CN115959895B - Microwave dielectric ceramic material, preparation method thereof and microwave dielectric ceramic device - Google Patents
Microwave dielectric ceramic material, preparation method thereof and microwave dielectric ceramic device Download PDFInfo
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Abstract
The application belongs to the technical field of ceramic materials, and particularly relates to a microwave dielectric ceramic material, a preparation method thereof and a microwave dielectric ceramic device. Wherein the chemical expression of the microwave dielectric ceramic material is xMg 2 SiO 4 -yA-zM wherein A comprises SiO 2 M comprises TiO 2 、CaTiO 3 、SrTiO 3 At least one of x, y and z together being 1. Through the synergistic interaction of the components in the microwave dielectric ceramic material, the microwave dielectric ceramic material has the characteristics of low dielectric constant, near-zero frequency temperature coefficient, high quality factor and the like, and epsilon r Is 9.4-11.64, the quality factor (Q multiplied by f) value is up to 92000GHz, and the resonant frequency temperature coefficient tau f The temperature is basically-10 to +10 ppm/DEG C, can be better used for preparing communication devices such as ceramic dielectric waveguides, monolithic filters, dielectric antennas and the like, and meets the technical requirements of systems such as communication base stations and the like.
Description
Technical Field
The application belongs to the technical field of ceramic materials, and particularly relates to a microwave dielectric ceramic material, a preparation method thereof and a microwave dielectric ceramic device.
Background
The microwave dielectric ceramic is a novel functional electronic ceramic, can be better used for preparing communication devices such as ceramic dielectric waveguides, monoblock filters, dielectric antennas and the like, and meets the technical requirements of a communication base station system.
Mg 2 SiO 4 Also called forsterite, belongs to an orthorhombic system. Mg of 2 SiO 4 Under the condition that no sintering aid is added, the ceramic has excellent microwave dielectric property after being sintered by solid phase reaction at 1350℃: dielectric constant epsilon r Approximately 6.9, a quality factor (Q×f) approximately 240000GHz, a resonant frequency temperature coefficient τ f The material is approximately equal to-67 ppm/DEG C, and can be used for manufacturing microwave substrates and millimeter wave devices. However Mg is 2 SiO 4 Ceramic τ f The value is more negative, the index requirement of the communication device cannot be met, the sintering temperature is higher, and the application range is greatly limited.
Disclosure of Invention
The purpose of the application is to provide a microwave dielectric ceramic material, a preparation method thereof and a microwave dielectric ceramic device, which aim to solve the problem of Mg to a certain extent 2 SiO 4 Ceramic τ f The values are negative, and the sintering temperature is high, so that the application range is greatly limited.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a microwave dielectric ceramic material having a chemical formula xMg 2 SiO 4 Y A-z M, wherein A comprises SiO 2 M comprises TiO 2 、CaTiO 3 、SrTiO 3 At least one of x, y and z together being 1.
In a second aspect, the present application provides a method for preparing a microwave dielectric ceramic material, including the steps of:
xMg according to chemical expression of microwave dielectric ceramic material 2 SiO 4 The stoichiometric ratio of the metal element in y A-z M is used for obtaining the raw material component, wherein A comprises SiO 2 M comprises TiO 2 、CaTiO 3 、SrTiO 3 At least one of x, y and z together being 1;
mixing and grinding the raw material components into mixed powder, and sintering the mixed powder into a mixed block;
grinding the mixed block into powder, mixing with a binder and a granulating auxiliary agent, and granulating to obtain granulated powder;
and (3) after the granulating powder is manufactured into a ceramic green body, sequentially performing glue discharging treatment and sintering treatment to obtain the microwave dielectric ceramic material.
In a third aspect, the present application provides a microwave dielectric ceramic device, where the microwave dielectric ceramic device includes the microwave dielectric ceramic material described above, or the microwave dielectric ceramic material prepared by the method described above.
The chemical expression of the microwave dielectric ceramic material provided by the first aspect of the application is xMg 2 SiO 4 Y A-z M, wherein A comprises SiO 2 M comprises TiO 2 、CaTiO 3 、SrTiO 3 At least one of x, y and z together being 1. On the one hand, a temperature coefficient tau with a lower sintering temperature and positive resonance frequency is chosen f Compounds of the value, e.g. TiO 2 、CaTiO 3 、SrTiO 3 One or more of them and Mg 2 SiO 4 The composite of the ceramics can effectively reduce Mg 2 SiO 4 Sintering temperature of ceramic, and its tau is regulated f The value is near zero. With the increase of the addition amount of M, mg 2 SiO 4 The densification sintering temperature of the M composite material is gradually reduced, and the dielectric constant epsilon r Linearly increasing, gradually decreasing the quality factor (Q x f) value, τ f The value changes from negative to positive. On the other hand, due to the added TiO 2 、CaTiO 3 、SrTiO 3 Equal positive tau f The compound has higher dielectric constant, so SiO is added simultaneously 2 The glass phase reduces the dielectric constant and sintering temperature of the composite ceramic and maintains good microwave dielectric property. And by addition of SiO 2 The glass phase enables xMg 2 SiO 4 When the sintering temperature of the-y A-z M ceramic composite material is reduced to 1100 ℃, the ceramic composite material still maintains good microwave dielectric property, and can be used for manufacturing microwave components. By xMg 2 SiO 4 The cooperative interaction of the components in the y A-z M microwave dielectric ceramic material,the microwave dielectric ceramic material has proper dielectric constant, near-zero frequency temperature coefficient and high quality factor, and the dielectric constant epsilon r Is 9.4-11.64, the quality factor (Q multiplied by f) value is up to 92000GHz, and the resonant frequency temperature coefficient tau f The method is basically-10 to +10 ppm/DEG C, can be better used for preparing communication devices such as ceramic dielectric waveguides, monoblock filters, dielectric antennas and the like, and meets the technical requirements of systems such as communication base stations and the like.
The preparation method of the microwave dielectric ceramic material provided in the second aspect of the application is based on the chemical expression xMg of the microwave dielectric ceramic material 2 SiO 4 After the raw material components are obtained according to the stoichiometric ratio of the metal elements in y A-z M, the raw material components are mixed and ground into mixed powder, and then the mixed powder is sintered to fully mix and dissolve the raw material components, so as to form a mixed block with uniformly dispersed components. And grinding the mixed block into powder, mixing and granulating with a binder and a granulating auxiliary agent, preparing a ceramic green body, and sequentially performing glue discharging treatment and sintering treatment to obtain the microwave dielectric ceramic material. On one hand, the preparation process is simple, the operation is convenient, the raw material cost is low, and the production process has good stability. On the other hand, tiO is used 2 、CaTiO 3 、SrTiO 3 One or more M substances, and SiO 2 Glass phase A material, with Mg 2 SiO 4 The ceramic is compounded, so that the sintering temperature of the microwave dielectric ceramic material can be effectively reduced, and the tau of the microwave dielectric ceramic material can be regulated f The value is near zero; meanwhile, the microwave dielectric ceramic material can keep better microwave dielectric property. Therefore, the prepared microwave dielectric ceramic material has proper dielectric constant, near-zero frequency temperature coefficient and high quality factor.
The microwave dielectric ceramic device provided by the third aspect of the application has the advantages that the microwave dielectric ceramic device comprises the microwave dielectric ceramic material with low dielectric constant, near-zero frequency temperature coefficient and high quality factor, so that the microwave dielectric ceramic device also has the performances of excellent dielectric constant, near-zero frequency temperature coefficient, high quality factor and the like. The method can be better used for preparing communication devices such as ceramic dielectric waveguides, monoblock filters, dielectric antennas and the like, and meets the technical requirements of systems such as communication base stations and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following description will briefly introduce the drawings that are needed in the embodiments or the description of the prior art, it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic flow chart of a preparation method of a microwave dielectric ceramic material according to an embodiment of the present application.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present application more clear, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of an association object, which means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c" may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application in the examples and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the examples of the present application may refer not only to specific contents of the respective components but also to the proportional relationship between the weights of the respective components, and thus, it is within the scope of the disclosure of the examples of the present application as long as the contents of the relevant components are scaled up or down according to the examples of the present application. Specifically, the mass in the examples of the present application may be a mass unit known in the chemical industry such as μ g, mg, g, kg.
The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
In a first aspect, an embodiment of the present application provides a microwave dielectric ceramic material, where the chemical expression of the microwave dielectric ceramic material is xMg 2 SiO 4 Y A-z M, wherein A comprises SiO 2 M comprises TiO 2 、CaTiO 3 、SrTiO 3 At least one of x, y and z together being 1.
The chemical expression of the microwave dielectric ceramic material provided by the first aspect of the embodiment of the application is xMg 2 SiO 4 Y A-z M, wherein A comprises SiO 2 M comprises TiO 2 、CaTiO 3 、SrTiO 3 At least one of x, y and z together being 1. On the one hand, a temperature coefficient tau with a lower sintering temperature and positive resonance frequency is chosen f Compounds of the value, e.g. TiO 2 、CaTiO 3 、SrTiO 3 One or more of them and Mg 2 SiO 4 The composite of the ceramics can effectively reduce Mg 2 SiO 4 Sintering temperature of ceramic, and its tau is regulated f The value is near zero. With the increase of the addition amount of M, mg 2 SiO 4 The densification sintering temperature of the M composite material is gradually reduced, and the dielectric constant epsilon r Linearly increasing, gradually decreasing the quality factor (Q x f) value, τ f The value changes from negative to positive. On the other hand, due to the added TiO 2 、CaTiO 3 、SrTiO 3 Equal positive tau f The compound has higher dielectric constant, so SiO is added simultaneously 2 The glass phase reduces the dielectric constant and sintering temperature of the composite ceramic and maintains good microwave dielectric property. And by addition of SiO 2 The glass phase enables xMg 2 SiO 4 When the sintering temperature of the-y A-z M ceramic composite material is reduced to 1100 ℃, the ceramic composite material still maintains good microwave dielectric property, and can be used for manufacturing microwave components. By xMg 2 SiO 4 The synergistic interaction of the components in the-y A-z M microwave dielectric ceramic material ensures that the microwave dielectric ceramic material has proper dielectric constant, near-zero frequency temperature coefficient and high quality factor, and the dielectric constant epsilon thereof r Is 9.4-11.64, the quality factor (Q multiplied by f) value is up to 92000GHz, and the resonant frequency temperature coefficient tau f The method is basically-10 to +10 ppm/DEG C, can be better used for preparing communication devices such as ceramic dielectric waveguides, monoblock filters, dielectric antennas and the like, and meets the technical requirements of systems such as communication base stations and the like.
In some embodiments, x is 50 to 80mol%, y is 12.5 to 30mol%, and z is 5 to 27.5mol%. With the increase of the addition amount of M, mg 2 SiO 4 The densification sintering temperature of the M composite material is gradually reduced, epsilon r Linearly increasing, gradually decreasing the Q×f value, τ f The value changes from negative to positive. When Mg is in 2 SiO 4 When the z value of the addition amount of M in the ceramic reaches 24wt%, the resonant frequency temperature of the materialThe coefficients are just adjusted to near zero. But due to the added M positive tau f The compounds have higher dielectric constants and can reduce Mg 2 SiO 4 Is used for the dielectric properties of the material. Therefore, 12.5 to 30mol% of SiO is added simultaneously 2 The glass phase reduces the dielectric constant and sintering temperature of the composite ceramic and maintains good microwave dielectric property. Microwave dielectric ceramic material xMg 2 SiO 4 In y A-z M, A comprises SiO 2 The molar content y of (C) is 12.5-30 mol%, and M comprises TiO 2 、CaTiO 3 、SrTiO 3 The total molar content z is 5-27.5 mol%, and in this case, the ceramic has better microwave dielectric property, smaller temperature coefficient of resonant frequency and better application property.
In some embodiments, the chemical composition of the microwave dielectric ceramic material includes xMg 2 SiO 4 -y SiO 2 -zTiO 2 Wherein the sum of x, y and z is 1. Further, x is 50 to 80mol%, y is 12.5 to 30mol%, and z is 5 to 27.5mol%.
In some embodiments, the chemical composition of the microwave dielectric ceramic material includes xMg 2 SiO 4 -y SiO 2 -zCaTiO 3 Wherein the sum of x, y and z is 1. Further, x is 50 to 80mol%, y is 12.5 to 30mol%, and z is 5 to 27.5mol%.
In some embodiments, the chemical composition of the microwave dielectric ceramic material includes xMg 2 SiO 4 -y SiO 2 -zSrTiO 3 Wherein the sum of x, y and z is 1. Further, x is 50 to 80mol%, y is 12.5 to 30mol%, and z is 5 to 27.5mol%.
In some embodiments, the chemical composition of the microwave dielectric ceramic material includes xMg 2 SiO 4 -y SiO 2 -zM, wherein M comprises TiO 2 And CaTiO 3 And/or SrTiO 3 Wherein the sum of x, y and z is 1. Further, x is 50 to 80mol%, y is 12.5 to 30mol%, and z is 5 to 27.5mol%. Simultaneously, a plurality of M-bit substances are doped, and the performance of the microwave dielectric ceramic material is regulated together, so that the microwave dielectric ceramic material can better meet the requirements of communication application.
The microwave dielectric ceramic material according to the above embodiment of the present application can be prepared by the following examples.
As shown in fig. 1, a second aspect of the embodiment of the present application provides a method for preparing a microwave dielectric ceramic material, which includes the following steps:
s10, xMg is carried out according to the chemical expression of the microwave dielectric ceramic material 2 SiO 4 The stoichiometric ratio of the metal element in y A-z M is used for obtaining the raw material component, wherein A comprises SiO 2 M comprises TiO 2 、CaTiO 3 、SrTiO 3 At least one of x, y and z together being 1;
s20, mixing and grinding the raw material components into mixed powder, and sintering the mixed powder into a mixed block;
s30, grinding the mixed block into powder, mixing the powder with a binder and a granulating auxiliary agent, and granulating to obtain granulated powder;
s40, after the granulated powder is manufactured into a ceramic green body, sequentially performing glue discharging treatment and sintering treatment on the ceramic green body to obtain the microwave dielectric ceramic material.
The preparation method of the microwave dielectric ceramic material provided in the second aspect of the embodiment of the application is according to the chemical expression xMg of the microwave dielectric ceramic material 2 SiO 4 After the raw material components are obtained according to the stoichiometric ratio of the metal elements in y A-z M, the raw material components are mixed and ground into mixed powder, and then the mixed powder is sintered to fully mix and dissolve the raw material components, so as to form a mixed block with uniformly dispersed components. And grinding the mixed block into powder, mixing and granulating with a binder and a granulating auxiliary agent, preparing a ceramic green body, and sequentially performing glue discharging treatment and sintering treatment to obtain the microwave dielectric ceramic material. On one hand, the preparation process is simple, the operation is convenient, the raw material cost is low, and the production process has good stability. On the other hand, tiO is used 2 、CaTiO 3 、SrTiO 3 One or more M substances, and SiO 2 Glass phase A material, with Mg 2 SiO 4 The ceramic is compounded, so that the sintering temperature of the microwave dielectric ceramic material can be effectively reduced, and the tau of the microwave dielectric ceramic material can be regulated f The value is near zero; at the same time, can make microwave dielectric ceramicThe material maintains good microwave dielectric properties. Therefore, the prepared microwave dielectric ceramic material has low dielectric constant, near-zero frequency temperature coefficient and high quality factor.
S10, according to the chemical expression xMg of the microwave dielectric ceramic material 2 SiO 4 The stoichiometric ratio of the metal element in y A-z M is used for obtaining the raw material component, wherein A comprises SiO 2 M comprises TiO 2 、CaTiO 3 、SrTiO 3 At least one of x, y and z together being 1. Wherein, tiO 2 、CaTiO 3 、SrTiO 3 One or more M substances with lower sintering temperature and positive tau f Compounds of the values, with Mg 2 SiO 4 The composite of the ceramics can effectively reduce Mg 2 SiO 4 Sintering temperature of ceramic, and its tau is regulated f The value is near zero. As the addition amount of M increases, xMg 2 SiO 4 -z M composite material with a gradual decrease in densification sintering temperature, epsilon r Linearly increasing, gradually decreasing the Q×f value, τ f The value changes from negative to positive. At the same time add SiO 2 The glass phase reduces the dielectric constant and sintering temperature of the composite ceramic and maintains good microwave dielectric property. And by addition of SiO 2 The glass phase enables Mg to be 2 SiO 4 When the sintering temperature of the-y A-z M ceramic composite material is reduced to 1100 ℃, the ceramic composite material still maintains good microwave dielectric property, and can be used for manufacturing microwave components.
In some embodiments, the microwave dielectric ceramic material has the chemical formula xMg 2 SiO 4 Y A-z M, wherein A comprises SiO 2 M comprises TiO 2 、CaTiO 3 、SrTiO 3 At least one of x, y and z is 1, x is 50 to 80mol%, y is 12.5 to 30mol%, and z is 5 to 27.5mol%.
In some embodiments, the chemical composition of the microwave dielectric ceramic material includes xMg 2 SiO 4 -y SiO 2 -zTiO 2 Wherein the sum of x, y and z is 1, x is 50 to 80mol%, y is 12.5 to 30mol%, and z is 5 to 27.5mol%.
In some embodiments, a microwave dielectric ceramic materialThe chemical composition of the material comprises xMg 2 SiO 4 -y SiO 2 -zCaTiO 3 Wherein the sum of x, y and z is 1, x is 50 to 80mol%, y is 12.5 to 30mol%, and z is 5 to 27.5mol%.
In some embodiments, the chemical composition of the microwave dielectric ceramic material includes xMg 2 SiO 4 -y SiO 2 -zSrTiO 3 Wherein the sum of x, y and z is 1, x is 50 to 80mol%, y is 12.5 to 30mol%, and z is 5 to 27.5mol%.
In some embodiments, the chemical composition of the microwave dielectric ceramic material includes xMg 2 SiO 4 -y SiO 2 -zM, wherein M comprises TiO 2 And CaTiO 3 And/or SrTiO 3 Wherein the sum of x, y and z is 1, x is 50 to 80mol%, y is 12.5 to 30mol%, and z is 5 to 27.5mol%.
In some embodiments, the feedstock component is selected from oxides or carbonates of metallic elements, and the like. In some embodiments, the feedstock components include magnesium oxide, silicon oxide, titanium oxide, calcium oxide, strontium carbonate, and the like.
In some embodiments, the feedstock component is an analytically pure purity standard; the high-purity raw material components can effectively reduce the introduction of impurity components, and avoid the influence of raw material impurities on the purity and electrochemical performance of the microwave dielectric ceramic material.
In the step S20, the raw material components are mixed and ground into mixed powder, and the mixed powder is sintered to fully mix the raw material components and form a mixed block with uniformly dispersed components.
In some embodiments, the step of mixing and grinding the raw material components into a mixed powder comprises: after the raw material components are mixed, the mass ratio of the raw materials to the balls to the water is 1: (1-3): ball milling for 2-6 hours under the condition of (1-2), drying and sieving to obtain mixed powder. In this case, the raw material components can be further refined and homogenized by the ball milling conditions, and the raw material components can be sufficiently and uniformly mixed during the milling process. In some embodiments, the drying temperature is 100-150 ℃ and the duration is 1-3 hours, and the water introduced in the ball milling is sufficiently removed to obtain the dry mixed powder.
In some embodiments, the conditions for sintering the mixed powder into a mixed mass include: sintering the mixed powder for 2-6 hours at 800-1100 ℃ to fully mix and dissolve the raw material components to form a mixed block with uniformly dispersed components. In some embodiments, the mixed powder is sintered at a temperature of 800-900 ℃, 900-1000 ℃, 1000-1100 ℃ and the like for 2-3 hours, 3-4 hours, 4-5 hours, 5-6 hours and other time periods to obtain a mixed block with uniformly dispersed components.
In the step S30, the mixed block is ground into powder, the raw material components in the powder are uniformly dispersed, and then the powder, the binder and the granulating auxiliary agent are mixed and granulated to obtain granulated powder.
In some embodiments, the powder has a particle size D50 (i.e., median particle size or median particle size) of less than 0.7 μm; the smaller the value of the granularity D50 is, the finer the ceramic blocks in the slurry are ground, the larger the surface activation energy of powder particles is, the solid phase reaction is facilitated during sintering, and the sintering temperature is reduced. In some embodiments, the powder has a particle size D50 of 0.01 to 0.1 μm, 0.1 to 0.2 μm, 0.2 to 0.3 μm, 0.3 to 0.4 μm, 0.4 to 0.5 μm, 0.5 to 0.6 μm, 0.6 to 0.7 μm, and not equal to 0.7 μm, etc.
In some embodiments, the step of grinding the mixed mass into a powder comprises: crushing the mixed block, and mixing and grinding the crushed mixed block with a dispersing agent to obtain powder; the dispersing agent is added for mixing and grinding, so that better powder refinement is facilitated, the dispersing agent can reduce interfacial tension between solid and liquid, and the affinity between solid particles and water is improved, so that the surfaces of the solid particles are easy to wet; the charge adsorption layer is formed on the surface of the solid particles, and the solid particles are far away due to electrostatic repulsive force, so that the system is uniform, the suspension performance is increased, and agglomeration and sedimentation are not easy to occur. The particle size D50 of the prepared powder is smaller than 0.7 mu m. In some specific embodiments, after the mixed block is subjected to secondary ball milling and crushing, dispersing agents are added into ball milling slurry, the ball milling slurry is ground and uniformly mixed, and then the ball milling slurry is transferred to a sand mill for continuous refinement until the particle size D50 of powder is smaller than 0.7 mu m.
In some embodiments, the mass ratio of powder to dispersant is 100: (0.2-0.4). In this case, the addition amount of the dispersant is advantageous for further refining the powder. If the dosage of the dispersing agent is too high, the area of the solid particle surface available for the dispersing agent to adsorb is limited, and after the dispersing agent reaches saturated adsorption on the particle surface, the redundant and unadsorbed dispersing agent enables the originally dispersed particles to agglomerate again through the bridge effect, so that flocculation phenomenon is generated, the stability is poor, the viscosity of the slurry is increased, the slurry is thickened, and the performances of the original slurry are reduced. If the amount of the dispersing agent is insufficient, the particle size of the powder is not easily refined, and the stability of the system is not easily improved. In some embodiments, the mass ratio of powder to dispersant may be 100: (0.2-0.3), 100: (0.3 to 0.4), and the like.
In some embodiments, the dispersant comprises: at least one of cellulose derivatives, fatty acid polyethylene glycol, polyacrylamide and polycarboxylate; the dispersing agents can reduce interfacial tension between solid and liquid, increase the affinity between solid particles and water, and enable the surfaces of the solid particles to be easy to wet; the charge adsorption layer is formed on the surface of the solid particles, and the solid particles are far away due to electrostatic repulsive force, so that the system is uniform, the suspension performance is increased, and agglomeration and sedimentation are not easy to occur.
In some embodiments, the granulation aid comprises: defoamers and lubricants, wherein the defoamers can reduce the surface tension of water, solutions, suspensions, etc., prevent foam formation, or reduce or eliminate original foam, improving the stability of the mixed slurry. The lubricant is used for reducing friction resistance among solid particles such as powder and the like and improving the mixing uniformity of all the components.
In some embodiments, the means of granulation employs spray granulation. In some specific embodiments, the mixed blocks are crushed, mixed and ground with a dispersing agent to obtain slurry of powder, and then binder, defoamer, lubricant and the like are added to prepare uniformly dispersed slurry, and spray granulation is carried out to obtain granulated powder with small particle size and high uniformity.
In some embodiments, the mass ratio of powder, binder, defoamer, and lubricant is 100: (2-5): (0.2-0.4): (1-3); in this case, it is more advantageous to prepare granulated powder having a small particle diameter and high uniformity. Wherein, the addition amount of the binder ensures the bonding and forming performance between the powder materials and avoids the influence of excessive addition on the physical and chemical properties of the ceramic material. The addition of the defoamer and the lubricant also effectively ensures the preparation of the granulated powder, and if the addition is too high, the ceramic which is subsequently prepared causes the green body to be too hard, and the physical and chemical properties of the ceramic material after the subsequent sintering can be influenced.
In some embodiments, the binder comprises: at least one of polyvinyl alcohol PVA and polyethylene glycol PEG; the adhesive can improve the bonding performance among the components, and is beneficial to powder molding to prepare device products. In some embodiments, the binder comprises both polyvinyl alcohol and polyethylene glycol, wherein the polyvinyl alcohol acts as an adhesive and the polyethylene glycol acts as a plasticizer, and the combination of the two better improves the adhesion performance between the components.
In some embodiments, the defoamer comprises: at least one of polyether defoamer and polysiloxane defoamer; these defoamers can reduce the surface tension of water, solutions, suspensions, etc., prevent foam formation, or reduce or eliminate the original foam, improving the stability of the mixed slurry.
In some embodiments, the wetting agent comprises: at least one of stearic acid, magnesium stearate and calcium stearate, which are used for reducing friction resistance among solid particles such as powder materials and improving the mixing uniformity of the components.
In the step S30, after the granulated powder is made into the ceramic green compact, the ceramic green compact is sequentially subjected to glue discharging treatment and sintering treatment, and the microwave dielectric ceramic material is obtained.
In some embodiments, the step of granulating the powder to produce a ceramic green body comprises: adding the granulated powder into a die, and performing dry pressing molding under the condition that the pressure is 100-300 MPa to obtain a ceramic green body. Under the pressure condition, the granulating powder is favorable to fully contact, shrinkage and void removal, and a stable ceramic green body is formed. In some embodiments, the pressure may be 100-150 MPa, 150-200 MPa, 200-250 MPa, 250-300 MPa, etc.
In some embodiments, the conditions of the glue removal process include: the ceramic green body is kept at 400-800 ℃ for 1-3 hours. In this case, a large amount of organic matters such as binders, dispersants, lubricants, defoamers and the like in the green body are oxidized and decomposed at high temperature and volatilized, so that the green body is prevented from deforming and cracking in the subsequent sintering process. Meanwhile, the carbon content of the organic matters is high, and the sintering quality is affected when the oxygen is insufficient to form a reducing atmosphere, so that the organic matters in the green body are required to be removed before the green body is sintered, and the requirements on the shape, the size and the quality of the product are ensured. In some embodiments, the ceramic green body is incubated at a temperature of 400-500 ℃, 500-600 ℃, 600-700 ℃, 700-800 ℃, etc., for 1-2 hours, 2-3 hours, etc.
In some embodiments, the conditions of the sintering process include: heating the product of the glue discharging treatment to 1100-1150 ℃ at the speed of 1-10 ℃/min, and preserving heat for 2-6 hours to obtain the microwave dielectric ceramic material. Due to the microwave dielectric ceramic material xMg 2 SiO 4 Y A-z M by doping A comprising SiO 2 M comprises TiO 2 、CaTiO 3 、SrTiO 3 At least one of the components in the ceramic green body can react to form the microwave dielectric ceramic material with excellent performance by effectively reducing the sintering temperature of the microwave dielectric ceramic material and preserving heat for 2-6 hours at 1100-1150 ℃, and the microwave dielectric ceramic material has lower dielectric constant, near-zero frequency temperature coefficient and high quality factor.
A third aspect of the embodiments of the present application provides a microwave dielectric ceramic device, where the microwave dielectric ceramic device includes the microwave dielectric ceramic material described above, or the microwave dielectric ceramic material prepared by the method described above.
The microwave dielectric ceramic device provided by the third aspect of the embodiment of the application, because the microwave dielectric ceramic device comprises the microwave dielectric ceramic material with low dielectric constant, near-zero frequency temperature coefficient and high quality factor, the microwave dielectric ceramic device also has excellent performances such as low dielectric constant, near-zero frequency temperature coefficient and high quality factor. The method can be better used for preparing communication devices such as ceramic dielectric waveguides, monoblock filters, dielectric antennas and the like, and meets the technical requirements of systems such as communication base stations and the like.
In order to make the implementation details and operations of the present application clearly understood by those skilled in the art, and make the microwave dielectric ceramic material and the preparation method thereof and the advanced performance of the microwave dielectric ceramic device of the embodiments of the present application significantly show, the following examples are given to illustrate the above technical solutions by using multiple embodiments.
Examples 1 to 11
Examples 1 to 11 respectively provide a microwave dielectric ceramic material with a chemical expression xMg 2 SiO 4 -ySiO 2 -zTiO 2 The specific values of x, y and z are shown in Table 1 below.
The preparation method comprises the following steps:
1. respectively according to the chemical expression xMg in the table 1 2 SiO 4 -ySiO 2 -zTiO 2 The mass of each raw material required was calculated, and the specific amounts thereof are shown in Table 1 below, wherein the raw materials were analytically pure, 99.9% by weight of MgO, 99.5% by weight of SiO 2 And 99.8wt% TiO 2 。
2. Accurately weighing the raw materials, pouring into a ball mill tank, adding deionized water and ZrO 2 A grinding ball; the weight ratio of the three components is as follows: and (3) material: ball: deionized water = 1:2:1.5; ball milling for 4 hours, drying the slurry at 120 ℃ for 2 hours, and sieving to obtain mixed powder; the mixed powder is put into an alumina crucible and synthesized for 4 hours at 950 ℃ to obtain a mixed block.
3. Performing secondary ball milling on the mixed block, adding 0.3wt% of dispersing agent with a certain proportion into slurry, grinding for 2 hours, transferring to a sand mill, and continuously refining until the particle size D50 of the mixed block is smaller than 0.7 mu m, so as to obtain powder with the particle size D50 smaller than 0.7 mu m; adding PVA1.7wt%, PEG1.7wt%, polyether defoamer 0.3wt% and stearic acid lubricant 2wt% into the slurry in a certain proportion, and carrying out spray granulation to obtain granulated powder;
4. putting the granulated powder into a die for dry pressing and forming, wherein the pressure is 150MPa, and obtaining a green sheet; and (3) preserving the temperature of the green sheet at 600 ℃ for 2 hours to remove organic matters, and then sintering at constant temperature for 4 hours at the temperature rising rate of 5 ℃/min to 1100-1150 ℃ to obtain a sintered body, namely the microwave dielectric ceramic material.
TABLE 1 xMg 2 SiO 4 -ySiO 2 -zTiO 2 Batching table
Examples 12 to 22
Examples 12 to 22 respectively provide a microwave dielectric ceramic material with a chemical expression xMg 2 SiO 4 -ySiO 2 -zCaTiO 3 The specific values of x, y and z are shown in Table 2 below.
The preparation method comprises the following steps:
2. respectively according to the chemical expression xMg in Table 2 2 SiO 4 -ySiO 2 -zCaTiO 3 The mass of each raw material required was calculated, and the specific amounts thereof are shown in Table 2 below, wherein the raw materials were analytically pure, 99.9% by weight of MgO, 99.5% by weight of SiO 2 99.5wt% CaCO 3 And 99.8wt% TiO 2 。
2. Accurately weighing the raw materials, pouring into a ball mill tank, adding deionized water and ZrO 2 A grinding ball; the weight ratio of the three components is as follows: and (3) material: ball: deionized water = 1:2:1.5; ball milling for 4 hours, drying the slurry at 120 ℃ for 2 hours, and sieving to obtain mixed powder; the mixed powder is put into an alumina crucible and synthesized for 4 hours at 1000 ℃ to obtain a mixed block.
3. Performing secondary ball milling on the mixed block, adding 0.3wt% of dispersing agent with a certain proportion into slurry, grinding for 2 hours, transferring to a sand mill, and continuously refining until the particle size D50 of the mixed block is smaller than 0.7 mu m, so as to obtain powder with the particle size D50 smaller than 0.7 mu m; adding PVA1.7wt%, PEG1.7wt%, polyether defoamer 0.3wt%, stearic acid lubricant 2wt% and the like into the slurry in a certain proportion, and performing spray granulation to obtain granulated powder;
4. putting the granulated powder into a die for dry pressing and forming, wherein the pressure is 150MPa, and obtaining a green sheet; and (3) preserving the temperature of the green sheet at 600 ℃ for 2 hours to remove organic matters, and then sintering at the constant temperature for 4 hours at the temperature rising rate of 5 ℃/min reaching 1150-1250 ℃ to obtain a sintered body, namely the microwave dielectric ceramic material.
TABLE 2 xMg 2 SiO 4 -ySiO 2 +zCaTiO 3 Batching table
Examples 23 to 33
Examples 23 to 33 respectively provide a microwave dielectric ceramic material with a chemical expression xMg 2 SiO 4 -ySiO 2 -zSrTiO 3 The specific values of x, y and z are shown in Table 3 below.
The preparation method comprises the following steps:
3. respectively according to the chemical expression xMg in the table 3 2 SiO 4 -ySiO 2 -zSrTiO 3 The mass of each raw material required was calculated, and the specific amounts thereof are shown in Table 3 below, wherein the raw materials were analytically pure, 99.9% by weight of MgO, 99.5% by weight of SiO 2 99.5wt% SrCO 3 And 99.8wt% TiO 2 。
2. Accurately weighing the raw materials, pouring into a ball mill tank, adding deionized water and ZrO 2 A grinding ball; the weight ratio of the three components is as follows: and (3) material: ball: deionized water = 1:2:1.5; ball milling for 4 hours, drying the slurry at 120 ℃ for 2 hours, and sieving to obtain mixed powder; the mixed powder is put into an alumina crucible and synthesized for 4 hours at 1000 ℃ to obtain a mixed block.
3. Performing secondary ball milling on the mixed block, adding 0.3wt% of dispersing agent with a certain proportion into slurry, grinding for 2 hours, transferring to a sand mill, and continuously refining until the particle size D50 of the mixed block is smaller than 0.7 mu m, so as to obtain powder with the particle size D50 smaller than 0.7 mu m; adding PVA1.7wt%, PEG1.7wt%, polyether defoamer 0.3wt%, stearic acid lubricant 2wt% and the like into the slurry in a certain proportion, and performing spray granulation to obtain granulated powder;
4. putting the granulated powder into a die for dry pressing and forming, wherein the pressure is 150MPa, and obtaining a green sheet; and (3) preserving the temperature of the green sheet at 600 ℃ for 2 hours to remove organic matters, and then sintering at the constant temperature for 4 hours at the temperature rising rate of 5 ℃/min reaching 1150-1250 ℃ to obtain a sintered body, namely the microwave dielectric ceramic material.
TABLE 3 xMg 2 SiO 4 -ySiO 2 +zSrTiO 3 Batching table
Further, to verify the progress of the examples of the present application, the microwave dielectric ceramic materials provided in each example were subjected to phase analysis using an X-ray diffractometer (type Rigaku d\max2550, 40kv,200 ma). Meanwhile, a vector network analyzer (Agilent 8722D) and a single-cavity and clamp testing instrument are adopted to test the microwave dielectric properties of the microwave dielectric ceramic material. The test results are shown in tables 4 to 6 below:
TABLE 4 xMg 2 SiO 4 -ySiO 2 +zTiO 2 Dielectric Properties of microwave ceramic Material
TABLE 5 xMg 2 SiO 4 -ySiO 2 +zCaTiO 3 Dielectric Properties of microwave ceramic Material
TABLE 6 xMg 2 SiO 4 -ySiO 2 -zSrTiO 3 Dielectric Properties of microwave ceramic Material
As can be seen from the test results, the microwave dielectric ceramic material prepared by the embodiments of the present application has excellent microwave dielectric properties, and the dielectric constant epsilon r 9.4 to 11.64, as low as 9.4; the quality factor (Q×f) is up to 92000GHz, and the resonant frequency temperature coefficient tau f Basically between-10 and +10 ppm/DEG C. The method can be better used for preparing communication devices such as ceramic dielectric waveguides, monoblock filters, dielectric antennas and the like, and meets the technical requirements of systems such as communication base stations and the like. In addition, the microwave dielectric ceramic has low cost of raw materials and good stability in production process.
The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, and alternatives falling within the spirit and principles of the present application.
Claims (8)
1. A microwave dielectric ceramic material is characterized in that the chemical expression of the microwave dielectric ceramic material is xMg 2 SiO 4 Y A-z M, wherein A is SiO 2 Glass phase, M is CaTiO 3 The sum of x, y and z is 1; the x is 50-60 mol%, the y is 25-30 mol%, and the z is 15-20 mol%; the sintering treatment conditions of the microwave dielectric ceramic material comprise: and heating the product of the glue discharging treatment to 1100-1150 ℃ at a speed of 1-10 ℃/min, and preserving heat for 2-6 hours.
2. A method for preparing a microwave dielectric ceramic material according to claim 1, comprising the steps of:
xMg according to chemical expression of microwave dielectric ceramic material 2 SiO 4 -y A-z M of metallic elementsThe stoichiometric ratio of the raw material components is obtained, wherein A is SiO 2 Glass phase, M is CaTiO 3 The sum of x, y and z is 1;
mixing and grinding the raw material components into mixed powder, and sintering the mixed powder into a mixed block;
grinding the mixed block into powder, mixing the powder with a binder and a granulating auxiliary agent, and granulating to obtain granulated powder;
after the granulating powder is manufactured into a ceramic green body, sequentially performing glue discharging treatment and sintering treatment on the ceramic green body, wherein the sintering treatment conditions comprise: and heating the product of the glue discharging treatment to 1100-1150 ℃ at a speed of 1-10 ℃/min, and preserving heat for 2-6 hours to obtain the microwave dielectric ceramic material.
3. The method of preparing a microwave dielectric ceramic material according to claim 2, wherein the raw material components are analytically pure purity standards;
and/or the step of mixing and grinding each of the raw material components into mixed powder comprises: after the raw material components are mixed, the mass ratio of the raw materials to the balls to the water is 1: (1-3): ball milling for 2-6 hours under the condition of (1-2), drying and sieving to obtain the mixed powder.
4. The method of preparing a microwave dielectric ceramic material according to claim 3, wherein the conditions for sintering the mixed powder into a mixed mass include: and sintering the mixed powder for 2-6 hours at the temperature of 800-1100 ℃ to obtain the mixed block.
5. The method for preparing a microwave dielectric ceramic material according to any one of claims 2 to 4, wherein the powder has a particle size D50 of less than 0.7 μm;
and/or the step of grinding the mixed mass into the powder comprises: crushing the mixed block, and mixing and grinding the crushed mixed block with a dispersing agent to obtain the powder;
and/or, the granulation aid comprises: defoamers and lubricants;
and/or, the granulating mode adopts spray granulation.
6. The method for preparing a microwave dielectric ceramic material according to claim 5, wherein the mass ratio of the powder to the dispersant is 100: (0.2 to 0.4);
and/or, the dispersant comprises: at least one of cellulose derivatives, fatty acid polyethylene glycol, polyacrylamide and polycarboxylate;
and/or the mass ratio of the powder, the binder, the defoamer and the lubricant is 100: (2-5): (0.2 to 0.4): (1-3);
and/or, the binder comprises: at least one of polyvinyl alcohol and polyethylene glycol;
and/or, the defoamer comprises: at least one of polyether defoamer and polysiloxane defoamer;
and/or, the lubricant comprises: at least one of stearic acid, magnesium stearate and calcium stearate.
7. The method of preparing a microwave dielectric ceramic material according to claim 6, wherein the step of preparing the granulated powder into a ceramic green body comprises: adding the granulated powder into a die, and performing dry press molding under the condition that the pressure is 100-300 MPa to obtain the ceramic green body;
and/or, the conditions of the glue discharging treatment comprise: and (3) preserving the temperature of the ceramic green body for 1-3 hours at the temperature of 400-800 ℃.
8. A microwave dielectric ceramic device, wherein the microwave dielectric ceramic device comprises the microwave dielectric ceramic material according to claim 1 or the microwave dielectric ceramic material prepared by the method according to any one of claims 2 to 7.
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