CN110746188A - Microwave dielectric ceramic composition, preparation method and application thereof, microwave dielectric ceramic, preparation method and application thereof, and microwave device - Google Patents

Microwave dielectric ceramic composition, preparation method and application thereof, microwave dielectric ceramic, preparation method and application thereof, and microwave device Download PDF

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CN110746188A
CN110746188A CN201911225406.9A CN201911225406A CN110746188A CN 110746188 A CN110746188 A CN 110746188A CN 201911225406 A CN201911225406 A CN 201911225406A CN 110746188 A CN110746188 A CN 110746188A
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dielectric ceramic
microwave dielectric
microwave
ceramic composition
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CN110746188B (en
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杨彬
付清波
杨月霞
应红
刘光明
宋锡滨
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Shandong Sinocera Functional Material Co Ltd
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Abstract

The invention relates to the field of electronic ceramics, and particularly provides a microwave dielectric ceramic composition, a preparation method and application thereof, microwave dielectric ceramic, a preparation method and application thereof, and a microwave device. The microwave dielectric ceramic composition comprises the following components in percentage by weight: 90-99.5 wt% of main material and 0.5-10 wt% of additive; the main materials comprise: mg (magnesium)xCa1‑xSmAlO4Wherein x is more than 0 and less than 0.4; the additive comprises: CaZrO3、Nb2O3、TiO2NiO and Tb4O7. The ceramic composition mainly adopts MgxCa1‑xSmAlO4The ceramic is a main material and is matched with a specific additive, so that the ceramic not only has medium and low dielectric constant, higher F and Q values and frequency temperature coefficients close to zero after being sintered into ceramic, but also can effectively reduce the sintering temperature of a ceramic body and reduce the production cost of the ceramic.

Description

Microwave dielectric ceramic composition, preparation method and application thereof, microwave dielectric ceramic, preparation method and application thereof, and microwave device
Technical Field
The invention relates to the field of electronic ceramics, in particular to a microwave dielectric ceramic composition, a preparation method and application thereof, microwave dielectric ceramic, a preparation method and application thereof and a microwave device.
Background
The microwave dielectric ceramic is a novel functional ceramic material developed in nearly thirty years, which is a ceramic material used as a dielectric material and completing one or more functions in a microwave frequency (mainly in a frequency range of 300 MHz-30 GHz) circuit and is a key material for manufacturing microwave dielectric filters and resonators. The microwave dielectric ceramic has the excellent performances of higher dielectric constant, lower dielectric loss, small temperature coefficient and the like, can meet the use requirements of miniaturization, integration, high reliability and low cost of a microwave circuit, and is suitable for manufacturing various microwave components. With the development of mobile communication technology, microwave dielectric ceramics have become one of the key projects for high-technology ceramic research.
The microwave dielectric ceramic is widely applied to the field of communication, and along with the development of communication technology, particularly microwave communication technology, for example, in 5G microwave communication technology, the requirements on the microwave dielectric ceramic are higher and higher, and the requirements on the use of a dielectric filter and a microwave antenna are more strict. Many researches on microwave dielectric materials and microwave dielectric ceramics at home and abroad also have many related patents, and microwave dielectric and ceramic series products are numerous, but most of the microwave dielectric and ceramic series products are based on 2-4G and the prior technical requirements, including test requirements or application environments. The key technology for 5G mobile communication is mainly embodied in two aspects of wireless transmission technology and network technology, the former mainly includes technologies such as large-scale antenna array, ultra-dense networking, novel multiple access and full-spectrum access, and the latter mainly includes self-organizing network (SON), soft-defined network (SDN) and network function Virtualization (VNF), and the latter mainly has higher reliability for microwave devices.
The filter applied to the microwave communication system is required to have stable performance, low insertion loss, small volume and low price. The high-performance microwave dielectric material is the core of a resonator type filter, and in a microwave communication system, the requirements on the main performance of the microwave dielectric material are as follows:
1) high dielectric constant. Microwave dielectric filters are made up of dielectric resonators whose resonant frequency is related to the dielectric constant of the dielectric material and the resonant dimensions of the resonator. Stated another way, at a particular frequency, the dimensions of the resonator are related to the dielectric constant of the dielectric material: the larger the dielectric constant of the dielectric material, the smaller the required dielectric ceramic bulk and the smaller the size of the resonator.
2) High quality factor. An important requirement of the filter is that the insertion loss is low, the dielectric loss of the microwave material is a main factor influencing the insertion loss of the dielectric filter, and the Q value (quality factor) of the microwave dielectric material is in inverse proportion to the dielectric loss, so that the use of the microwave dielectric material with high quality factor is beneficial to reducing the insertion loss of the microwave dielectric filter.
3) A frequency temperature coefficient close to zero. The working temperature of the communication device cannot be constant, if the resonant temperature frequency of the microwave dielectric material is changed greatly, the carrier signal of the filter can drift under different air temperatures, so that the use performance of the device is affected, and the requirement that the resonant frequency of the material cannot fluctuate too much along with the temperature is met.
At present, the microwave dielectric material system with a dielectric constant of about 20 mainly comprises: ba (Mn)1/3Ta2/3)O3，MgTiO3·CaTiO3，Ca1+xSmyNd1-yAlO4Etc. wherein Ba (Mn)1/3Ta2/3)O3The production process has strict control conditions and high production cost; MgTiO 23·CaTiO3The system F is lower than Q value (less than or equal to 60000); and Ca1+xSmyNd1-yAlO4The sintering temperature of the system is higher (more than 1400 ℃).
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a microwave dielectric ceramic composition which mainly adopts MgxCa1-xSmAlO4The ceramic is a main material and is matched with a specific additive, so that the ceramic not only has medium and low dielectric constant, higher F and Q values and frequency temperature coefficients close to zero after being sintered into ceramic, but also can effectively reduce the sintering temperature of a ceramic body and reduce the production cost of the ceramic.
The second purpose of the invention is to provide a preparation method of the microwave dielectric ceramic composition.
The third purpose of the invention is to provide the application of the microwave dielectric ceramic composition.
The fourth purpose of the invention is to provide a microwave dielectric ceramic.
The fifth purpose of the invention is to provide a preparation method of the microwave dielectric ceramic.
The sixth purpose of the invention is to provide the application of the microwave dielectric ceramic.
A seventh object of the present invention is to provide a microwave device.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the invention provides a microwave dielectric ceramic composition, which comprises the following components in percentage by weight: 90-99.5 wt% of main material and 0.5-10 wt% of additive;
the main materials comprise: mg (magnesium)xCa1-xSmAlO4Wherein x is more than 0 and less than 0.4;
the additive comprises: CaZrO3、Nb2O3、TiO2NiO and Tb4O7。
As a further preferable technical scheme, the microwave dielectric ceramic composition comprises the following components in percentage by weight: 92-99 wt% of main material and 1-8 wt% of additive;
preferably, the microwave dielectric ceramic composition comprises the following components in percentage by weight: 92.5-97 wt% of main material and 3-7.5 wt% of additive;
preferably, CaZrO3The content of (B) is 0.1-0.6 wt%;
preferably, Nb2O3The content of (B) is 0.1-7 wt%;
preferably, TiO2The content of (B) is 0.1-5 wt%;
preferably, the content of NiO is 0.1-1 wt%;
preferably, Tb4O7The content of (B) is 0.1-0.5 wt%;
preferably, the additive further comprises MoO3And/or LaAlO3；
Preferably, MoO3Is 0 to 0.5 wt%, excluding 0;
preferably, LaAlO3Is 0 to 3 wt%, excluding 0.
As a further preferable technical scheme, the specific surface area of the microwave dielectric ceramic composition is 4-8m2/g。
In a second aspect, the present invention provides a preparation method of the microwave dielectric ceramic composition, including: and mixing the main material and the additive, and then optionally crushing to obtain the microwave dielectric ceramic composition.
As a further preferred technical scheme, the main material is prepared by the following method: mixing the main materials with the raw materials and calcining to obtain the main materials;
preferably, the raw materials for the main material comprise magnesium compound, calcium compound and Sm2O3And Al2O3；
Preferably, the compound of magnesium comprises MgO, Mg (OH)2Or MgCO3At least one of;
preferably, the compound of calcium comprises CaO, Mg (OH)2Or CaCO3At least one of;
preferably, the specific surface area of each raw material for the main materials is 8-15m independently2/g；
Preferably, the particle size of each additive is less than 300 nm;
preferably, the calcination temperature is 1150-1250 ℃ and the calcination time is 2-5 h.
In a third aspect, the invention provides an application of the microwave dielectric ceramic composition or the microwave dielectric ceramic composition obtained by the preparation method in preparation of microwave dielectric ceramics.
In a fourth aspect, the present invention provides a microwave dielectric ceramic prepared from the above microwave dielectric ceramic composition or the microwave dielectric ceramic composition obtained by the above preparation method.
In a fifth aspect, the invention provides a preparation method of a microwave dielectric ceramic, comprising the following steps: the microwave dielectric ceramic composition or the microwave dielectric ceramic composition obtained by the preparation method is sequentially granulated, formed and sintered to obtain microwave dielectric ceramic;
preferably, binders used for granulation include PVA, PEG, and acrylic acid;
preferably, the total content of PVA, PEG and acrylic acid in the granules obtained after granulation is from 2 to 5% by weight;
preferably, the sintering temperature is 1250-.
In a sixth aspect, the invention provides an application of the microwave dielectric ceramic or the microwave dielectric ceramic prepared by the method in preparation of microwave devices;
preferably, the microwave device comprises a microwave filter or a microwave antenna.
In a seventh aspect, the present invention provides a microwave device, including the above microwave dielectric ceramic or the microwave dielectric ceramic prepared by the above method;
preferably, the microwave device comprises a microwave filter or a microwave antenna.
Compared with the prior art, the invention has the beneficial effects that:
the microwave dielectric ceramic composition provided by the invention mainly adopts MgxCa1-xSmAlO4(x is more than 0 and less than 0.4) as main material, CaSmAlO4The sintering temperature can be reduced by doping a certain content of Mg, and NiO and Tb are added as additives4O7The addition of (b) also mainly plays a role in reducing the sintering temperature,meanwhile, the device also has the functions of adjusting and balancing Q value and frequency temperature coefficient; additive CaZrO3、Nb2O3And TiO2The addition of (2) mainly plays a role in adjusting and balancing the dielectric constant and the temperature coefficient of frequency.
The microwave dielectric ceramic composition has the advantages that the specific components with specific contents are adopted, so that the microwave dielectric ceramic composition not only has medium and low dielectric constant (15-22 can be continuously adjusted), higher F & ltx & gt Q value (60000- & lt 85000- & gt) and frequency temperature coefficient (within-5 ppm/& lt DEG & gtC) close to zero after being sintered into ceramic, but also has the effect of reducing the sintering temperature (1250 & ltx & gt 1400 ℃) of the ceramic body, and the production cost is reduced.
Drawings
FIG. 1 shows Mg synthesized in example 220.2Ca0.8SmAlO4An XRD pattern of (a);
FIG. 2 is an SEM image of the particle morphology obtained after granulation of the microwave dielectric ceramic composition in example 22;
FIG. 3 is an SEM photograph of the surface of a ceramic body of the microwave dielectric ceramic composition of example 22 after sintering to obtain a microwave dielectric ceramic;
FIG. 4 is an SEM photograph of a cross section of a ceramic body of the microwave dielectric ceramic composition of example 22 after sintering to obtain a microwave dielectric ceramic.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
According to one aspect of the invention, a microwave dielectric ceramic composition is provided, which comprises the following components in percentage by weight: 90-99.5 wt% of main material and 0.5-10 wt% of additive;
the main materials comprise: mg (magnesium)xCa1-xSmAlO4Wherein x is more than 0 and less than 0.4;
the additive comprises: CaZrO3、Nb2O3、TiO2、NiO and Tb4O7。
The microwave dielectric ceramic composition mainly adopts MgxCa1-xSmAlO4(x is more than 0 and less than 0.4) as main material, CaSmAlO4The sintering temperature can be reduced by doping a certain content of Mg, and NiO and Tb are added as additives4O7The addition of the catalyst also mainly plays a role in reducing the sintering temperature, and simultaneously has a certain function of adjusting and balancing the Q value and the frequency temperature coefficient; additive CaZrO3、Nb2O3And TiO2The addition of (2) mainly plays a role in adjusting and balancing the dielectric constant and the temperature coefficient of frequency.
The microwave dielectric ceramic composition has the advantages that the specific components with specific contents are adopted, so that the microwave dielectric ceramic composition not only has medium and low dielectric constant (15-22 can be continuously adjusted), higher F & ltx & gt Q value (60000- & lt 85000- & gt) and frequency temperature coefficient (within-5 ppm/& lt DEG & gtC) close to zero after being sintered into ceramic, but also has the effect of reducing the sintering temperature (1250 & ltx & gt 1400 ℃) of the ceramic body, and the production cost is reduced.
In the present invention, the content of the main material is typically, but not limited to, 90 wt%, 90.5 wt%, 91 wt%, 91.5 wt%, 92 wt%, 92.5 wt%, 93 wt%, 93.5 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, or 99.5 wt%; the amount of additive is typically, but not limited to, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%. X in the main material is typically, but not limited to, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, or 0.39.
The above-mentioned "main material" means a material that is decisive for the microwave dielectric properties of the microwave dielectric ceramic composition.
In a preferred embodiment, the microwave dielectric ceramic composition comprises the following components in parts by weight: 92-99 wt% of main material and 1-8 wt% of additive;
preferably, the microwave dielectric ceramic composition comprises the following components in percentage by weight: 92.5-97 wt% of main material and 3-7.5 wt% of additive.
A large number of tests and analyses show that when the contents of the main material and the additive are in the preferable range, the obtained ceramic composition has more excellent comprehensive dielectric property after being sintered into ceramic, the frequency temperature coefficient is closer to zero, and the temperature stability is higher.
In a preferred embodiment, CaZrO3The content of (B) is 0.1-0.6 wt%. CaZrO3Typically but not limited to 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt% or 0.6 wt%.
Preferably, Nb2O3The content of (B) is 0.1-7 wt%. Nb2O3Typically but not limited to, 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt% or 7 wt%.
Preferably, TiO2The content of (B) is 0.1-5 wt%. TiO 22Typically but not limited to, 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt% or 5 wt%.
Preferably, the content of NiO is 0.1 to 1 wt%. The amount of NiO is typically, but not limited to, 0.1 wt%, 0.2 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt%, or 1 wt%.
Preferably, Tb4O7The content of (B) is 0.1-0.5 wt%. Tb4O7Typically but not limited to 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt% or 0.5 wt%.
When the content of each additive is within the above range, the effect of adjusting the dielectric properties and sintering temperature of the ceramic composition becomes wider, and the balance between the dielectric properties and sintering temperature of the sintered ceramic becomes higher.
In a preferred embodiment, the additive further comprises MoO3And/or LaAlO3。
Preferably, MoO3Is 0 to 0.5 wt%, excluding 0. MoO3Typically but not limited to 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt% or 0.5 wt%.
Preferably, LaAlO3Is 0 to 3 wt%, excluding 0. LaAlO3In an amount of typically, but not limitingly0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt% or 3 wt%.
MoO3Can further reduce the sintering temperature of the ceramic composition, LaAlO3The dielectric properties can be further adjusted and balanced, enabling a further reduction in the sintering temperature and/or a further improvement in the dielectric properties of the ceramic composition when at least one of the above two substances is included in the additive.
It should be understood that the above additive content refers to the weight percentage of the additive to the total weight of the microwave dielectric ceramic composition.
In a preferred embodiment, the microwave dielectric ceramic composition has a specific surface area of 4 to 8m2(ii) in terms of/g. The above specific surface area is typically, but not limited to, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5 or 8m2(ii) in terms of/g. When the specific surface area of the ceramic composition is within the above range, the subsequent process steps (such as, but not limited to, granulation, molding, sintering, and the like) in preparing the ceramic body are facilitated, the preparation efficiency is improved, and the preparation cost is reduced. The specific surface area refers to the specific surface area obtained by a low-temperature liquid nitrogen adsorption dynamic chromatography test.
According to another aspect of the present invention, there is provided a method for preparing the microwave dielectric ceramic composition, comprising: and mixing the main material and the additive, and then optionally crushing to obtain the microwave dielectric ceramic composition.
The method has simple, scientific and reasonable process, can obtain the microwave dielectric ceramic composition with the required formula, and the ceramic composition not only has medium and low dielectric constant, higher F x Q value and frequency temperature coefficient close to zero after being sintered into ceramic, but also has the function of reducing the sintering temperature of the ceramic body and has lower production cost.
In a preferred embodiment, the main material is prepared by the following method: the main material is obtained by mixing the raw materials and calcining.
Preferably, the raw materials for the main material comprise magnesium compound, calcium compound and Sm2O3And Al2O3. The raw materials have wide sources and low priceThe production cost of the ceramic composition can be reduced.
Preferably, the compound of magnesium comprises MgO, Mg (OH)2Or MgCO3At least one of (1). Compounds of magnesium include, but are not limited to, MgO, Mg (OH)2，MgCO3MgO and Mg (OH)2Combination of MgO and MgCO3Combination of (3), Mg (OH)2And MgCO3Or MgO, Mg (OH)2And MgCO3Combinations of (a), (b), and the like.
Preferably, the compound of calcium comprises CaO, Mg (OH)2Or CaCO3At least one of (1). The calcium compound comprises CaO, Mg (OH)2，CaCO3CaO and Mg (OH)2Combination of (3), Mg (OH)2And CaCO3Combinations of CaO and CaCO3Or CaO, Mg (OH)2And CaCO3Combinations of (a), (b), and the like.
Preferably, the specific surface area of each raw material for the main materials is 8-15m independently2(ii) in terms of/g. The above specific surface area is typically, but not limited to, 8, 9, 10, 11, 12, 13, 14 or 15m2(ii) in terms of/g. The contact area between the raw materials for the main material with the specific surface area is relatively larger, which is beneficial to the full proceeding of the solid phase reaction between the raw materials, leads the raw materials to be completely reacted and improves the Mg contentxCa1-xSmAlO4Yield and purity of (b).
Optionally, the method further comprises a step of crushing after mixing the raw materials for the main material, and then calcining. If the specific surface area of the raw materials for the main material is not up to the requirement (i.e. the preferred 8-15m is not up to)2In terms of/g), it is first comminuted until the desired range is reached.
Optionally, the comminuting comprises: mixing the main material with the first dispersant, and then performing primary ball milling and primary sand milling in sequence until the specific surface area of the mixture reaches 8-15m2/g。
Optionally, the first dispersant is added in an amount of 0.2-2%. The addition amount of the first dispersant accounts for the total weight of the raw materials for the main material. The first dispersant may be added in an amount of 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, or 2%.
Optionally, the ratio of material to water in the primary ball milling and the primary sand milling is 1 (0.4-1.2). The "material-water ratio" refers to the weight ratio of solid material to water, and may be, for example, 1: 0.4, 1: 0.6, 1: 0.8, 1: 1 or 1: 1.2.
optionally, a zirconium ball with the diameter of 0.65mm is selected as a medium for grinding in one-time sanding.
Preferably, the particle size of each additive is less than 300 nm. The particle size of the additive may be, for example, 10, 50, 100, 150, 200, 250 or 300 nm. The grain diameter of the additive is more reasonable, the specific surface area of the additive is larger, and the contact surface with the main material is larger, so that the adjustment effect of the additive on the dielectric property and the sintering temperature of the ceramic composition is stronger.
It should be understood that the higher the purity of the additive, the better, optionally greater than 99.5%.
Preferably, the calcination temperature is 1150-1250 ℃ and the calcination time is 2-5 h. The above calcination temperatures are typically, but not limited to, 1150, 1160, 1170, 1180, 1190, 1200, 1210, 1220, 1230, 1240, or 1250 ℃; the above calcination times are typically, but not limited to, 2, 2.5, 3, 3.5, 4, 4.5 or 5 hours. At the above temperature and time, Mg can be synthesizedxCa1- xSmAlO4And the ceramic has higher activity, and is beneficial to reducing the sintering temperature of a subsequent ceramic body (microwave dielectric ceramic). If the calcining temperature is too low or the calcining time is too short, the target compound cannot be synthesized, and basic support cannot be provided for the performance of the subsequent porcelain body; if the calcination temperature is too high or the calcination time is too long, MgxCa1-xSmAlO4The activity of (2) is reduced, resulting in an excessively high sintering temperature of the porcelain body.
After calcination as described above, MgxCa1-xSmAlO4Has a specific surface area of 1 to 2.5m2/g。
Optionally, the comminuting comprises: mixing MgxCa1-xSmAlO4And the mixture of the additive and the second dispersing agent are mixed, and then secondary ball milling and secondary sand milling are carried out in sequence.
Optionally, the addition of a second dispersantThe amount is 0.5-2%. The "amount added" means that the second dispersant is Mg by weightxCa1-xSmAlO4And the percentage of the total weight of the additive. The second dispersant may be added in an amount of 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8% or 2%.
Optionally, the ratio of material to water in the secondary ball milling and the secondary sanding is 1 (0.4-1). The "material-water ratio" refers to the weight ratio of solid material to water, and may be, for example, 1: 0.4, 1: 0.6, 1: 0.8 or 1: 1.
optionally, a zirconium ball with the diameter of 1.5mm is selected as a medium for secondary sanding. The specific surface area of the ceramic composition after secondary sanding reaches 4-8m2/g。
Optionally, an additive CaZrO3And LaAlO3Can be prepared from outsourcing products or synthesized by self.
CaZrO3The synthesis method of (2) may be, for example: with CaCO3And ZrO2Mixing and grinding the raw materials, calcining for 2-5h at the temperature of 1180-1250 ℃, and then grinding the average particle size to be less than or equal to 300nm by using a sand mill.
LaAlO3The synthesis method of (2) may be, for example: with La2O3And Al2O3Mixing and grinding the raw materials, calcining for 2-5h at the temperature of 1180-1250 ℃, and then grinding the average particle size to be less than or equal to 300nm by using a sand mill.
According to another aspect of the present invention, there is provided a use of the above microwave dielectric ceramic composition in the preparation of microwave dielectric ceramics. The microwave dielectric ceramic composition is applied to the preparation of microwave dielectric ceramics, so that the sintering temperature (1250-.
According to another aspect of the present invention, there is provided a microwave dielectric ceramic prepared using the above microwave dielectric ceramic composition. The microwave dielectric ceramic is prepared by adopting the microwave dielectric ceramic composition, so that the microwave dielectric ceramic at least has the advantages of good dielectric property, low sintering temperature and low cost.
According to another aspect of the present invention, there is provided a method for preparing a microwave dielectric ceramic, comprising: and (3) granulating, molding and sintering the microwave dielectric ceramic composition in sequence to obtain the microwave dielectric ceramic. The method adopts the microwave dielectric ceramic composition as a main raw material for preparation, can effectively reduce the sintering temperature of the ceramic, reduce the production cost and simultaneously ensure that the ceramic has good dielectric property.
Preferably, the binder used for granulation includes PVA, PEG and acrylic acid. PVA: polyvinyl alcohol, Polyvinyl alcohol. PEG: polyethylene glycol, Polyethylene glycol. The adhesive has good adhesion effect, and the formed particles are more regular and have less pits and the like.
It should be understood that, when the PVA and PEG are both solid and the acrylic acid is liquid, and the mixture of the three is used as a binder, the PVA and PEG are dissolved in water (for example, at 65-85 deg.C), and then mixed with the acrylic acid, and the content of the effective component in the binder can be, for example, 10-30 wt%.
Optionally, PVA and PEG are respectively dissolved in water at 65-85 ℃ to prepare PVA glue and PEG glue with the effective component content of 10-30 wt%, then the PVA glue, the PEG glue and acrylic acid are sequentially added into the ceramic slurry, and the mixture is fully stirred to uniformly mix the glue and the ceramic slurry.
Preferably, the total content of PVA, PEG and acrylic acid in the resulting granules after granulation is from 2 to 5% by weight. The total amount is typically, but not limited to, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%.
Optionally, the granulation comprises spray granulation.
Optionally, after granulation, a vibrating sieving machine is used for sieving treatment, powder below 80 meshes and powder above 300 meshes are reserved, and powder above 80 meshes and powder below 300 meshes are discarded or recycled for re-granulation.
Preferably, the sintering temperature is 1250-. The sintering temperature is typically, but not limited to, 1250, 1260, 1270, 1280, 1290, 1300, 1310, 1320, 1330, 1340, 1350, 1360, 1370, 1380, 1390, or 1400 ℃. Sintering at the sintering temperature to obtain compact ceramic body with density up toTo 5.1-5.4g/cm3The ceramic material is not easy to crack, the finished product has high qualification rate and good dielectric property.
According to another aspect of the present invention, there is provided a use of the above microwave dielectric ceramic in the preparation of a microwave device. The microwave dielectric ceramic is applied to the preparation of microwave devices, so that the microwave dielectric property of the microwave devices can be effectively improved, the temperature stability of the microwave devices is improved, and the production cost is reduced.
Preferably, the microwave device comprises a microwave filter or a microwave antenna.
According to another aspect of the present invention, there is provided a microwave device comprising the above microwave dielectric ceramic. The microwave device comprises the microwave dielectric ceramic, so that the microwave dielectric ceramic has the advantages of good microwave dielectric property, high temperature stability and low cost.
Preferably, the microwave device comprises a microwave filter or a microwave antenna.
The present invention will be described in further detail with reference to examples and comparative examples.
Example 1
A microwave dielectric ceramic composition comprises the following components in percentage by weight: 90 wt% of main material and 10 wt% of additive;
the main materials comprise: mg (magnesium)0.2Ca0.8SmAlO4；
The additive comprises: CaZrO31wt％、Nb2O38wt％、TiO20.5 wt%, NiO 0.5 wt% and Tb4O71wt％；
The specific surface area of the microwave dielectric ceramic composition is 3m2/g。
Example 2
A microwave dielectric ceramic composition comprises the following components in percentage by weight: 99.5 wt% of main material and 0.5 wt% of additive;
the main materials comprise: mg (magnesium)0.2Ca0.8SmAlO4；
The additive comprises: CaZrO30.1wt％、Nb2O30.1wt％、TiO20.1 wt%, NiO 0.1 wt% and Tb4O70.1wt％。
Example 3
A microwave dielectric ceramic composition comprises the following components in percentage by weight: 95 wt% of main material and 5 wt% of additive;
the main materials comprise: mg (magnesium)0.2Ca0.8SmAlO4；
The additive comprises: CaZrO31wt％、Nb2O30.5wt％、TiO22 wt%, NiO 1 wt% and Tb4O70.5wt％。
Unlike examples 1 and 2, in this example, the total content of the main material and the total content of the additives were within the preferred range of the present invention, and the respective contents of the additives were different from those of examples 1 and 2.
Example 4
A microwave dielectric ceramic composition, different from example 3, in this example, CaZrO30.5wt％、Nb2O33wt％、TiO21 wt%, NiO 0.3 wt% and Tb4O70.2 wt%. The rest is the same as in example 3.
The content of each additive in this example is within the preferred range of the present invention.
Example 5
A microwave dielectric ceramic composition, different from example 4, in this example, the additives include: CaZrO30.5wt％、Nb2O33wt％、TiO21wt％、NiO 0.2wt％、Tb4O70.2 wt% and MoO30.1 wt%. The rest is the same as in example 4.
The additive in this example also contained MoO3The content of NiO was different from that in example 4.
Example 6
A microwave dielectric ceramic composition, different from example 4, in this example, the additives include: CaZrO30.5wt％、Nb2O33wt％、TiO21wt％、NiO 0.2wt％、Tb4O70.2 wt% and LaAlO30.1 wt%. The rest is the same as in example 4.
The additive in this example also contained LaAlO3The content of NiO was different from that in example 4.
Example 7
A microwave dielectric ceramic composition, different from example 4, in this example, the additives include: CaZrO30.5wt％、Nb2O30.5wt％、TiO20.2wt％、NiO 0.2wt％、Tb4O70.1wt％、MoO30.5 wt% and LaAlO33 wt%. The rest is the same as in example 4.
The additive in this example also contained MoO3And LaAlO3，Nb2O3、TiO2NiO and Tb4O7The content of (a) is different from that of example 4.
Examples 8 to 11
A microwave dielectric ceramic composition, different from example 7, in examples 8-11, the main material includes Mg0.05Ca0.95SmAlO4、Mg0.1Ca0.9SmAlO4、Mg0.3Ca0.7SmAlO4And Mg0.38Ca0.62SmAlO4。
Examples 12 to 14
A microwave dielectric ceramic composition, different from example 7, in examples 12 to 14, the specific surface areas of the microwave dielectric ceramic compositions were 4, 6 and 8m, respectively2/g。
The specific surface areas of the ceramic compositions of examples 12 to 14 are within the preferred range of the present invention.
The preparation method of the microwave dielectric ceramic composition in each embodiment comprises the following steps:
(a) adding MgO, CaCO3、Sm2O3And Al2O3Mixing and calcining to obtain a main material; MgO, CaCO3、Sm2O3And Al2O3Has a specific surface area of 7m2(ii)/g; the calcining temperature is 1280 ℃, and the calcining time is 1.5 h;
(b) and (3) mixing the main material with an additive (the particle size is 350nm) to obtain the microwave dielectric ceramic composition.
Examples 15 to 17
A microwave dielectric ceramic composition, different from example 12, the ceramic compositions of examples 15-17 were prepared using MgO, CaCO3、Sm2O3And Al2O3The specific surface areas of (a) are respectively 8, 12 and 15m2(ii) in terms of/g. The rest is the same as in example 12.
MgO, CaCO in examples 15 to 173、Sm2O3And Al2O3The specific surface area of (b) is within the preferred range of the present invention.
Examples 18 to 19
A microwave dielectric ceramic composition, different from example 17, the ceramic compositions of examples 18-19 were prepared such that the particle sizes of the additives were 100 nm and 300nm, respectively. The rest is the same as in example 17.
The particle size of the additives of examples 18-19 are within the preferred range of the present invention.
Examples 20 to 22
A microwave dielectric ceramic composition, different from example 19, the ceramic compositions of examples 20-21 were prepared at the calcination temperatures of 1150, 1200 and 1250 deg.C, respectively, and the calcination times of 5, 3.5 and 2 hours, respectively. The rest is the same as in example 19.
The calcination temperature and calcination time in examples 20 to 22 were within the preferred ranges of the present invention.
Comparative example 1
A microwave dielectric ceramic composition, different from example 1, in this comparative example, Sr is used as the main material0.2Ca0.8SmAlO4. The rest is the same as in example 1.
Comparative example 2
A microwave dielectric ceramic composition comprises the following components in percentage by weight: 88 wt% of main material and 12 wt% of additive;
the main materials comprise: mg (magnesium)0.2Ca0.8SmAlO4；
The additive comprises: CaZrO31wt％、Nb2O310wt％、TiO20.5wt％NiO 0.5 wt% and Tb4O71wt％；
The specific surface area of the microwave dielectric ceramic composition is 3m2/g。
The rest is the same as in example 1.
Comparative example 3
A microwave dielectric ceramic composition comprises the following components in percentage by weight: 99.8 wt% of main material and 0.2 wt% of additive;
the main materials comprise: mg (magnesium)0.2Ca0.8SmAlO4；
The additive comprises: CaZrO30.05wt％、Nb2O30.05wt％、TiO20.05 wt%, NiO 0.02 wt% and Tb4O70.03wt％；
The specific surface area of the microwave dielectric ceramic composition is 3m2/g。
The rest is the same as in example 1.
The contents of the main material and the additive in comparative examples 2 and 3 were out of the ranges provided by the present invention.
Comparative example 4
A microwave dielectric ceramic composition comprises the following components in percentage by weight: 90 wt% of main material and 10 wt% of additive;
the main materials comprise: mg (magnesium)0.2Ca0.8SmAlO4；
The additive comprises: CaZrO35 wt% and Tb4O75wt％；
The specific surface area of the microwave dielectric ceramic composition is 3m2/g。
No Nb is contained in this comparative example2O3、TiO2And NiO, CaZrO3And Tb4O7The contents of (A) are different from each other, and the rest is the same as example 1.
Comparative example 5
A microwave dielectric ceramic composition comprises the following components in percentage by weight: 90 wt% of main material and 10 wt% of additive;
the main materials comprise: mg (magnesium)0.2Ca0.8SmAlO4；
The additive comprises: nb2O38wt％、TiO21 wt% and NiO 1 wt%;
the specific surface area of the microwave dielectric ceramic composition is 3m2/g。
CaZrO not contained in this comparative example3And Nb2O3，TiO2The contents of NiO and NiO were varied, and the same as in example 1 was repeated.
The microwave dielectric ceramic compositions in the above examples and comparative examples are respectively adopted to prepare microwave dielectric ceramics, and the preparation method comprises the following steps: and (2) sequentially granulating, forming and sintering the microwave medium ceramic compositions to obtain the microwave medium ceramic, wherein binders used for granulating are PVA, PEG and acrylic acid, the total content of the PVA, the PEG and the acrylic acid in the granules obtained after granulation is 4 wt%, and the sintering temperature is 1300 ℃. The dielectric properties of each microwave dielectric ceramic were then tested and the results are shown in table 1.
TABLE 1
Figure BDA0002299516110000181
Figure BDA0002299516110000191
As can be seen from Table 1, the comprehensive dielectric properties of the microwave dielectric ceramics prepared by the embodiments are superior to those of various proportions, so that the microwave dielectric ceramic composition provided by the invention is scientifically and reasonably matched and can effectively improve the dielectric properties of the microwave dielectric ceramics.
As can be seen from FIG. 1, the XRD pattern is similar to that of Mg0.2Ca0.8SmAlO4Are consistent with the standard chart and have no impurity peak, which indicates that the required Mg is obtained0.2Ca0.8SmAlO4. As can be seen from FIG. 2, the ceramic dielectric ceramic composition after granulation yielded spherical or nearly spherical particles with regular morphology and no surface pits. As can be seen from fig. 3 and 4, after the microwave dielectric ceramic composition is sintered into a microwave dielectric ceramic, the surface and the cross section of the ceramic have high denseness and the porosity is extremely low.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (10)

1. A microwave dielectric ceramic composition is characterized by comprising the following components in percentage by weight: 90-99.5 wt% of main material and 0.5-10 wt% of additive;
the main materials comprise: mg (magnesium)xCa1-xSmAlO4Wherein x is more than 0 and less than 0.4;
the additive comprises: CaZrO3、Nb2O3、TiO2NiO and Tb4O7。
2. A microwave dielectric ceramic composition according to claim 1, comprising the following components in amounts: 92-99 wt% of main material and 1-8 wt% of additive;
preferably, the microwave dielectric ceramic composition comprises the following components in percentage by weight: 92.5-97 wt% of main material and 3-7.5 wt% of additive;
preferably, CaZrO3The content of (B) is 0.1-0.6 wt%;
preferably, Nb2O3The content of (B) is 0.1-7 wt%;
preferably, TiO2The content of (B) is 0.1-5 wt%;
preferably, the content of NiO is 0.1-1 wt%;
preferably, Tb4O7The content of (B) is 0.1-0.5 wt%;
preferably, the additive further comprises MoO3And/or LaAlO3；
Preferably, MoO3Is 0 to 0.5 wt%, excluding 0;
preferably, LaAlO3Is 0 to 3 wt%, excluding 0.
3. A microwave dielectric ceramic composition according to claim 1 or 2, wherein the microwave dielectric ceramic composition has a specific surface area of 4 to 8m2/g。
4. A method of making a microwave dielectric ceramic composition as claimed in any one of claims 1 to 3, comprising: and mixing the main material and the additive, and then optionally crushing to obtain the microwave dielectric ceramic composition.
5. The preparation method according to claim 4, wherein the main material is prepared by the following method: mixing the main materials with the raw materials and calcining to obtain the main materials;
preferably, the raw materials for the main material comprise magnesium compound, calcium compound and Sm2O3And Al2O3；
Preferably, the compound of magnesium comprises MgO, Mg (OH)2Or MgCO3At least one of;
preferably, the compound of calcium comprises CaO, Mg (OH)2Or CaCO3At least one of;
preferably, the specific surface area of each raw material for the main materials is 8-15m independently2/g；
Preferably, the particle size of each additive is less than 300 nm;
preferably, the calcination temperature is 1150-1250 ℃ and the calcination time is 2-5 h.
6. Use of the microwave dielectric ceramic composition according to any one of claims 1 to 3 or the microwave dielectric ceramic composition obtained by the preparation method according to claim 4 or 5 for preparing a microwave dielectric ceramic.
7. A microwave dielectric ceramic obtained from the microwave dielectric ceramic composition according to any one of claims 1 to 3 or the microwave dielectric ceramic composition obtained by the production method according to claim 4 or 5.
8. A preparation method of microwave dielectric ceramic is characterized by comprising the following steps: sequentially granulating, forming and sintering the microwave dielectric ceramic composition as claimed in any one of claims 1 to 3 or the microwave dielectric ceramic composition obtained by the preparation method as claimed in claim 4 or 5 to obtain a microwave dielectric ceramic;
preferably, binders used for granulation include PVA, PEG, and acrylic acid;
preferably, the total content of PVA, PEG and acrylic acid in the granules obtained after granulation is from 2 to 5% by weight;
preferably, the sintering temperature is 1250-.
9. Use of the microwave dielectric ceramic of claim 7 or the microwave dielectric ceramic prepared by the method of claim 8 in the preparation of microwave devices;
preferably, the microwave device comprises a microwave filter or a microwave antenna.
10. A microwave device comprising the microwave dielectric ceramic of claim 7 or prepared by the method of claim 8;
preferably, the microwave device comprises a microwave filter or a microwave antenna.
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Denomination of invention: Microwave dielectric ceramic composition and its preparation method and application, microwave dielectric ceramic and its preparation method and application, microwave device

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