CN111763083A - Low-temperature sintered ultralow-loss microwave dielectric ceramic and preparation method and application thereof - Google Patents

Low-temperature sintered ultralow-loss microwave dielectric ceramic and preparation method and application thereof Download PDF

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CN111763083A
CN111763083A CN202010543700.0A CN202010543700A CN111763083A CN 111763083 A CN111763083 A CN 111763083A CN 202010543700 A CN202010543700 A CN 202010543700A CN 111763083 A CN111763083 A CN 111763083A
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dielectric ceramic
microwave dielectric
temperature
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mgtio
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CN111763083B (en
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刘子峰
陈晓敏
徐越
王文利
王娜娜
贺琰
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Suzhou Cheersson Precision Industry Co ltd
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Abstract

The invention discloses a low-temperature sintered microwave dielectric ceramic and a preparation method and application thereof, wherein the method comprises the following steps: mixing the main crystal phase material and the doping material, adding water, ball-milling, drying to prepare premixed powder, mixing the premixed powder with a binder and acetic acid, pouring the premixed powder into a heatable mould, and carrying out temperature programming and sintering under the pressurization condition to prepare the material; controlling the pressure under the pressurizing condition to be 300-400MPa, and carrying out temperature programming to comprise the following stages: raising the temperature from room temperature to 250 ℃ at a certain speed, and preserving the heat; then heating to 450-500 ℃, and preserving heat; the microwave dielectric ceramic prepared by the method and the application thereof in preparing microwave communication devices; the method can prepare the microwave dielectric ceramic material at extremely low sintering temperature, greatly reduces the production cost and the difficulty, and ensures that the prepared material has excellent Q' f value, proper dielectric constant and near-zero temperature coefficient of resonance frequency, thereby meeting the application under the microwave condition.

Description

Low-temperature sintered ultralow-loss microwave dielectric ceramic and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electronic information functional materials and devices, and particularly relates to a microwave dielectric ceramic with medium and low dielectric constant, high quality factor Qxf and resonance frequency temperature coefficient tau f close to zero, a preparation method and application thereof, which can be used for manufacturing microwave devices such as dielectric resonators, filters, duplexers and the like.
Background
The fifth generation (5G) communication will become the mainstream wireless protocol in the fields of mobile phones, WIFI, global positioning systems, intelligent transportation systems, internet of things and the like in the next 10 years. According to the regulations of the world wireless society, the final working frequency band allocated for 5G is 24-30GHz or 60-70 GHz, and the delay time of signal transmission is less than 1 ms. Unlike 2G/3G/4G mobile communication, the carrier frequency of 5G is extended to the millimeter wave band, which has a great influence on the development of microwave dielectric ceramics. In addition, a high quality factor (Q × f) is required to reduce energy loss, and a temperature coefficient of the resonance frequency (τ f) is also required to be almost zero to maintain operation stability.
The microwave dielectric ceramic material is ceramic which is used as a dielectric material in a microwave frequency band circuit and completes one or more functions. The material is widely used as microwave components such as resonators, filters, dielectric substrates, dielectric guided wave loops and the like in modern communication, and is a key basic material of modern communication technology. At present, microwave dielectric ceramic materials are applied to portable mobile phones, television satellite receivers, military radars and the like, and play an increasingly important role in the miniaturization and integration processes of modern communication tools.
The material is the basis of the device, and with the development of microwave dielectric ceramic devices, the corresponding dielectric ceramic applied to the microwave frequency band mainly meets the following requirements: the dielectric constant is proper to facilitate the miniaturization of the device and the signal transmission speed, the Q multiplied by f value is ultrahigh, and the temperature coefficient of the resonant frequency is close to zero.
Magnesium metatitanate is an important microwave dielectric ceramic material, and is abundant in raw materials and low in cost, so that the magnesium metatitanate is concerned by people, is one of microwave dielectric ceramic materials which are most widely applied at present, and can be used for manufacturing thermal compensation capacitors, multilayer ceramic capacitors, dielectric filters, dielectric resonators and the like. Known as MgTiO3The dielectric properties of (1) are r 17, Q × f 160,000GHz, τ f-50 ppm/DEG C, and because the temperature coefficient of resonance frequency is negative, CaTiO is generally adopted3Adjusting to approach zero, CaTiO3The MCT system ceramic with the dielectric properties of r 170, Q × f 3500GHz and tau f +800 ppm/DEG C is a good microwave dielectric ceramic material, but the CaTiO system ceramic is a good microwave dielectric ceramic material3The existing method can not meet the requirements of low insertion loss microwave devices, and the sintering temperature of the system is 1400-1450 ℃, the sintering temperature is high, the sintering cost is high, and the application of MCT system ceramic materials is limited.
Disclosure of Invention
The invention aims to overcome one or more defects in the prior art and provide an improved preparation method of ultralow-loss microwave dielectric ceramic, the method can prepare the microwave dielectric ceramic material at an extremely low sintering temperature, and the prepared microwave dielectric ceramic material has an excellent Qxf value, a proper dielectric constant and a near-zero resonant frequency temperature coefficient and meets the use requirements under the microwave condition.
The invention also provides the microwave dielectric ceramic prepared by the method.
The invention also provides the application of the microwave dielectric ceramic prepared by the method in the preparation of microwave communication devices.
In order to achieve the purpose, the invention adopts a technical scheme that:
a process for preparing low-temp sintered microwave dielectric ceramic whose main crystal phase material contains MgTiO3、CaTiO3(ii) a To be provided withThe MgTiO is contained in the main crystal phase material according to mol percentage390-98mol% of the CaTiO32-10mol% of the total;
the microwave dielectric ceramic also comprises a doping material, wherein the doping material accounts for 0.001-0.45mol% of the main crystal phase material in terms of mol%, and comprises Nb2O5；
The preparation method of the microwave dielectric ceramic comprises the following steps:
(1) mixing the main crystal phase material and the doping material according to the formula amount, adding water, ball-milling and drying to prepare premixed powder;
(2) mixing the premixed powder, a binder for preparing the microwave dielectric ceramic and acetic acid, pouring the mixture into a heatable mould, and carrying out temperature programming and sintering under a pressurized condition to prepare the microwave dielectric ceramic, wherein the microwave dielectric ceramic comprises the following chemical components: (1-x) MgTiO3-xCaTiO3-yNb2O5，0.02≤x≤0.1，0.00001≤y≤0.0045；
Wherein the pressure under the pressurization condition is controlled to be 300-400MPa, and the programmed temperature rise comprises the following stages: heating from room temperature to 250 ℃ at the speed of 1-4 ℃/min, and preserving heat; then heating from 150-250 ℃ to 450-500 ℃ at a speed of 3-8 ℃/min, and preserving the heat.
According to some preferred aspects of the present invention, in the step (1), the mass ratio of the materials, the ball milling beads and the water during the ball milling process is controlled to be 1: 2-4: 1.1-1.6. More preferably, in the step (1), the mass ratio of the materials, the ball milling beads and the water in the ball milling process is controlled to be 1: 2.5-3.5: 1.3-1.6. According to a specific aspect of the invention, in the step (1), the mass ratio of the materials, the ball milling beads and the water in the ball milling process is controlled to be 1:3: 1.5.
According to a preferred aspect of the present invention, in the step (1), the main crystal phase material is formed of MgTiO3And CaTiO3And (4) forming.
In some embodiments of the invention, the MgTiO is3Is prepared by the following steps: weighing magnesium element-containing salt or oxide thereof, titanium element-containing salt or oxide thereof, and adding waterBall milling, filtering and drying, presintering at the temperature of 1000-1150 ℃ to prepare the material.
In some embodiments of the invention, the CaTiO is3Is prepared by the following steps: weighing salt or oxide thereof containing calcium element, salt or oxide thereof containing titanium element, adding water, ball milling, filtering, drying, presintering at 1000-1150 deg.C to obtain the final product.
According to some preferred aspects of the present invention, in step (2), the pressure under the pressurization condition is controlled to be 300-: heating from room temperature to 180-220 ℃ at the speed of 2-4 ℃/min, and preserving heat; then raising the temperature from 220 ℃ at the speed of 4-6 ℃/min to 500 ℃ at the speed of 480 ℃ and preserving the temperature. According to a specific aspect of the present invention, in step (2), the pressure under the pressurization condition is controlled to be 300MPa, and the temperature programming includes the following stages: heating from room temperature to 200 ℃ at the speed of 3 ℃/min, and preserving heat; then the temperature is raised from 200 ℃ to 500 ℃ at the speed of 5 ℃/min, and the temperature is preserved.
According to some specific and preferred aspects of the present invention, in the step (2), the binder for preparing the microwave dielectric ceramic is polyvinyl alcohol, and the polyvinyl alcohol is added in the form of an aqueous solution of polyvinyl alcohol, and the polyvinyl alcohol is added in an amount of 5 to 15% by mass of the premixed powder.
According to some preferred aspects of the present invention, in the step (2), the acetic acid is added in the form of an aqueous solution of acetic acid, and the amount of the acetic acid added is 10 to 20% by mass of the premixed powder. In the invention, acetic acid is added into the materials before temperature rise sintering, which is beneficial to reducing the sintering temperature.
In some embodiments of the present invention, in the step (2), the material obtained by mixing the premixed powder and the binder for preparing microwave dielectric ceramics is sieved, and the sieved material is mixed with the acetic acid and poured into a heatable mold.
The invention provides another technical scheme that: the microwave dielectric ceramic is prepared by the preparation method of the low-temperature sintering type microwave dielectric ceramic.
The invention provides another technical scheme that: an application of the microwave dielectric ceramic in the preparation of microwave communication devices.
The dielectric property of the microwave dielectric ceramic material can meet the following parameter requirements, the dielectric constant r is 19.2-21.5, the Q multiplied by f can be higher than 60000Ghz, and tau f is approximately equal to 0 +/-2.5 ppm/DEG C.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the method for preparing the microwave dielectric ceramic has simple process, low production cost and easy realization, particularly can realize low-temperature sintering, greatly reduces the production cost and the production difficulty, and the prepared microwave dielectric ceramic material obtains ideal Qxf value, nearly zero tau f value and proper dielectric constant and can meet the use requirement under the microwave condition.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
Not specifically illustrated in the following examples, all starting materials are commercially available or prepared by methods conventional in the art.
Example 1
This example provides a microwave dielectric ceramic with a chemical composition of 95MgTiO3-5CaTiO3-0.1Nb2O5The preparation method comprises the following steps:
(1) preparation of MgTiO3Powder and CaTiO3Powder body
MgO and TiO as raw materials2Proportioning materials according to a stoichiometric ratio of 1:1, putting the materials obtained by proportioning, ball milling beads and pure water into a ball mill according to a mass ratio of 1:3:1.5 for wet ball milling, wherein the ball milling time is 10 hours, the rotating speed is 180r/min, obtaining slurry-like raw materials, putting the obtained slurry-like raw materials into an oven, drying the slurry-like raw materials at 100 ℃ to constant weight, obtaining dry mixed materials, and mixing the obtained materialsSieving the material with a 60-mesh sieve for dispersion, and presintering the material in a high-temperature furnace for 2 hours at the presintering temperature of 1100 ℃ to obtain MgTiO3Powder;
raw material CaCO3、TiO2Proportioning according to a stoichiometric ratio of 1:1, putting the materials obtained by proportioning, ball milling beads and pure water in a ball mill according to a mass ratio of 1:3:1.5 for wet ball milling, wherein the ball milling time is 10 hours, the rotating speed is 180r/min, obtaining slurry-like raw materials, putting the obtained slurry-like raw materials into an oven, drying at 100 ℃ to constant weight, obtaining dry mixed materials, sieving the obtained mixed materials with a 60-mesh sieve for dispersing, then putting the mixed materials into a high-temperature furnace for presintering for 2 hours at the presintering temperature of 1100 ℃, and obtaining CaTiO3And (3) powder.
(2) MgTiO prepared in the step (1)3Powder, CaTiO3Powder and Nb2O5Mixing the powder according to a molar ratio of 95:5:0.1, adding pure water, and putting the materials, the ball milling beads and the pure water in a ball mill according to a mass ratio of 1:3:1.5 for grinding for 10 hours to form premixed slurry; drying the obtained premixed slurry in an oven at 100 ℃ to constant weight to obtain premixed powder, sieving the premixed powder by a 60-mesh standard sieve, adding a polyvinyl alcohol solution (containing polyvinyl alcohol accounting for 10 wt% of the premixed powder) into the sieved material, uniformly mixing, and sieving by the 60-mesh standard sieve; adding acetic acid solution (containing acetic acid 10 wt% of the premixed powder) into the sieved material, stirring to obtain paste, pouring into a heatable mold with diameter of 15mm, setting a pressurizing program, pressurizing to 300MPa, heating the pressurized mold to 200 ℃ at a speed of 3 ℃/min under the pressure condition, preserving heat for 1h, heating to 500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling with a furnace to obtain the microwave dielectric ceramic 95MgTiO3-5CaTiO3-0.1Nb2O5。
And (3) later-stage mechanical processing: sintered 95MgTiO3-5CaTiO3-0.1Nb2O5And grinding and polishing the ceramic to obtain a ceramic finished product with a flat and smooth surface, and testing the microwave dielectric property of the cylindrical ceramic at the resonant frequency by adopting a Keysight E5232B vector network analyzer.
Example 2
This example provides a microwave dielectric ceramic having a chemical composition of 95MgTiO3-5CaTiO3-0.2Nb2O5The preparation method comprises the following steps:
(1) preparation of MgTiO3Powder and CaTiO3Powder body
MgO and TiO as raw materials2Proportioning according to a stoichiometric ratio of 1:1, putting the materials obtained by proportioning, ball milling beads and pure water in a ball mill according to a mass ratio of 1:3:1.5 for wet ball milling, wherein the ball milling time is 10 hours, the rotating speed is 180r/min, obtaining slurry-like raw materials, putting the obtained slurry-like raw materials into an oven, drying the slurry-like raw materials at 100 ℃ to constant weight, obtaining dry mixed materials, sieving the obtained mixed materials with a 60-mesh sieve for dispersing, then putting the mixed materials into a high-temperature furnace for presintering for 2 hours at the presintering temperature of 1100 ℃, and obtaining MgTiO3Powder;
raw material CaCO3、TiO2Proportioning according to a stoichiometric ratio of 1:1, putting the materials obtained by proportioning, ball milling beads and pure water in a ball mill according to a mass ratio of 1:3:1.5 for wet ball milling, wherein the ball milling time is 10 hours, the rotating speed is 180r/min, obtaining slurry-like raw materials, putting the obtained slurry-like raw materials into an oven, drying at 100 ℃ to constant weight, obtaining dry mixed materials, sieving the obtained mixed materials with a 60-mesh sieve for dispersing, then putting the mixed materials into a high-temperature furnace for presintering for 2 hours at the presintering temperature of 1100 ℃, and obtaining CaTiO3And (3) powder.
(2) MgTiO prepared in the step (1)3Powder, CaTiO3Powder and Nb2O5Mixing the powder according to a molar ratio of 95:5:0.2, adding pure water, and putting the materials, the ball milling beads and the pure water in a ball mill according to a mass ratio of 1:3:1.5 for grinding for 10 hours to form premixed slurry; drying the obtained premixed slurry in an oven at 100 ℃ to constant weight to obtain premixed powder, sieving the premixed powder by a 60-mesh standard sieve, adding a polyvinyl alcohol solution (containing polyvinyl alcohol accounting for 10 wt% of the premixed powder) into the sieved material, uniformly mixing, and sieving by the 60-mesh standard sieve; adding acetic acid solution (containing acetic acid 10 wt% of the premixed powder), stirring to obtain paste, pouring into a heatable mold with diameter of 15mm, setting pressurizing program, pressurizing to 300MPa, heating the pressurized mold to 200 deg.C at 3 deg.C/min under the pressure condition, maintaining for 1 hr, and heating to 500 deg.C at 5 deg.C/minKeeping the temperature at 2h, and then cooling the product along with the furnace to obtain the microwave dielectric ceramic 95MgTiO3-5CaTiO3-0.2Nb2O5。
And (3) later-stage mechanical processing: sintered 95MgTiO3-5CaTiO3-0.2Nb2O5And grinding and polishing the ceramic to obtain a ceramic finished product with a flat and smooth surface, and testing the microwave dielectric property of the cylindrical ceramic at the resonant frequency by adopting a Keysight E5232B vector network analyzer.
Example 3
This example provides a microwave dielectric ceramic with a chemical composition of 95MgTiO3-5CaTiO3-0.25Nb2O5The preparation method comprises the following steps:
(1) preparation of MgTiO3Powder and CaTiO3Powder body
MgO and TiO as raw materials2Proportioning according to a stoichiometric ratio of 1:1, putting the materials obtained by proportioning, ball milling beads and pure water in a ball mill according to a mass ratio of 1:3:1.5 for wet ball milling, wherein the ball milling time is 10 hours, the rotating speed is 180r/min, obtaining slurry-like raw materials, putting the obtained slurry-like raw materials into an oven, drying the slurry-like raw materials at 100 ℃ to constant weight, obtaining dry mixed materials, sieving the obtained mixed materials with a 60-mesh sieve for dispersing, then putting the mixed materials into a high-temperature furnace for presintering for 2 hours at the presintering temperature of 1100 ℃, and obtaining MgTiO3Powder;
raw material CaCO3、TiO2Proportioning according to a stoichiometric ratio of 1:1, putting the materials obtained by proportioning, ball milling beads and pure water in a ball mill according to a mass ratio of 1:3:1.5 for wet ball milling, wherein the ball milling time is 10 hours, the rotating speed is 180r/min, obtaining slurry-like raw materials, putting the obtained slurry-like raw materials into an oven, drying at 100 ℃ to constant weight, obtaining dry mixed materials, sieving the obtained mixed materials with a 60-mesh sieve for dispersing, then putting the mixed materials into a high-temperature furnace for presintering for 2 hours at the presintering temperature of 1100 ℃, and obtaining CaTiO3And (3) powder.
(2) MgTiO prepared in the step (1)3Powder, CaTiO3Powder and Nb2O5Mixing the powder according to a molar ratio of 95:5:0.25, adding pure water, and placing the materials, the ball milling beads and the pure water into a ball according to a mass ratio of 1:3:1.5Grinding for 10 hours in a grinder to form premixed slurry; drying the obtained premixed slurry in an oven at 100 ℃ to constant weight to obtain premixed powder, sieving the premixed powder by a 60-mesh standard sieve, adding a polyvinyl alcohol solution (containing polyvinyl alcohol accounting for 10 wt% of the premixed powder) into the sieved material, uniformly mixing, and sieving by the 60-mesh standard sieve; adding acetic acid solution (containing acetic acid 10 wt% of the premixed powder) into the sieved material, stirring to obtain paste, pouring into a heatable mold with diameter of 15mm, setting a pressurizing program, pressurizing to 300MPa, heating the pressurized mold to 200 ℃ at a speed of 3 ℃/min under the pressure condition, preserving heat for 1h, heating to 500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling with a furnace to obtain the microwave dielectric ceramic 95MgTiO3-5CaTiO3-0.25Nb2O5。
And (3) later-stage mechanical processing: sintered 95MgTiO3-5CaTiO3-0.25Nb2O5And grinding and polishing the ceramic to obtain a ceramic finished product with a flat and smooth surface, and testing the microwave dielectric property of the cylindrical ceramic at the resonant frequency by adopting a Keysight E5232B vector network analyzer.
Example 4
This example provides a microwave dielectric ceramic with a chemical composition of 95MgTiO3-5CaTiO3-0.35Nb2O5The preparation method comprises the following steps:
(1) preparation of MgTiO3Powder and CaTiO3Powder body
MgO and TiO as raw materials2Proportioning according to a stoichiometric ratio of 1:1, putting the materials obtained by proportioning, ball milling beads and pure water in a ball mill according to a mass ratio of 1:3:1.5 for wet ball milling, wherein the ball milling time is 10 hours, the rotating speed is 180r/min, obtaining slurry-like raw materials, putting the obtained slurry-like raw materials into an oven, drying the slurry-like raw materials at 100 ℃ to constant weight, obtaining dry mixed materials, sieving the obtained mixed materials with a 60-mesh sieve for dispersing, then putting the mixed materials into a high-temperature furnace for presintering for 2 hours at the presintering temperature of 1100 ℃, and obtaining MgTiO3Powder;
raw material CaCO3、TiO2Proportioning the materials according to the stoichiometric ratio of 1:1, and mixing the materials, the ball milling beads and the pure water according to the mass ratio of 1:3:1.5Performing wet ball milling in a ball mill for 10h at a rotation speed of 180r/min to obtain slurry raw material, drying the slurry raw material in an oven at 100 ℃ to constant weight to obtain dry mixture, sieving the mixture with a 60-mesh sieve for dispersion, and presintering in a high temperature furnace for 2h at a presintering temperature of 1100 ℃ to obtain CaTiO3And (3) powder.
(2) MgTiO prepared in the step (1)3Powder, CaTiO3Powder and Nb2O5Mixing the powder according to a molar ratio of 95:5:0.35, adding pure water, and putting the materials, the ball milling beads and the pure water in a ball mill according to a mass ratio of 1:3:1.5 for grinding for 10 hours to form premixed slurry; drying the obtained premixed slurry in an oven at 100 ℃ to constant weight to obtain premixed powder, sieving the premixed powder by a 60-mesh standard sieve, adding a polyvinyl alcohol solution (containing polyvinyl alcohol accounting for 10 wt% of the premixed powder) into the sieved material, uniformly mixing, and sieving by the 60-mesh standard sieve; adding acetic acid solution (containing acetic acid accounting for 15 wt% of the premixed powder) into the sieved material, stirring uniformly to form paste, pouring the paste into a heatable mold with the diameter of 15mm, setting a pressurizing program, pressurizing to 300MPa, heating the pressurized mold to 200 ℃ at the speed of 3 ℃/min under the pressure condition, preserving heat for 1h, heating to 500 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and cooling with a furnace to obtain the microwave dielectric ceramic 95MgTiO3-5CaTiO3-0.35Nb2O5。
And (3) later-stage mechanical processing: sintered 95MgTiO3-5CaTiO3-0.35Nb2O5And grinding and polishing the ceramic to obtain a ceramic finished product with a flat and smooth surface, and testing the microwave dielectric property of the cylindrical ceramic at the resonant frequency by adopting a Keysight E5232B vector network analyzer.
Example 5
This example provides a microwave dielectric ceramic with a chemical composition of 95MgTiO3-5CaTiO3-0.45Nb2O5The preparation method comprises the following steps:
(1) preparation of MgTiO3Powder and CaTiO3Powder body
MgO and TiO as raw materials2Proportioning according to the stoichiometric ratio of 1:1,putting the materials obtained by proportioning, ball milling beads and pure water into a ball mill according to the mass ratio of 1:3:1.5 for wet ball milling, wherein the ball milling time is 10 hours, the rotating speed is 180r/min, obtaining slurry-like raw materials, putting the obtained slurry-like raw materials into an oven, drying the slurry-like raw materials at 100 ℃ to constant weight, obtaining dry mixed materials, sieving the obtained mixed materials by a 60-mesh sieve, dispersing the mixed materials, putting the mixture into a high-temperature furnace, presintering for 2 hours, and the presintering temperature is 1100 ℃, thus obtaining MgTiO3Powder;
raw material CaCO3、TiO2Proportioning according to a stoichiometric ratio of 1:1, putting the materials obtained by proportioning, ball milling beads and pure water in a ball mill according to a mass ratio of 1:3:1.5 for wet ball milling, wherein the ball milling time is 10 hours, the rotating speed is 180r/min, obtaining slurry-like raw materials, putting the obtained slurry-like raw materials into an oven, drying at 100 ℃ to constant weight, obtaining dry mixed materials, sieving the obtained mixed materials with a 60-mesh sieve for dispersing, then putting the mixed materials into a high-temperature furnace for presintering for 2 hours at the presintering temperature of 1100 ℃, and obtaining CaTiO3And (3) powder.
(2) MgTiO prepared in the step (1)3Powder, CaTiO3Powder and Nb2O5Mixing the powder according to a molar ratio of 95:5:0.45, adding pure water, and putting the materials, the ball milling beads and the pure water in a ball mill according to a mass ratio of 1:3:1.5 for grinding for 10 hours to form premixed slurry; drying the obtained premixed slurry in an oven at 100 ℃ to constant weight to obtain premixed powder, sieving the premixed powder by a 60-mesh standard sieve, adding a polyvinyl alcohol solution (containing polyvinyl alcohol accounting for 10 wt% of the premixed powder) into the sieved material, uniformly mixing, and sieving by the 60-mesh standard sieve; adding acetic acid solution (containing acetic acid accounting for 15 wt% of the premixed powder) into the sieved material, stirring uniformly to form paste, pouring the paste into a heatable mold with the diameter of 15mm, setting a pressurizing program, pressurizing to 300MPa, heating the pressurized mold to 200 ℃ at the speed of 3 ℃/min under the pressure condition, preserving heat for 1h, heating to 500 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and cooling with a furnace to obtain the microwave dielectric ceramic 95MgTiO3-5CaTiO3-0.45Nb2O5。
And (3) later-stage mechanical processing: sintered 95MgTiO3-5CaTiO3-0.45Nb2O5The ceramic is ground and polished to obtain a polished ceramic,and (3) obtaining a ceramic finished product with a smooth surface, and testing the microwave dielectric property of the cylindrical ceramic at the resonant frequency by adopting a Keysight E5232B vector network analyzer.
Example 6
This example provides a microwave dielectric ceramic with a chemical composition of 96MgTiO3-4CaTiO3-0.15Nb2O5The preparation method comprises the following steps:
(1) preparation of MgTiO3Powder and CaTiO3Powder body
MgO and TiO as raw materials2Proportioning according to a stoichiometric ratio of 1:1, putting the materials obtained by proportioning, ball milling beads and pure water in a ball mill according to a mass ratio of 1:3:1.5 for wet ball milling, wherein the ball milling time is 10 hours, the rotating speed is 180r/min, obtaining slurry-like raw materials, putting the obtained slurry-like raw materials into an oven, drying the slurry-like raw materials at 100 ℃ to constant weight, obtaining dry mixed materials, sieving the obtained mixed materials with a 60-mesh sieve for dispersing, then putting the mixed materials into a high-temperature furnace for presintering for 2 hours at the presintering temperature of 1100 ℃, and obtaining MgTiO3Powder;
raw material CaCO3、TiO2Proportioning according to a stoichiometric ratio of 1:1, putting the materials obtained by proportioning, ball milling beads and pure water in a ball mill according to a mass ratio of 1:3:1.5 for wet ball milling, wherein the ball milling time is 10 hours, the rotating speed is 180r/min, obtaining slurry-like raw materials, putting the obtained slurry-like raw materials into an oven, drying at 100 ℃ to constant weight, obtaining dry mixed materials, sieving the obtained mixed materials with a 60-mesh sieve for dispersing, then putting the mixed materials into a high-temperature furnace for presintering for 2 hours at the presintering temperature of 1100 ℃, and obtaining CaTiO3And (3) powder.
(2) MgTiO prepared in the step (1)3Powder, CaTiO3Powder and Nb2O5Mixing the powder according to a molar ratio of 96:4:0.15, adding pure water, and putting the materials, the ball milling beads and the pure water in a ball mill according to a mass ratio of 1:3:1.5 for grinding for 10 hours to form premixed slurry; drying the obtained premixed slurry in an oven at 100 ℃ to constant weight to obtain premixed powder, sieving the premixed powder by a 60-mesh standard sieve, adding a polyvinyl alcohol solution (containing polyvinyl alcohol accounting for 9 wt% of the premixed powder) into the sieved material, uniformly mixing, and sieving by the 60-mesh standard sieve; taking, screening and blankingAdding acetic acid solution (containing acetic acid accounting for 15 wt% of the premixed powder), stirring uniformly to obtain paste, pouring into a heatable mold with diameter of 15mm, setting a pressurizing program, pressurizing to 300MPa, heating the pressurized mold to 200 ℃ at a speed of 3 ℃/min under the pressure condition, preserving heat for 1h, heating to 500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling with a furnace to obtain the microwave dielectric ceramic 96MgTiO3-4CaTiO3-0.15Nb2O5。
And (3) later-stage mechanical processing: the sintered 96MgTiO is sintered3-4CaTiO3-0.15Nb2O5And grinding and polishing the ceramic to obtain a ceramic finished product with a flat and smooth surface, and testing the microwave dielectric property of the cylindrical ceramic at the resonant frequency by adopting a Keysight E5232B vector network analyzer.
Example 7
This example provides a microwave dielectric ceramic with a chemical composition of 97MgTiO3-3CaTiO3-0.15Nb2O5The preparation method comprises the following steps:
(1) preparation of MgTiO3Powder and CaTiO3Powder body
MgO and TiO as raw materials2Proportioning according to a stoichiometric ratio of 1:1, putting the materials obtained by proportioning, ball milling beads and pure water in a ball mill according to a mass ratio of 1:3:1.5 for wet ball milling, wherein the ball milling time is 10 hours, the rotating speed is 180r/min, obtaining slurry-like raw materials, putting the obtained slurry-like raw materials into an oven, drying the slurry-like raw materials at 100 ℃ to constant weight, obtaining dry mixed materials, sieving the obtained mixed materials with a 60-mesh sieve for dispersing, then putting the mixed materials into a high-temperature furnace for presintering for 2 hours at the presintering temperature of 1100 ℃, and obtaining MgTiO3Powder;
raw material CaCO3、TiO2Proportioning according to a stoichiometric ratio of 1:1, putting the materials obtained by proportioning, ball milling beads and pure water in a ball mill according to a mass ratio of 1:3:1.5 for wet ball milling, wherein the ball milling time is 10 hours, the rotating speed is 180r/min, obtaining slurry-like raw materials, putting the obtained slurry-like raw materials into an oven, drying at 100 ℃ to constant weight, obtaining dry mixed materials, sieving the obtained mixed materials by a 60-mesh sieve for dispersion, then putting the mixed materials into a high-temperature furnace for presintering for 2 hours at the presintering temperature of 1100 ℃, and preparing the mixed materials into the slurry-like raw materialsTo obtain CaTiO3And (3) powder.
(2) MgTiO prepared in the step (1)3Powder, CaTiO3Powder and Nb2O5Mixing the powder according to a molar ratio of 97:3:0.15, adding pure water, and putting the materials, the ball milling beads and the pure water in a ball mill according to a mass ratio of 1:3:1.5 for grinding for 10 hours to form premixed slurry; drying the obtained premixed slurry in an oven at 100 ℃ to constant weight to obtain premixed powder, sieving the premixed powder by a 60-mesh standard sieve, adding a polyvinyl alcohol solution (containing polyvinyl alcohol accounting for 8.5 wt% of the premixed powder) into the sieved material, uniformly mixing, and sieving by the 60-mesh standard sieve; adding acetic acid solution (containing acetic acid accounting for 15 wt% of the premixed powder) into the sieved material, stirring uniformly to form paste, pouring the paste into a heatable mold with the diameter of 15mm, setting a pressurizing program, pressurizing to 300MPa, heating the pressurized mold to 200 ℃ at the speed of 3 ℃/min under the pressure condition, preserving heat for 1h, heating to 500 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and cooling with a furnace to obtain the microwave dielectric ceramic 97MgTiO3-3CaTiO3-0.15Nb2O5。
And (3) later-stage mechanical processing: the sintered 97MgTiO is sintered3-3CaTiO3-0.15Nb2O5And grinding and polishing the ceramic to obtain a ceramic finished product with a flat and smooth surface, and testing the microwave dielectric property of the cylindrical ceramic at the resonant frequency by adopting a Keysight E5232B vector network analyzer.
Example 8
This example provides a microwave dielectric ceramic with a chemical composition of 92MgTiO3-8CaTiO3-0.15Nb2O5The preparation method comprises the following steps:
(1) preparation of MgTiO3Powder and CaTiO3Powder body
MgO and TiO as raw materials2Proportioning according to a stoichiometric ratio of 1:1, putting the materials obtained by proportioning, ball milling beads and pure water in a ball mill according to a mass ratio of 1:3:1.5 for wet ball milling for 10 hours at a rotating speed of 180r/min to obtain a slurry raw material, putting the slurry raw material in an oven, drying at 100 ℃ to constant weight to obtain a dry mixture, sieving the obtained mixture with a 60-mesh sieveDispersing, presintering in a high temperature furnace at 1100 deg.C for 2 hr to obtain MgTiO3Powder;
raw material CaCO3、TiO2Proportioning according to a stoichiometric ratio of 1:1, putting the materials obtained by proportioning, ball milling beads and pure water in a ball mill according to a mass ratio of 1:3:1.5 for wet ball milling, wherein the ball milling time is 10 hours, the rotating speed is 180r/min, obtaining slurry-like raw materials, putting the obtained slurry-like raw materials into an oven, drying at 100 ℃ to constant weight, obtaining dry mixed materials, sieving the obtained mixed materials with a 60-mesh sieve for dispersing, then putting the mixed materials into a high-temperature furnace for presintering for 2 hours at the presintering temperature of 1100 ℃, and obtaining CaTiO3And (3) powder.
(2) MgTiO prepared in the step (1)3Powder, CaTiO3Powder and Nb2O5Mixing the powder according to a molar ratio of 92:8:0.15, adding pure water, and putting the materials, the ball milling beads and the pure water in a ball mill according to a mass ratio of 1:3:1.5 for grinding for 10 hours to form premixed slurry; drying the obtained premixed slurry in an oven at 100 ℃ to constant weight to obtain premixed powder, sieving the premixed powder by a 60-mesh standard sieve, adding a polyvinyl alcohol solution (containing 7 wt% of polyvinyl alcohol in the premixed powder) into the sieved material, uniformly mixing, and sieving by the 60-mesh standard sieve; adding acetic acid solution (containing acetic acid accounting for 15 wt% of the premixed powder) into the sieved material, stirring uniformly to form paste, pouring the paste into a heatable mold with the diameter of 15mm, setting a pressurizing program, pressurizing to 300MPa, heating the pressurized mold to 200 ℃ at the speed of 3 ℃/min under the pressure condition, preserving heat for 1h, heating to 500 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and cooling with a furnace to obtain the microwave dielectric ceramic 92MgTiO3-8CaTiO3-0.15Nb2O5。
And (3) later-stage mechanical processing: sintered 92MgTiO3-8CaTiO3-0.15Nb2O5And grinding and polishing the ceramic to obtain a ceramic finished product with a flat and smooth surface, and testing the microwave dielectric property of the cylindrical ceramic at the resonant frequency by adopting a Keysight E5232B vector network analyzer.
Comparative example 1
Basically, the method is the same as the method in the embodiment 3, and the method only differs from the method in that: the pressure conditions were replaced with "set pressurization program, pressurization to 200 MPa".
Comparative example 2
Basically, the method is the same as the method in the embodiment 3, and the method only differs from the method in that: the pressure condition is replaced by 'no pressurization', namely, the temperature rise is carried out under the condition of normal pressure.
Comparative example 3
Basically, the method is the same as the method in the embodiment 3, and the method only differs from the method in that: the step of heating to 500 ℃ at the speed of 5 ℃/min and keeping the temperature for 2h is replaced by the step of heating to 300 ℃ at the speed of 5 ℃/min and keeping the temperature for 2 h.
Comparative example 4
Basically, the method is the same as the method in the embodiment 3, and the method only differs from the method in that: the pressure condition is replaced by a set pressurizing program, the pressure is increased to 200MPa, the temperature is increased to 500 ℃ at the speed of 5 ℃/min and is kept for 2h, and the temperature is increased to 400 ℃ at the speed of 5 ℃/min and is kept for 2 h.
Comparative example 5
Basically, the method is the same as the method in the embodiment 3, and the method only differs from the method in that: no acetic acid solution is added in the step (2).
Performance testing
Grinding and polishing the microwave dielectric ceramics obtained in the above examples 1 to 5 and comparative examples 1 to 5 to obtain a ceramic finished product with a smooth surface, and testing the microwave dielectric properties of the cylindrical ceramic at the resonance frequency by using a Keysight E5232B vector network analyzer as shown in the following Table 1 (dielectric constant test System (dielectric resonator method))f)：
TABLE 1
Numbering Bulk density g/cm3 εr Q×f Ghz τf ppm/℃
Example 1 3.91 19.2 53250 2.32
Example 2 3.93 20.3 57895 2.30
Example 3 3.95 21.5 57585 2.31
Example 4 3.94 20.8 60431 2.28
Example 5 3.93 19.5 55168 2.30
Comparative example 1 3.81 18.7 11256 2.33
Comparative example 2 3.87 19.2 5256 2.31
Comparative example 3 3.90 19.9 9656 2.32
Comparative example 4 3.89 18.9 3251 2.33
Comparative example 5 4.10 18.1 1035 5.66
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

Claims (10)

1. A process for preparing low-temp sintered microwave dielectric ceramic whose main crystal phase material contains MgTiO3、CaTiO3Characterized in that the MgTiO is contained in the main crystal phase material according to mol percentage390-98mol% of the CaTiO32-10mol% of the total;
the microwave dielectric ceramic also comprises a doping material, wherein the doping material accounts for 0.001-0.45mol% of the main crystal phase material in terms of mol%, and comprises Nb2O5；
The preparation method of the microwave dielectric ceramic comprises the following steps:
(1) mixing the main crystal phase material and the doping material according to the formula amount, adding water, ball-milling and drying to prepare premixed powder;
(2) mixing the premixed powder, a binder for preparing the microwave dielectric ceramic and acetic acid, pouring the mixture into a heatable mould, and carrying out temperature programming and sintering under a pressurized condition to prepare the microwave dielectric ceramic, wherein the microwave dielectric ceramic comprises the following chemical components: (1-x) MgTiO3-xCaTiO3-yNb2O5，0.02≤x≤0.1，0.00001≤y≤0.0045；
Wherein the pressure under the pressurization condition is controlled to be 300-400MPa, and the programmed temperature rise comprises the following stages: heating from room temperature to 250 ℃ at the speed of 1-4 ℃/min, and preserving heat; then heating from 150-250 ℃ to 450-500 ℃ at a speed of 3-8 ℃/min, and preserving the heat.
2. The preparation method of the low-temperature sintered microwave dielectric ceramic according to claim 1, wherein in the step (1), the mass ratio of the materials, the ball milling beads and the water is controlled to be 1: 2-4: 1.1-1.6 in the ball milling process.
3. The method for preparing a low-temperature sintered microwave dielectric ceramic according to claim 1, wherein in the step (1), the material having a main crystal phase is MgTiO3And CaTiO3And (4) forming.
4. The method of claim 3, wherein the MgTiO is selected from the group consisting of MgTiO, and MgTiO3Is prepared by the following steps: weighing magnesium-containing salt or oxide thereof, titanium-containing salt or oxide thereof, adding water for ball milling, filtering and drying, and presintering at 1000-1150 ℃;
the CaTiO3Is prepared by the following steps: weighing salt or oxide thereof containing calcium element, salt or oxide thereof containing titanium element, adding water, ball milling, filtering, drying, presintering at 1000-1150 deg.C to obtain the final product.
5. The method according to claim 1, wherein in step (2), the pressure under the pressurization condition is controlled to be 300-350MPa, and the temperature programming comprises the following steps: heating from room temperature to 180-220 ℃ at the speed of 2-4 ℃/min, and preserving heat; then raising the temperature from 220 ℃ at the speed of 4-6 ℃/min to 500 ℃ at the speed of 480 ℃ and preserving the temperature.
6. The method for preparing low-temperature sintered microwave dielectric ceramic according to claim 1, wherein in the step (2), the binder for preparing the microwave dielectric ceramic is polyvinyl alcohol, the polyvinyl alcohol is added in the form of an aqueous solution of polyvinyl alcohol, and the addition amount of the polyvinyl alcohol is 5-15% of the premixed powder by mass percentage.
7. The method for preparing a low-temperature sintered microwave dielectric ceramic according to claim 1, wherein the acetic acid is added in the form of an aqueous solution of acetic acid in the step (2), and the amount of the acetic acid added is 10 to 20% by mass of the premixed powder.
8. The method according to claim 1, wherein in the step (2), the mixture of the premixed powder and the binder for preparing the microwave dielectric ceramic is sieved, and the sieved material is mixed with the acetic acid and poured into a heatable mold.
9. A microwave dielectric ceramic produced by the method for producing a low-temperature-sintered microwave dielectric ceramic according to any one of claims 1 to 8.
10. Use of the microwave dielectric ceramic of claim 9 in the manufacture of a microwave communication device.
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CN113354409A (en) * 2021-06-07 2021-09-07 臻金新材(深圳)有限公司 Microwave dielectric ceramic and preparation method thereof
CN114920551A (en) * 2022-04-18 2022-08-19 浙江钛迩赛新材料有限公司 Method for reducing cracking failure by reinforcing 5G ceramic filter material
CN115304367A (en) * 2022-07-21 2022-11-08 苏州市职业大学 Preparation method and product of microwave dielectric ceramic
CN115304367B (en) * 2022-07-21 2023-03-28 苏州市职业大学 Preparation method and product of microwave dielectric ceramic

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