CN114685159B - Magnesium titanate-based microwave medium composite powder material and preparation method thereof - Google Patents
Magnesium titanate-based microwave medium composite powder material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a magnesium titanate-based microwave medium composite powder material and a preparation method thereof. The magnesium metatitanate-based powder material prepared by the invention has uniform granularity, high sintering activity and compact ceramic structure after sintering, can realize good co-firing with a metal electrode, has excellent electrical properties, and can be widely applied to manufacturing of various microwave electronic components such as GPS antennas, multilayer ceramic capacitors, dielectric resonators, filters, dielectric substrates, diplexers, dielectric waveguides and the like.
Description
Technical Field
The invention relates to the technical field of manufacturing of microwave dielectric ceramic powder materials, in particular to a magnesium titanate-based microwave dielectric composite powder material and a preparation method thereof.
Background
The microwave refers to electromagnetic waves with the frequency range from 300MHz to 300GHz, the frequency range is between ultrashort waves and infrared rays, and along with the application development requirement of a communication technology, the successful landing of 5G communication and the high-frequency selection of 6G in the future, the microwave dielectric ceramic meets new application requirement and development opportunity under the opportunity. MgTiO 3 The material has a high quality factor, is an important microwave dielectric material, and is commonly used for manufacturing microwave devices such as GPS antennas, dielectric substrates, diplexers, dielectric waveguides, dielectric antenna multilayer ceramic capacitors, dielectric resonators and the like. But all the passive devices are prepared by the method and the electrode materialThe materials are co-fired, the sintering temperature of the electrode material is generally below 1300 ℃, the higher the sintering temperature is, the more expensive the inner electrode is, and MgTiO 3 The sintering temperature of the ceramic is higher and is about 1450 ℃, the sintering range is narrow, the grain size is easy to grow up at +/-20 ℃, the electrical reliability is low, and the application requirement of the subsequent preparation device is seriously influenced. Meanwhile, the temperature coefficient of the resonance frequency of the magnesium titanate is larger, and the magnesium titanate is not suitable for being used at a higher temperature, so that the wide application of the magnesium titanate in the field of microwave communication is limited, and therefore, the magnesium titanate-based powder material with low sintering temperature and good resonance temperature coefficient is obtained through doping modification and has very important significance.
At present, most magnesium meta-titanate based composite powder is still produced and prepared by a traditional solid phase method. The doped powder prepared by the method can not fundamentally solve the problems of large particle size, wide particle size distribution range and uneven doping, so that the sintered ceramic body inevitably has pores, the existence of the pores can reduce the sintering density of the material, and the dielectric loss of the material is further increased. Meanwhile, the thermal stability of the air hole is poor, so that the thermal expansion coefficient of the material is increased, the temperature stability of the material is reduced, and the temperature coefficient of the resonance frequency of the material is greatly shifted. Therefore, people gradually start to directly prepare the magnesium titanate-based composite powder material by adopting a liquid phase method, the subsequent sintering activity and compactness of the material are improved, and the application reliability and stability of the subsequent microwave dielectric passive device are optimized.
The overall level of the domestic microwave dielectric ceramic material has a certain gap compared with the American, japanese and Germany, and mainly shows that the preparation and dispersion technology of the high-end powder is far behind; the manufacturing equipment processing technology is behind, although foreign advanced process equipment is introduced, the investment is large, great pressure is brought to enterprises, the development of electronic ceramics is limited, and the reliability and the stability of the product cannot be temporarily compared with those of foreign products due to the processing level difference of imitation equipment. Electronic ceramic materials with good performance can be prepared under laboratory conditions, but most of the materials stay in laboratory sample stages, and partial products are produced in a transfer mode, so that the problems of high finished products, relatively low reliability and the like exist.
Disclosure of Invention
In view of the above, the invention discloses a magnesium titanate-based microwave medium composite powder material and a preparation method thereof, so as to realize the purposes that the magnesium titanate-based composite powder material has uniform granularity, high sintering activity, compact ceramic structure after sintering and good co-sintering with a metal electrode.
The invention provides a technical scheme, in particular to a magnesium titanate-based microwave medium composite powder material which comprises the following effective components in percentage by mass: mgTiO 3 90-96% of doping agent: er (Er) 2 O 3 /Tm 2 O 3 0.05～1.0％、CeO 2 /V 2 O 5 0.05～1.0％、Yb 2 O 3 0.05～1.0％、Ni 2 O 3 /Sb 2 O 3 0.05～1.0％、MnCO 3 /MnO 2 0.05～1.0％、Nb 2 O 5 0.05～1.0％、Al 2 O 3 0.05～1.0％。SrO/ZrO 2 /CaO 0.05～1.0％。
Further, the magnesium titanate-based microwave medium composite powder material comprises the following effective components in percentage by mass: mgTiO 3 90-96% of doping agent: er (Er) 2 O 3 /Tm 2 O 3 0.05～1.0％、CeO 2 /V 2 O 5 0.05～1.0％、 Yb 2 O 3 0.05～1.0％、Ni 2 O 3 /Sb 2 O 3 0.05～1.0％、MnCO 3 /MnO 2 0.05～1.0％、Nb 2 O 5 0.05～1.0％、Al 2 O 3 0.05～1.0％、SrO/ZrO 2 /CaO 0.05～1.0％、B 2 O 3 0.02～3％、ZnO 0.03～3％、SiO 2 0.05～3％、 Co 2 O 3 0～0.05％、CuO 0.00～0.05％。
The preparation method of the magnesium titanate-based microwave medium composite powder material comprises the following steps:
1) Preparing magnesium metatitanate powder;
2) Performing high-energy ball milling on the prepared dopant according to the mass percentage content to obtain a composite dopant;
3) Performing secondary ball milling on the magnesium metatitanate powder and the composite doping agent according to the mass percentage ratio;
4) Vacuum freeze drying to obtain powder after secondary ball milling;
5) And presintering the dried powder to finally obtain the magnesium titanate-based microwave medium composite powder material.
Further improved, the step 1) adopts a hydrothermal ball milling method to prepare magnesium metatitanate powder according to MgO and TiO 2 The magnesium source and the titanium source were introduced in a molar ratio of 1:1.
Further improved, the hydrothermal ball milling method for preparing the magnesium metatitanate powder specifically comprises the following steps: water, ethanol and butanol are used as mixed solvents, wherein water: ethanol: the volume ratio of butanol is 1.5-2:1:1, tetrabutyl titanate is selected as a titanium source, magnesium acetate is selected as a magnesium source, the hydrothermal time is 24-72 hours, the ball milling speed is 100-150 rpm, the synthesized powder is repeatedly washed by deionized water, and then is calcined at 400-600 ℃ for 60-150min, and the powder is ground for later use.
And further improving, wherein in the step 2), a high-energy ball milling method is adopted to perform high-energy ball milling on various dopants, wherein the ball milling revolution is controlled between 5500 and 6000 revolutions per minute, and the high-energy ball milling time is controlled between 0.5 and 1.5 hours.
Further improved, the grinding balls in the step 3) are toughened alumina balls, the grinding medium is a mixed solution of absolute ethyl alcohol and deionized water, the ball milling speed is 4000-6000 rpm, the ball milling time is 0.5-3 hours, and the magnesium metatitanate powder and the composite doping agent are mixed: toughened alumina spheres: the mass ratio of the grinding medium is 1:1.6 to 2.2:0.6 to 1.8.
Further improved, the temperature of the dried powder for presintering is 600-800 ℃.
The magnesium titanate-based microwave medium composite powder material is prepared by combining a hydrothermal ball milling method and a high-energy ball milling method, wherein the magnesium source and the titanium source are introduced into the magnesium titanate-based microwave medium composite powder material in a solution form when the magnesium metatitanate is prepared by the hydrothermal ball milling method. The magnesium metatitanate-based powder material prepared by the invention has uniform granularity, high sintering activity and compact ceramic structure after sintering, can realize good co-firing with a metal electrode, has excellent electrical properties, and can be widely applied to manufacturing of various microwave electronic components such as GPS antennas, multilayer ceramic capacitors, dielectric resonators, filters, dielectric substrates, diplexers, dielectric waveguides and the like.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure of the invention as claimed.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated below, but not necessarily all implementations consistent with the invention. Rather, they are merely examples of systems consistent with aspects of the invention as detailed in the accompanying claims.
In order to solve the problems of high sintering temperature, narrow sintering temperature range, poor subsequent sintering activity and compactness of the magnesium titanate-based microwave medium composite powder material and the like of the ceramic body in the prior art, the embodiment provides the magnesium titanate-based microwave medium composite powder material and the preparation method thereof.
In particular to a magnesium titanate-based microwave medium composite powder material which comprises the following effective components in percentage by mass: mgTiO 3 90-96% of doping agent: er (Er) 2 O 3 /Tm 2 O 3 0.05～1.0％、CeO 2 /V 2 O 5 0.05～1.0％、Yb 2 O 3 0.05～ 1.0％、Ni 2 O 3 /Sb 2 O 3 0.05～1.0％、MnCO 3 /MnO 2 0.05～1.0％、Nb 2 O 5 0.05～1.0％、Al 2 O 3 0.05～ 1.0％。SrO/ZrO 2 /CaO 0.05～1.0％。
Further optimized, the magnesium titanate-based microwave medium composite powder material provided by the embodiment can also comprise the following effective components in percentage by mass: mgTiO 3 90-96% of doping agent: er (Er) 2 O 3 /Tm 2 O 3 0.05～1.0％、CeO 2 /V 2 O 5 0.05～1.0％、Yb 2 O 3 0.05～1.0％、Ni 2 O 3 /Sb 2 O 3 0.05～1.0％、MnCO 3 /MnO 2 0.05～1.0％、 Nb 2 O 5 0.05～1.0％、Al 2 O 3 0.05～1.0％、SrO/ZrO 2 /CaO 0.05～1.0％、B 2 O 3 0.02～3％、ZnO 0.03～3％、SiO 2 0.05～3％、Co 2 O 3 0～0.05％、CuO 0.00～0.05％。
The selected dopant is Mg 4+ Doping modification is carried out on ions with close radius, wherein Er is as follows 2 O 3 /Tm 2 O 3 、Ni 2 O 3 、 Yb 2 O 3 Sb 2 O 3 Mainly plays a role in inhibiting the growth of crystal grains, thereby improving the reliability and stability of the application of the final microwave dielectric material.
CaO, srO, znO can synergistically improve the quality factor of the material and improve MgTiO to a small extent 3 The dielectric constant of the ceramic, and thus the electrical performance of the device.
CeO 2 /V 2 O 5 Can synergistically improve the quality factor and dielectric constant of the material, and meanwhile CeO 2 The abnormal growth of crystal grains of the magnesium meta-titanate system material in the sintering process can be effectively inhibited;
ZnO、B 2 O 3 、SiO 2 co in a small amount 2 O 3 Forming glass phase with CuO, the reduction degree of sintering temperature is greatest, and the flow mass transfer is higher than that of the common solid phase diffusion due to the existence of the glass phaseMass transfer is fast, so that the material transmission process is accelerated, the material moves to the surface under the action of vapor pressure, and the material is filled with Sb 2 O 3 The glass phase can form good meshing between crystal grains and spinel in the cooling process, and the concentration of crystal boundary defects is reduced. In addition, the mass transfer of the whole system is faster along with the chemical reaction of the solid-liquid interface in the process, so that the sintering temperature of the ceramic body is greatly reduced, the ceramic body has a higher quality factor, and meanwhile, the ceramic body has a certain moisture-proof effect.
The doping agent is cooperatively introduced by a plurality of rare earth ions, so that the frequency temperature characteristic of the magnesium meta-titanate matrix composite powder is greatly improved, and the comprehensive electrical property of the material is improved.
The preparation method of the magnesium titanate-based microwave medium composite powder material comprises the following steps:
1) Preparing magnesium metatitanate powder; preparing magnesium metatitanate powder by adopting a hydrothermal ball milling method according to MgO and TiO 2 The magnesium source and the titanium source are introduced in a ratio of 1:1.
The preparation of the magnesium metatitanate powder by the hydrothermal ball milling method specifically comprises the following steps: water, ethanol and butanol are used as mixed solvents, wherein water: ethanol: the volume ratio of butanol is 1.5-2:1:1, tetrabutyl titanate is selected as a titanium source, magnesium acetate is selected as a magnesium source, the hydrothermal time is 24-72 hours, the ball milling speed is 100-150 rpm, the synthesized powder is repeatedly washed by deionized water, and then is calcined at 400-600 ℃ for 60-150min, and the powder is ground for later use.
Magnesium meta-titanate MgTiO prepared by hydrothermal ball mill 3 The powder is the main body which finally forms the microwave dielectric ceramic structure, and the active ingredients are introduced into the magnesium source and the titanium source in the form of solution when the hydrothermal ball milling method is adopted to prepare the magnesium metatitanate. The magnesium metatitanate-based powder material prepared by the embodiment has uniform granularity, high sintering activity and compact ceramic structure after sintering, can realize good co-firing with a metal electrode, has excellent electrical properties, and can well solve the defects of high powder dispersibility, large granularity and the like by adopting a hydrothermal ball milling method capable of being industrially produced to prepare the magnesium metatitanate main body material.
2) Performing high-energy ball milling on the prepared dopant according to the mass percentage according to the mole ratio calculation to obtain a composite dopant; specifically, high-energy ball milling is carried out on various dopants by adopting a high-energy ball milling method, wherein the ball milling revolution is controlled between 5500 and 6000 revolutions per minute, and the high-energy ball milling time is controlled between 0.5 and 1.5 hours.
3) Performing secondary ball milling on the magnesium metatitanate powder and the composite doping agent according to the mass percentage;
specifically, the grinding balls are toughened alumina balls, the grinding medium is absolute ethyl alcohol, the ball milling speed is 4000-6000 rpm, the ball milling time is 0.5-3 hours, and the magnesium metatitanate powder and the composite doping agent are mixed: toughened alumina spheres: the mass ratio of the absolute ethyl alcohol is 1:1.6 to 2.2:0.6 to 1.8.
The step adopts the combination of high-energy primary ball milling and secondary ball milling to introduce the doping agent, thereby greatly improving the granularity uniformity and the like of the final synthesized magnesium titanate-based composite powder;
4) Vacuum freeze drying to obtain powder after secondary ball milling;
the high-energy ball milling method adopted by the embodiment is a mechanochemical method, the powder formed after the high-energy ball milling has large surface energy, is unstable in thermodynamics and has the tendency of automatic aggregation, and the powder particles can be gradually enlarged and cross-linked into a chain or net structure;
second, the wet particles contain a large amount of liquid (organic solvent and water), and as the liquid evaporates, voids appear in the particles, forming a large meniscus in the voids, which press the particles together under capillary shrinkage. The greater the surface tension of the liquid in the particles, the greater the capillary action and the greater the subsequent aggregation between particles with conventional drying processes.
The powder after the vacuum freeze drying treatment and secondary ball milling is characterized in that the processed wet powder is frozen and then heated under a certain negative pressure, so that the moisture in the material is sublimated from solid state to gas state directly, thereby removing the moisture in the wet material, when the liquid medium is frozen into ice, the volume of the liquid medium is expanded, so that the particles which are originally close to each other are effectively and properly separated, meanwhile, the 'liquid bridge' among the particles is frozen into the 'solid bridge', and the relative positions among the particles are fixed at the moment and cannot be close to each other.
In addition, the interfacial tension between the solid water molecules and the particles is far smaller than that between the liquid water molecules and the particles, so that aggregation of particles in the drying process is prevented, the serious agglomeration phenomenon caused by 'liquid bridge' is effectively avoided, and the dispersibility and sintering activity of the powder are greatly improved.
5) And presintering the dried powder to finally obtain the magnesium titanate-based microwave medium composite powder material.
The temperature of the dried powder for presintering is 600-800 ℃.
According to the embodiment, the liquid phase method is adopted to directly prepare the magnesium titanate-based powder material, the subsequent sintering activity and compactness of the material are improved, and further the application reliability and stability of the microwave dielectric passive device are optimized.
The invention will be further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
The magnesium titanate-based microwave medium composite powder material comprises the following active ingredients in percentage by mass according to the mole ratio: mgTiO 3 95%, dopant: er (Er) 2 O 3 /Tm 2 O 3 0.05％、CeO 2 /V 2 O 5 0.03％、Yb 2 O 3 0.05％、Ni 2 O 3 /Sb 2 O 3 0.02％、MnCO 3 /MnO 2 0.01％、Nb 2 O 5 1.0％、Al 2 O 3 0.02％、SrO/ZrO 2 /CaO 0.08％、B 2 O 3 2％、ZnO 2.2％、SiO 2 1.0％、Co 2 O 3 0.05％、CuO 0.01％。
Preparing magnesium metatitanate powder by adopting a hydrothermal ball milling process, and mixing the magnesium metatitanate powder with water, ethanol and butanol serving as mixed solvents in a volume ratio of 2:1:1; the titanium source is tetrabutyl titanate, and the magnesium source is magnesium acetate Mg (CH) 3 COO) 2 ·4H 2 O, the hydrothermal time is 72 hours, the ball milling speed is 120 r/min, the synthesized powder is repeatedly washed by deionized water, and then is calcined at a low temperature of 450 ℃ for 120min, and the powder is ground for later use.
Er in the formula is prepared by adopting a high-energy ball milling method 2 O 3 /Tm 2 O 3 0.05％、CeO 2 /V 2 O 5 0.03％、Yb 2 O 3 0.05％、 Ni 2 O 3 /Sb 2 O 3 0.02％、MnCO 3 /MnO 2 0.01％、Nb 2 O 5 1.0％、Al 2 O 3 0.02％、SrO/ZrO 2 /CaO 0.08％、 B 2 O 3 2％、ZnO 2.2％、SiO 2 1.0％、Co 2 O 3 0.05 percent of CuO and 0.01 percent of CuO are subjected to high-energy ball milling, the ball milling revolution is controlled between 5600 revolutions per minute, and the high-energy ball milling time is controlled to be 1.5 hours.
Preparing magnesium metatitanate powder prepared by hydrothermal ball milling and the prepared composite doping agent by a secondary high-energy ball milling method, wherein a grinding medium is toughened alumina balls, the grinding medium is mixed with deionized water by absolute ethyl alcohol, the volume ratio is 1:4, the revolution is 5600rmp/min, the ball milling time is 2.5 hours, and the materials are: ball: the mass ratio of water to ethanol is 1:2:1.
the ball-milled material is subjected to drying treatment by adopting a vacuum freeze-drying process.
And (5) carrying out a pre-sintering process at 680 ℃ on the dried powder.
Adding PVA with the mass fraction of 3% into the ground powder, granulating, tabletting and forming, wherein the diameter of the wafer is 15mm, and the thickness is 2mm.
The pressed wafer is heated to 600 ℃ for glue discharging treatment by 2 DEG/min, then sintered to porcelain at 1230 ℃, and then coated with surface electrode for electrical property test.
The magnesium titanate-based microwave medium composite powder prepared by the embodiment has a dielectric constant as high as 42, a quality factor as high as 75640, and a frequency temperature coefficient approaching 0 and being-5 ppm through performance test.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
Claims (3)
1. The preparation method of the magnesium titanate-based microwave medium composite powder material is characterized by comprising the following effective components in percentage by mass: mgTiO 3 90-96% of doping agent: er (Er) 2 O 3 And Tm 2 O 3 0.05～1.0%，CeO 2 And V 2 O 5 0.05～1.0%，Yb 2 O 3 0.05～1.0%，Ni 2 O 3 And Sb (Sb) 2 O 3 0.05～1.0%，MnCO 3 And MnO 2 0.05～1.0%，Nb 2 O 5 0.05～1.0%，Al 2 O 3 0.05～1.0%，SrO、ZrO 2 And CaO 0.05-1.0%; or comprises the following effective components in percentage by mass: mgTiO 3 90-96% of doping agent: er (Er) 2 O 3 And Tm 2 O 3 0.05～1.0%，CeO 2 And V 2 O 5 0.05～1.0%，Yb 2 O 3 0.05～1.0%，Ni 2 O 3 And Sb (Sb) 2 O 3 0.05～1.0%，MnCO 3 And MnO 2 0.05～1.0%，Nb 2 O 5 0.05～1.0%，Al 2 O 3 0.05～1.0%，SrO、ZrO 2 And CaO 0.05-1.0%, B 2 O 3 0.02～3%，ZnO 0.03～3%，SiO 2 0.05～3%，Co 2 O 3 0～0.05%，CuO 0.00～0.05%；
The preparation method comprises the following steps:
1) Preparing magnesium metatitanate powder;
2) Mixing the prepared dopants according to the mass percentage ratio, and performing high-energy ball milling to obtain a composite dopant;
3) Performing secondary ball milling on the magnesium metatitanate powder and the composite doping agent according to the mass percentage ratio;
4) Vacuum freeze drying to obtain powder after secondary ball milling;
5) Presintering the dried powder to finally obtain the magnesium titanate-based microwave medium composite powder material;
the step 1) is to prepare magnesium metatitanate powder by adopting a hydrothermal ball milling method according to MgO and TiO 2 Introducing a magnesium source and a titanium source in a molar ratio of 1:1;
the preparation of the magnesium metatitanate powder by the hydrothermal ball milling method specifically comprises the following steps: water, ethanol and butanol are used as mixed solvents, wherein water: ethanol: the volume ratio of butanol is 1.5-2:1:1, tetrabutyl titanate is selected as a titanium source, magnesium acetate is selected as a magnesium source, the hydrothermal time is 24-72 hours, the ball milling speed is 100-150 r/min, the synthesized powder is repeatedly washed by deionized water, and then calcined at a low temperature of 400-600 ℃ for 60-150min, and the obtained product is ground for later use;
and 2) performing high-energy ball milling on various dopants by adopting a high-energy ball milling method, wherein the ball milling revolution is controlled to be 5500-6000 rpm, and the high-energy ball milling time is controlled to be 0.5-1.5 hours.
2. The method for preparing the magnesium titanate-based microwave medium composite powder material according to claim 1, wherein in the step 3), grinding balls are toughened alumina balls in the secondary ball milling, the grinding medium is a mixed solution of absolute ethyl alcohol and deionized water, the ball milling speed is 4000-6000 rpm, the ball milling time is 0.5-3 hours, and the mixture of magnesium metatitanate powder and composite doping agent: toughened alumina spheres: the mass ratio of the grinding medium is 1:1.6 to 2.2:0.6 to 1.8.
3. The method for preparing a magnesium titanate-based microwave dielectric composite powder material according to claim 1, wherein the temperature at which the dried powder is pre-sintered is 600-800 ℃.
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