CN108147809B - Medium-low temperature sintered barium-titanium series microwave dielectric material and preparation method thereof - Google Patents
Medium-low temperature sintered barium-titanium series microwave dielectric material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a medium and low temperature sintered barium-titanium microwave dielectric material and a preparation method thereof, wherein the microwave dielectric material comprises the following components: main materials, auxiliary materials, modified additives and sintering aids; wherein the main material is TiO2(ii) a The auxiliary material is BaTiO3(ii) a The modified additive is Al2O3、MnO、SnO2、CoO、Nb2O5And ZrO2At least three of them. Through the technical scheme of the invention, the preparation of the primary finished powder is realized, the ceramic body can be sintered at medium and low temperature, the sintered ceramic body is compact, has no impurities and few defects, the relative dielectric constant is adjustable, the frequency temperature characteristic is stable, the quality factor is high, the production cost and the production period are greatly saved, the industrial production is easy to realize, and the batch production conversion from the material formula to the microwave dielectric material product can be quickly and stably realized.
Description
Technical Field
The invention relates to the technical field of microwave dielectric materials, in particular to a medium-low temperature sintered barium-titanium microwave dielectric material and a preparation method thereof.
Background
In 2017, the world mobile communication meeting pushes the 5G development in China all the time, and the 5G network business is strived to be realized in 2020. The most remarkable characteristic of the 5G era is high speed and high capacity, a higher frequency band is required to be used, a super high frequency band (300 MHz-3 GHz) is used before 4G, and 5G mainly develops to an ultrahigh frequency (3 GHz-30 GHz) and even a higher frequency band. The main microwave dielectric ceramic devices include filters, dielectric resonators, duplexers, dielectric antennas, dielectric substrates, capacitors, dielectric waveguide transmission lines and the like, and in order to meet the upgrade of the 5G technology, the high-performance microwave dielectric ceramic devices play an important role. The 5G communication brings new growth opportunities for the radio frequency device industry, on one hand, the number of frequency bands needing to be processed by a radio frequency module is greatly increased, on the other hand, the processing difficulty of high-frequency band signals is increased, the performance requirements of a system on a filter are also greatly improved, and the microwave dielectric ceramic plays an irreplaceable role in the microwave dielectric ceramic.
At present, microwave dielectric ceramic materials with medium dielectric constants are widely applied in the microwave dielectric ceramic industry, the Q & f value is low and is basically concentrated between 5000 and 30000, the sintering temperature is generally concentrated in a higher range of 1250-1300 ℃, and the ceramic material patent with low sintering temperature is accompanied with the defects of high cost and low Q & f, for example, as described in patent CN1609050A, the main material is Ca (Li 1609050A)1/3Nb2/3)O3And CaTiO3The sintering temperature is about 900 ℃, but the raw material sources of Li and Nb (niobium) are expensive, and the Q.f value is only 6000 to 10000; CN102584233A discloses a medium-high dielectric constant low-temperature co-fired ceramic material, the main phase of the ceramic material comprises 15-35% of Nb2O510-25% of ZnO, 10-25% of BaO and 10-20% of TiO21 to 10% of ZrO21 to 8 percent of Sm2O3And a small amount of La2O3The fluxing agent comprises 5-10% of SnO25 to 10% of CuO, 5 to 10% of SiO2And 1-5% of B2O3In addition, the alloy also comprises 0-5% of Al2O3And 0-5% of LiF, wherein the sintering temperature is 830-880 ℃, but the ceramic material contains expensive Sm and La, so that the raw material cost is high.
With the increasing awareness of environmental and energy protection in industrial production, the energy consumption of industrial production increasingly becomes an important assessment target for energy protection. Therefore, the sintering process with energy consumption accounting for a large proportion in the production process of the ceramic material also needs to be adjusted correspondingly, namely, the sintering temperature of the microwave medium ceramic material is reduced as much as possible while the performance of the product is maintained, and meanwhile, the raw material cost of the ceramic material also needs to be reduced.
Disclosure of Invention
Aiming at least one of the problems, the invention provides a medium-low temperature sintered barium-titanium microwave dielectric material and a preparation method thereof, which adopt a simple preparation process to prepare finished powder and avoid BaO-TiO2The microwave ceramic sintered block is a complex preparation process (material preparation, ball milling, drying, crushing, calcination and the like are required to be carried out according to a proper metering ratio), the one-time preparation of finished powder is realized, the sintered ceramic block can be sintered at a medium-low temperature (900-1170 ℃), the sintered ceramic body is compact, free of impurities and few in defects, the relative dielectric constant of the sintered ceramic body is adjustable within a range of 28-48, the production cost and the production period are greatly saved, the industrial production is easy to realize, and the batch production conversion from a material formula to a microwave dielectric material product can be quickly and stably realized.
In order to achieve the purpose, the invention provides a medium-low temperature sintered barium-titanium microwave dielectric material, which comprises the following components: main materials, auxiliary materials, modified additives and sintering aids; wherein the main material is TiO2(ii) a The auxiliary material is BaTiO3(ii) a The modified additive is Al2O3、MnO、SnO2、CoO、Nb2O5And ZrO2At least three of (1); the molar parts of the main material, the auxiliary material, the modified additive and the sintering aid are as follows: the TiO is250-75 parts; the BaTiO315-30 parts; the Al is2O31-5 parts; 0.2-0.6 part of MnO; the SnO20-2 parts; 0.2-0.8 part of CoO; the Nb2O50 to 3 parts; the ZrO20 to 3 parts; 5-20 parts of the sintering aid.
In the above technical solution, preferably, the sintering aid is B2O3、SiO2、ZnO、Li2CO3One or more of MgO, BaO and CuO.
In the above technical solution, preferably, the sintering aid is LBS sintering aid, LMZBS sintering aid, and/or BCB sintering aid; the LBS sintering aid is prepared from Li in a molar ratio of 3: 2: 62CO3、H3BO3And SiO2(ii) a The LMThe raw materials for preparing the ZBS sintering aid comprise Li with the molar ratio of 3: 2: 12CO3、Mg(OH)2、H3BO3ZnO and SiO2(ii) a The raw material for preparing the BCB sintering aid comprises BaCO with the molar ratio of 1: 23CuO and H3BO3。
The invention also provides a preparation method of the medium-low temperature sintered barium-titanium microwave dielectric material according to the technical scheme, which comprises the following steps: TiO the main material2The auxiliary material BaTiO3Mixing the modified additive and the sintering aid in proportion; adding zirconia balls into the mixture for ball milling, drying and sieving.
In the above technical solution, preferably, the sintering aid is formed by B2O3、SiO2、ZnO、Li2CO3One or more of MgO, BaO and CuO are mixed according to a certain proportion, zirconia balls are added for ball milling, and the mixture is prepared by drying, sieving and calcining.
Further, granulating the medium-low temperature sintered barium-titanium microwave medium material in the technical scheme; preparing the granulated microwave medium material into a green body; and removing the glue from the blank, sintering the blank after the glue is removed, preserving the heat for 2-8 hours, and naturally cooling to room temperature.
In the technical scheme, preferably, the microwave dielectric material is made into a blank under the pressure of 4-6 MPa, the blank is subjected to glue discharging in the environment of glue discharging temperature of 500 ℃, heating rate of 1-3 ℃/min and heat preservation for 2-4 hours, and the sintering temperature of the blank is 900-1170 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. realizes sintering at medium and low temperature (900-1170 ℃), has uniform components, narrow particle size distribution, good dispersibility, good formability, compact ceramic body after sintering, no impurities and few defects, and has adjustable relative dielectric constant in the range of 28-48 and loss tangent of less than 5 multiplied by 10 at room temperature-4Insulation resistivity > 1X 1013Omega cm, stable temperature characteristics of capacity, and good quality factor Q.fIs high.
2. The low dielectric microwave dielectric material is prepared by one-step material preparation, and BaO-TiO is reduced2The microwave ceramic sintering process is a complex process (such as material preparation, ball milling, drying, crushing, calcining and the like) for preparing the microwave ceramic sintering block, simplifies the preparation process of finished powder, has lower sintering temperature, can reduce energy consumption, greatly saves the production cost and period, is easy to realize industrial production, and can quickly and stably realize batch production conversion from a material formula to a microwave dielectric material product.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention is described in further detail below:
the invention provides a medium and low temperature sintered barium-titanium microwave dielectric material, which comprises the following components: main materials, auxiliary materials, modified additives and sintering aids; wherein the main material is TiO2(ii) a The auxiliary material is BaTiO3(ii) a The modified additive is Al2O3、MnO、SnO2、CoO、Nb2O5And ZrO2At least three of (a); the sintering aid is B2O3、SiO2、ZnO、Li2CO3One or more of MgO, BaO, and CuO; the molar parts of the main material, the auxiliary material, the modified additive and the sintering aid are as follows: the TiO is250-75 parts; the BaTiO315-30 parts; the Al is2O31-5 parts; 0.2-0.6 part of MnO; the SnO20 to 2 parts; 0.2-0.8 part of CoO; the Nb2O50 to 3 parts; the ZrO20 to 3 parts; 5-20 parts of the sintering aid.
In the above technical solution, preferably, the sintering aid is LBS sintering aid, LMZBS sintering aid, and/or BCB sintering aid; the LBS sintering aid is prepared from Li in a molar ratio of 3: 2: 62CO3、H3BO3And SiO2(ii) a The LMZBS sintering aid is prepared from raw materials including Li in a molar ratio of 3: 2: 12CO3、Mg(OH)2、H3BO3ZnO and SiO2(ii) a The raw material for preparing the BCB sintering aid comprises BaCO with the molar ratio of 1: 23CuO and H3BO3。
Further, the preparation method of the sintering aid comprises the following steps:
(1) the preparation method of the LBS sintering aid comprises the following steps: weighing raw material Li according to the molar ratio of 3: 2: 62CO3、H3BO3、SiO2Mixing, adding zirconium oxide (ZrO)2) Ball milling is carried out on the ball for 6 hours, the ball is dried for 10 hours at 80 ℃ until being dried, and the ball is obtained after being screened by a 100-mesh sieve and calcined for 4 hours at 600 ℃.
(2) The preparation method of the LMZBS sintering aid comprises the following steps: weighing raw material Li according to the molar ratio of 3: 2: 12CO3、Mg(OH)2、H3BO3、ZnO、SiO2Mixing, adding zirconia balls for ball milling for 6 hours, drying at 80 ℃ for 10 hours until the mixture is dried, sieving with a 100-mesh sieve, and calcining at 560 ℃ for 4 hours to obtain the zirconia ball-milling catalyst.
(3) The preparation method of the BCB sintering aid comprises the following steps: will analyze pure BaCO3CuO and H3BO3Mixing according to the mol ratio of 1: 2, adding zirconia balls for ball milling, wherein the ball milling time is 5 hours, drying for 10 hours at 80 ℃ until the materials are dried, sieving by a 100-mesh sieve, and then preserving the heat for 3 hours at 650 ℃.
Specifically, the main material TiO is proportionally mixed according to the formula in Table 12BaTiO as auxiliary material3Mixing the modified additive and the sintering aid, adding zirconia balls for ball milling for 5 hours, drying for 6 hours at 120 ℃, and sieving by a 100-mesh sieve to obtain the medium-low temperature sintered barium-titanium microwave dielectric material.
TABLE 1 formulation of medium-low temperature sintering medium microwave dielectric material (mol%)
Adding 6.5 wt% of PVA (Polyvinyl Alcohol) aqueous solution into the microwave medium material prepared according to the formula proportion in the table 1 for bonding and granulation; pressing into a wafer and a cylindrical blank under the pressure of 4MPa and 6MPa respectively, removing the adhesive from the blank, keeping the temperature at 500 ℃ and the heating rate at 2 ℃/min for 3 hours, and removing the adhesive; and sintering the green body after the binder removal at 900-1170 ℃, preserving the heat for 2-8 hours, and naturally cooling to room temperature along with a furnace to obtain the microwave dielectric ceramic material.
In the invention, because the formula components and the sintering process are properly selected, the BaTiO is realized3With TiO2Low temperature chemical combination reaction to produce BaO-TiO2Series of compounds, and realizes the sintering densification of the ceramic material. In general, BaO-TiO2The synthesis temperature of the compound solid phase method and the sintering porcelain-forming temperature are as high as 1300-1400 ℃. Compared with the prior industrial production process, the BaO-TiO is saved2The compound synthesis process simplifies the production process, saves the cost and is more beneficial to the industrial production of the microwave dielectric material.
Coating silver paste on two surfaces of the fired wafer, firing silver electrodes, and testing the room-temperature electrical properties of the capacitor after the capacitor is manufactured, wherein the test results are shown in table 2: relative dielectric constant εr28 to 48, and a loss tangent of less than 5 x 10-4Insulation resistivity greater than 1 x 1013Ω · cm, TCf (Temperature Coefficient of resonance frequency) is generally small.
TCf is an important parameter for measuring the temperature stability of the resonant frequency of the resonator, and the larger TCf is, the larger the drift of the center frequency along with the change of temperature is, and the higher stability of the device in the environment of temperature change cannot be ensured. In order to make the electronic circuit work stably, a dielectric material with a small temperature coefficient of frequency should be selected as much as possible. The TCf calculation formula is:
in the above formula, the temperature is T0The resonant frequency of time is f0Resonant frequency of f at temperature TT。
After sintering, the diameter of the cylindrical sample is 8.4 +/-0.5 mm, the thickness of the cylindrical sample is 5.0 +/-1.0 mm, and the quality factor Q.f value of the cylindrical sample is 17430-40253 GHz.
TABLE 2 Properties of microwave dielectric ceramic materials
The above is an embodiment of the invention, and the medium-low temperature sintered barium-titanium microwave dielectric material and the preparation method thereof provided by the invention are prepared by one-step material preparation, so that BaO-TiO is reduced2The microwave ceramic sintering block is a complex process (comprising material preparation, ball milling, drying, crushing, calcining and the like) for preparing the microwave ceramic sintering block, can be sintered at a medium-low temperature (900-1170 ℃) and has an adjustable relative dielectric constant in a range of 28-48. The microwave material is prepared by adopting a simple process, so that the production cost and the production period are greatly saved, the industrial production is easy to realize, and the batch production conversion from the material formula to the microwave dielectric material product can be quickly and stably realized.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A medium-low temperature sintered barium-titanium microwave dielectric material is characterized by comprising: main materials, auxiliary materials, modified additives and sintering aids;
wherein the main material is TiO2；
The auxiliary material is BaTiO3；
The modified additive is Al2O3、MnO、SnO2、CoO、Nb2O5And ZrO2At least three of (1);
the components are counted by the molar fraction,
the TiO is250-75 parts;
the BaTiO315-30 parts;
the Al is2O31-5 parts;
0.2-0.6 part of MnO;
the SnO20 to 2 parts;
0.2-0.8 part of CoO;
the Nb2O50 to 3 parts;
the ZrO20 to 3 parts;
5-20 parts of the sintering aid.
2. The preparation method of the medium and low temperature sintered barium-titanium microwave dielectric material of claim 1, which is characterized by comprising the following steps:
TiO the main material2The auxiliary material BaTiO3Mixing the modified additive and the sintering aid in proportion;
adding zirconia balls into the mixture for ball milling, drying and sieving.
3. The method for preparing the medium and low temperature sintered barium-titanium microwave dielectric material according to claim 2, further comprising:
granulating the dried and sieved powdery microwave medium material;
preparing the granulated microwave medium material into a blank body;
and removing the glue from the blank, sintering the blank after the glue is removed, wherein the sintering temperature of the blank is 900-1170 ℃, and naturally cooling to room temperature after heat preservation for 2-8 hours.
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| CN108484160A (en) * | 2018-06-25 | 2018-09-04 | 苏州博恩希普新材料科技有限公司 | Nine barium phthalate base microwave dielectric ceramic materials of one kind and preparation method |
| CN108752016A (en) * | 2018-08-22 | 2018-11-06 | 山东国瓷功能材料股份有限公司 | A kind of microwave-medium ceramics sintering aid and preparation method thereof |
| CN111099892A (en) * | 2020-01-03 | 2020-05-05 | 山东国瓷功能材料股份有限公司 | Barium titanate-based two-phase composite microwave dielectric ceramic material and preparation method thereof |
| CN114262219B (en) * | 2021-12-31 | 2022-09-06 | 北京元六鸿远电子科技股份有限公司 | Microwave dielectric ceramic material with ultrahigh temperature stability and preparation method and application thereof |
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