-4h to obtain the final product.
5. The method for producing a ceramic device according to claim 4, wherein: the material B is prepared by mixing ZnO, mgO and Nb 2 O 5 Weighing according to a molar ratio of 0.8.
6. The method for producing a ceramic device according to claim 5, characterized in that: the main material is obtained by mixing and grinding a material A and a material B according to the mass ratio of 90-93% and 7-10%, drying, and then pre-sintering at 950-1050 ℃ for 0.5-3h.
7. The method of manufacturing a ceramic device according to claim 1, wherein a pressure of gas at the time of sintering is 2MPa.
8. A ceramic device produced by the method for producing a ceramic device according to any one of claims 1 to 7.
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