CN112939595A - Microwave dielectric ceramic material with near-zero temperature coefficient at high temperature and preparation method thereof - Google Patents
Microwave dielectric ceramic material with near-zero temperature coefficient at high temperature and preparation method thereof Download PDFInfo
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Abstract
The invention provides a microwave dielectric ceramic material with a near-zero temperature coefficient at a high temperature and a preparation method thereof, relating to the field of information functional materials. The ceramic material comprises a base material and a modified additive, wherein the chemical expression of the base material is as follows: (Mg, Ca, Sr)xLn2y(Si,Ti)O2+x+3yWherein x is more than or equal to 0.80 and less than or equal to 1.20 and 0.00<Y is less than or equal to 0.03, Ln is selected from one or more of La, Y, Ce, Sm, Dy, Ho, Er and Nd; the mass fraction of the base material in the microwave dielectric ceramic material is 98.5-100 wt%; the mass fraction of the modified additive in the microwave dielectric ceramic material is 0-1.5 wt%. The material is a lead-free environment-friendly material, a ceramic base material is synthesized once by adopting solid phase synthesis, a certain amount of doped modified additives are added, the dielectric constant of the manufactured electronic ceramic device is 17-25, and the quality factor is not less than40000GHz, temperature coefficient tau f (-55-125 ℃): less than +/-5 ppm/deg.C, and the temp. coefficient tau f less than +/-5 ppm/deg.C in the full temp. range of 180 deg.C. The material has good uniformity, is suitable for manufacturing microwave devices, and is particularly suitable for being used in environments with large temperature difference.
Description
Technical Field
The invention relates to the field of information functional materials, in particular to a microwave dielectric ceramic material with a near-zero temperature coefficient at high temperature and a preparation method thereof.
Background
Microwave dielectric ceramic material is rapidly developed in recent yearsA novel functional ceramic material. It has the characteristics of low dielectric loss, high dielectric constant epsilon, stable dielectric constant temperature coefficient tau f and the like. The material is a core basic material of a novel microwave circuit and a device including a dielectric resonator, a filter, an oscillator, a duplexer, an antenna, a dielectric substrate and the like, and has wide application in modern microwave communication and satellite navigation systems and equipment. In recent years, microwave devices have been rapidly developed in a direction of miniaturization, integration, and low power consumption, especially, mass production and low price for civil use, and thus a large number of microwave dielectric ceramic materials suitable for various microwave frequency bands have been developed. However, the current climate environment has high temperature, the high density integration and the limited heat dissipation capability in a small space range, and the microwave device itself generates heat, so that the problem that the temperature coefficient (tau f) of the microwave device is large at high temperature needs to be solved urgently>+/-5 ppm/DEG C) to improve the stability of the whole machine. For example, magnesium metatitanate (MgO. TiO) having an ilmenite structure2) The microwave dielectric ceramic material is an important microwave dielectric ceramic material due to relatively cheap raw materials and excellent microwave performance, but the high-temperature coefficient is-50 ppm/DEG C, so that the practical application of the microwave dielectric ceramic material is influenced. In the dielectric constant range of 17-25, the temperature coefficient τ f is > +/-5 ppm/deg.C at 125 deg.C and over the entire temperature range of 180 deg.C, which is not favorable for use in complex temperature environments.
Disclosure of Invention
The invention aims to provide a microwave dielectric ceramic material with a near-zero temperature coefficient at a high temperature and a preparation method thereof, and aims to solve the problems that the conventional microwave dielectric ceramic material with a dielectric constant of 17-25 is large in temperature coefficient and poor in performance reliability. The invention adopts one-time synthesis of ceramic base material and a certain doping amount to obtain the microwave dielectric ceramic material with near-zero temperature coefficient at high temperature, and solves the problems of difficult production and large temperature coefficient of the microwave device in the dielectric constant range.
The invention adopts the following scheme to achieve the aim.
The invention firstly provides a microwave dielectric ceramic material with near-zero temperature coefficient at high temperature, which comprises a base material and a modified additive, wherein the chemical expression of the base material is as follows: (Mg, Ca, Sr)xLn2y(Si,Ti)O2+x+3yWherein x is more than or equal to 0.80 and less than or equal to 1.20 and 0.00<Y is less than or equal to 0.03, Ln is selected from one or more of La, Y, Ce, Sm, Dy, Ho, Er and Nd; the mass fraction of the base material in the microwave dielectric ceramic material is 98.5-100 wt%; the mass fraction of the modified additive in the microwave dielectric ceramic material is 0-1.5 wt%. (Mg, Ca, Sr)xIt is expressed to include Mg, Ca and Sr elements, and their sum of coefficients in the chemical expression is x. (Si, Ti) means that Si and Ti are included and the sum of their coefficients in the chemical expression is 1. The valences of Ln in the chemical expression are all + 3.
As a further improvement of the microwave dielectric ceramic material, the modified additive is selected from Sb2O3、ZnO、MnCO3、BaCO3、Al2O3、Nb2O5、ZrO2、Cr2O3、Fe2O3One or more of (a).
As a further improvement of the microwave dielectric ceramic material, the mass fraction range of each modified additive in the microwave dielectric ceramic material is as follows: sb2O30 to 1.0% of ZnO, 0 to 1.0% of MnCO30 to 1.0% of BaCO30 to 1.0% of Al2O30 to 1.0% of Nb2O50 to 1.0% of ZrO20 to 1.0% of Cr2O30 to 0.3% of Fe2O30 to 0.3%.
As a further improvement of the microwave dielectric ceramic material, in the chemical expression of the base material, the subscript coefficient of Mg is 0.6-0.9, the subscript coefficient of Ca is 0.05-0.25, and the subscript coefficient of Sr is 0.0005-0.15.
As a further improvement of the microwave dielectric ceramic material, the subscript coefficient of Si is 0.2-0.5, and the subscript coefficient of Ti is 0.5-0.8.
The invention secondly provides a preparation method of the microwave dielectric ceramic material, which comprises the following steps:
s1 synthetic base material (Mg, Ca, Sr)xLn2y(Si,Ti)O2+x+3yWherein x is more than or equal to 0.80 and less than or equal to 1.20 and 0.00<y is less than or equal to 0.03: will Ln2O3、Mg(OH)2、CaCO3、SrCO3、SiO2And TiO2Mixing according to the proportion, carrying out wet ball milling, and calcining for 2-4 hours at the temperature of 1150-1250 ℃ in air atmosphere to obtain an initial base material;
and S2, mixing the initial base material obtained in the step S1 with the modified additive, adding water for wet ball milling, performing uniform refining treatment, and drying the ball-milled material to obtain the microwave dielectric ceramic material in a powder state.
As a further improvement of the preparation method of the microwave dielectric ceramic material, in step S2, the particle size of the ball-milled material is 0.6-1.5 um.
As a further improvement of the preparation method of the microwave dielectric ceramic material, the preparation method also comprises the following steps:
s3, adding a binder, a plasticizer and a dispersant into the microwave dielectric ceramic material in a powder state, performing ball milling for 1-2 hours to obtain slurry, drying to obtain powder, and pressing the powder into a green body;
s4, removing glue: placing the green body in a temperature range of 500-650 ℃, and preserving heat for 16-32 hours to obtain a green body;
s5, sintering: keeping the blank after the glue discharging at 1280-1390 ℃ for 3-5 hours in an air atmosphere;
s6, annealing: and after sintering, keeping the temperature for 1-2 hours at 950-1050 ℃ to obtain the formed microwave dielectric ceramic material.
As a further improvement of the preparation method of the microwave dielectric ceramic material, the adhesive is polyvinyl alcohol or acrylic resin or a mixture of the polyvinyl alcohol and the acrylic resin, the plasticizer is polyethylene glycol or acrylic resin or a mixture of the polyethylene glycol and the acrylic resin, and the dispersing agent is carboxylic acid ammonium salt.
As a further improvement of the preparation method of the microwave dielectric ceramic material, the heating rate of the glue discharging process of the step S4 is less than 10 ℃/h, and the heating rate of the sintering process of the step S5 is 150-200 ℃/h.
The formed microwave dielectric ceramic material has a temperature dielectric constant of 17-25 and a temperature coefficient tau f (-55-125 ℃): +/-5 ppm/deg.C, and Qf value greater than or equal to 40000 GHz.
The invention has the beneficial effects that: the base material is synthesized at one time, the problem of poor material uniformity caused by mixing of a plurality of synthetic materials is solved, the problem of poor stability of a prepared microwave device in a complex temperature environment due to the temperature coefficient of being more than +/-5 ppm/DEG C at a high temperature (125 ℃) is solved, and the prepared powdery microwave dielectric ceramic material has good material uniformity and meets the requirements of the microwave device. The powder is sintered at 1280-1390 ℃ to obtain the microwave dielectric ceramic device with microwave performance. The ceramic material can form a ceramic material with a room temperature dielectric constant of 17-25, a Qf value of more than or equal to 40000GHz and a temperature coefficient tau f (-55-125 ℃): less than +/-5 ppm/DEG C, and the full temperature is 180℃: less than +/-5 ppm/DEG C, meets the manufacturing requirement of microwave devices (such as filters, antenna sheets and the like), and is particularly suitable for being used in an environment with large temperature difference.
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. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention firstly provides a microwave dielectric ceramic material with near-zero temperature coefficient at high temperature, which comprises a base material and a modified additive, wherein the chemical expression of the base material is as follows: (Mg, Ca, Sr)xLn2y(Si,Ti)O2+x+3yWherein x is more than or equal to 0.80 and less than or equal to 1.20 and 0.00<Y is less than or equal to 0.03, Ln is selected from one or more of La, Y, Ce, Sm, Dy, Ho, Er and Nd; the mass fraction of the base material in the microwave dielectric ceramic material is 98.5-100 wt%; the mass fraction of the modified additive in the microwave dielectric ceramic material is 0-1.5 wt%. (Mg, Ca, Sr)xExpressed to include Mg, Ca and Sr elements and their coefficients in the chemical expression sum up tox. (Si, Ti) means that Si and Ti are included and the sum of their coefficients in the chemical expression is 1. The valences of Ln in the chemical expression are all + 3.
Wherein the modifying additive is selected from Sb2O3、ZnO、MnCO3、BaCO3、Al2O3、Nb2O5、ZrO2、Cr2O3、Fe2O3One or more of (a).
The mass fraction range of each modified additive in the microwave dielectric ceramic material is as follows: sb2O30 to 1.0% of ZnO, 0 to 1.0% of MnCO30 to 1.0% of BaCO30 to 1.0% of Al2O30 to 1.0% of Nb2O50 to 1.0% of ZrO20 to 1.0% of Cr2O30 to 0.3% of Fe2O30 to 0.3%.
In the chemical expression of the base material, the subscript coefficient of Mg is 0.6-0.9, the subscript coefficient of Ca is 0.05-0.25, and the subscript coefficient of Sr is 0.0005-0.15. .
Wherein the subscript coefficient of Si is 0.2-0.5, and the subscript coefficient of Ti is 0.5-0.8.
The invention also provides a preparation method of the microwave dielectric ceramic material, which comprises the following steps:
preparing base material powder: weighing Ln with corresponding mass according to the proportion of each metal element in the compound2O3(wherein Ln is selected from one or more of La, Y, Ce, Sm, Dy, Ho, Er and Nd), Mg (OH)2、CaCO3、SrCO3、SiO2、TiO2Placing the mixture into a ball mill, and taking the solid materials according to the mass ratio: water 1: (1.0-2.0), adding water according to the proportion, ball-milling and uniformly mixing, drying by using a spray drying tower or other methods after the sand milling treatment reaches a certain particle size (the particle size D50 is 0.6-1.5um under a laser particle size analyzer), calcining for 2-4 hours in an air atmosphere furnace at the temperature of 1150-1250 ℃, and finally obtaining the chemical expression: (Mg, Ca, Sr)xLn2y(Si,Ti)O2+x+3yA starting base powder. Wherein, Mg (OH)2The raw material preferably has a specific surface area of more than 8.0m2Powder of/g, TiO2The raw material preferably has a specific surface area of more than 7.0m2Powder per gram.
Preparing formula powder: mixing the initial base material powder obtained in the step (i) with various modifying additives Sb2O3、ZnO、MnCO3、BaCO3、Al2O3、Nb2O5、ZrO2、Cr2O3、Fe2O3One or more of the microwave dielectric ceramic materials are weighed according to the formula of the microwave dielectric ceramic materials, placed in a ball mill and prepared into solid materials according to the mass ratio: water 1: (0.6-1.0) adding water for wet sanding, wherein the materials are required to be uniformly mixed, and the average particle size of the sanded powder is 0.60-1.5um measured by a laser particle sizer. And drying the mixture by using a spray drying tower or other methods after the ball milling is finished to obtain the powdery microwave dielectric ceramic material.
Further, the preparation method of the microwave dielectric ceramic material of the invention also comprises the following steps:
thirdly, adding a proper amount of adhesive, plasticizer, dispersant and the like into the microwave dielectric ceramic material in the powder state, using zirconia balls as grinding media to perform ball milling in a ball milling tank for 1-2 hours to obtain slurry, and performing centrifugal spray drying to obtain spherical particle powder with good fluidity.
In a preferred mode, the adhesive is polyvinyl alcohol or acrylic resin or a mixture of the polyvinyl alcohol and the acrylic resin, the plasticizer is polyethylene glycol or acrylic resin or a mixture of the polyethylene glycol and the acrylic resin, and the dispersing agent is carboxylic acid ammonium salt.
And fourthly, pressing the spherical particle powder into a green body device.
Fifthly, placing the green device in the temperature range of 500-650 ℃, preserving heat for 16-32 hours, removing organic matters in the green sheet, and requiring the temperature rise speed in the whole glue removing process to be less than 10 ℃/hour.
Sixthly, sintering: and sintering the green body after the glue removal in air, heating to 1280-1390 ℃ at a heating rate of 150-200 ℃/h, and keeping the temperature for 3-5 hours. Sintering can move the grain boundary of the powder particles in the ceramic body, the air holes are gradually eliminated, and the body shrinks into a compact ceramic body with certain strength.
And (c) annealing treatment: and (3) after high-temperature sintering, keeping the furnace temperature within the range of 950-1050 ℃ for 1-2 hours to obtain the formed microwave dielectric ceramic material. Annealing can reduce the internal stress of the blank, refine crystal grains, close microcracks, improve the tissue structure of the material and improve the mechanical property of the ceramic.
Testing devices: and performing microwave performance test at the frequency of 5-8GHz by adopting an Agilent network.
According to the test result: the formed microwave dielectric ceramic material has a temperature dielectric constant of 17-25 and a temperature coefficient tau f (-55-125 ℃): +/-5 ppm/deg.C, and Qf value greater than or equal to 40000 GHz.
Because of MgO-SiO2Has low dielectric constant (< 8.5) and high Qf value (> 200000GHz), but has tf value of about-60 ppm/DEG C, so that the material with positive temperature coefficient needs to be doped to ensure the temperature stability of the microwave device so as to meet the practical requirement of electronic circuits, and the CaSiO is used for passing through3，CaTiO3Or CaSiTiO3The equal regulation is mainly used, besides ensuring lower sintering temperature, tau f can be approached to zero, but the combination of the type can realize that the dielectric constant 20 is at the level and the temperature coefficient tau f is at the temperature(-55℃～25℃)-τf(125℃-25℃)> +/-10 ppm/deg.C. The invention is in CaTiO3On the basis of the method, Ln and Sr elements and single CaTiO are introduced3Adjusting temperature coefficient ratio of (Ca, Sr) O-Ln2O3-TiO2Besides high dielectric constant and positive temperature coefficient, the material has high quality factor, and the frequency at different temperatures approaches to the frequency point of 25 ℃ to different degrees along with the change of the (Ca, Sr)/Ln quantity, thereby causing tauf(-55℃～25℃)≤±5ppm/℃，τf(125℃-25℃)Less than or equal to +/-5 ppm/DEG C, and can realize tau f(-55℃～25℃)-τf(125℃-25℃)Variation within. + -. 10 ppm/DEG C. The base material of the invention is carried out by adopting a one-time mixing and calcining way, thereby greatly improvingThe industrial and economic performance is improved, and the operation complexity is reduced.
Examples
The embodiment provides a microwave dielectric ceramic material with a near-zero temperature coefficient at high temperature and a preparation method ji thereof, and the scheme of the invention is not limited to the embodiment.
(1) According to the chemical expression: (Mg, Ca, Sr)xLn2y(Si,Ti)O2+x+3yWherein x is more than or equal to 0.80 and less than or equal to 1.20 and 0.00<y is less than or equal to 0.03, and three groups of Ln with corresponding mass are weighed according to the raw material formula shown in Table 12O3、Mg(OH)2、CaCO3、SrCO3、SiO2And TiO2Sequentially placing the materials in a ball mill, wherein each group of solid materials comprises the following components in percentage by mass: deionized water 1: 1.5, adding deionized water for wet ball milling, drying by a spray drying tower after ball milling, and calcining for 3 hours at 1240 ℃ in an air furnace. In each group of samples: in MSCT1, x is 0.85 and y is 0.03; in MSCT2, x is 0.95 and y is 0.02; in MSCT3, x is 1.05 and y is 0.01.
TABLE 1(Mg, Ca, Sr)xLn2y(Si,Ti)O2+x+3yEXAMPLES formulations
(2) Weighing the base material obtained in the step (1) and various modified additives according to the chemical compositions of the samples in the table 2, placing the base material and the modified additives into a ball mill in groups, and taking the solid materials according to the mass ratio of each group: deionized water 1: deionized water is added in a proportion of 0.8 for wet sanding, the materials are required to be uniformly mixed, and the average particle size of the sanded powder is 0.60-1.5um by using a laser particle sizer. After sanding, adding an adhesive, a plasticizer and a dispersant which respectively account for 0.5-6% of the total mass, drying by using a spray drying tower after uniform dispersion, and pressing the dried powder into a cylindrical green compact wafer; setting a temperature curve, and firstly placing the temperature curve in 600 ℃ for heat preservation for 24 hours to carry out glue discharging, wherein the heating rate of the whole glue discharging process is 8 ℃/hour; heating to 1285-1385 ℃ at the heating rate of 150 ℃/h, and preserving heat for 3 h for sintering; and (4) after high-temperature sintering, keeping the temperature at 1000 ℃ for 1.5 hours to obtain the formed microwave dielectric ceramic material resonant column.
TABLE 2 chemical composition of microwave dielectric ceramic material samples
The microwave performance test was performed on the formed microwave dielectric ceramic material, and the test results are shown in table 3. The samples No. 1 to 15 in Table 3 were taken from the samples No. 1 to 15 in Table 2, and the same numbers correspond one to one.
Table 3 test results of various electrical properties of the resonant column made by sintering the microwave dielectric ceramic material sample
As can be seen from Table 3, the formed ceramic material produced by the above process can be in the temperature range of 1285 ℃ to 1385 ℃. By adjusting the compounding ratio of the materials, the material can form a material with the room temperature dielectric constant of 17-22 and the temperature coefficient tau f (-55-125 ℃): +/-5 ppm/DEG C, namely at the low temperature of-55 ℃ and the high temperature of 125 ℃, the temperature coefficient is close to 0, the Qf value is more than or equal to 40000GHz, and the microwave performance parameters are continuously adjustable, so that the application requirement of low temperature coefficient can be met under the medium-low room temperature dielectric constant and the complex temperature environment (-55 ℃ -125 ℃) of the microwave device, meanwhile, the bending strength can reach more than 200MPa, and the problem of large frequency offset caused by severe outdoor environment can be solved.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claims, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A microwave dielectric ceramic material with near-zero temperature coefficient at high temperature comprises a base material and a modified additive, and is characterized in that: the chemical expression of the base material is as follows: (Mg, Ca, Sr)xLn2y(Si,Ti)O2+x+3yWherein x is more than or equal to 0.80 and less than or equal to 1.20 and 0.00<Y is less than or equal to 0.03, Ln is selected from one or more of La, Y, Ce, Sm, Dy, Ho, Er and Nd; the mass fraction of the base material in the microwave dielectric ceramic material is 98.5-100 wt%; the mass fraction of the modified additive in the microwave dielectric ceramic material is 0-1.5 wt%.
2. A microwave dielectric ceramic material according to claim 1, wherein: the modifying additive is selected from Sb2O3、ZnO、MnCO3、BaCO3、Al2O3、Nb2O5、ZrO2、Cr2O3、Fe2O3One or more of (a).
3. A microwave dielectric ceramic material as claimed in claim 2, wherein the mass fraction of each of the modifying additives in the microwave dielectric ceramic material is: sb2O30 to 1.0% of ZnO, 0 to 1.0% of MnCO30 to 1.0% of BaCO30 to 1.0% of Al2O30 to 1.0% of Nb2O50 to 1.0% of ZrO20 to 1.0% of Cr2O30 to 0.3% of Fe2O30 to 0.3%.
4. A microwave dielectric ceramic material as claimed in claim 1 wherein in the chemical expression of the base material, the subscript index of Mg is 0.6 to 0.9, the subscript index of Ca is 0.05 to 0.25, and the subscript index of Sr is 0.0005 to 0.15.
5. A microwave dielectric ceramic material as claimed in claim 1, wherein the subscript index of Si is 0.2 to 0.5 and the subscript index of Ti is 0.5 to 0.8.
6. A method for preparing a microwave dielectric ceramic material as claimed in any one of claims 1 to 5, comprising the following steps:
s1 synthetic base material (Mg, Ca, Sr)xLn2y(Si,Ti)O2+x+3yWherein x is more than or equal to 0.80 and less than or equal to 1.20 and 0.00<y is less than or equal to 0.03: will Ln2O3、Mg(OH)2、CaCO3、SrCO3、SiO2And TiO2Mixing according to the proportion, carrying out wet ball milling, and calcining for 2-4 hours at the temperature of 1150-1250 ℃ in air atmosphere to obtain an initial base material;
and S2, mixing the initial base material obtained in the step S1 with the modified additive, adding water for wet ball milling, performing uniform refining treatment, and drying the ball-milled material to obtain the microwave dielectric ceramic material in a powder state.
7. The preparation method according to claim 6, wherein in step S2, the particle size of the ball-milled material is 0.6-1.5 um.
8. The method of claim 6, further comprising the steps of:
s3, adding a binder, a plasticizer and a dispersant into the microwave dielectric ceramic material in a powder state, performing ball milling for 1-2 hours to obtain slurry, drying to obtain powder, and pressing the powder into a green body;
s4, removing glue: placing the green body in a temperature range of 500-650 ℃, and preserving heat for 16-32 hours to obtain a green body;
s5, sintering: keeping the blank after the glue discharging at 1280-1390 ℃ for 3-5 hours in an air atmosphere;
s6, annealing: and after sintering, keeping the temperature for 1-2 hours at 950-1050 ℃ to obtain the formed microwave dielectric ceramic material.
9. The preparation method according to claim 8, wherein the binder is polyvinyl alcohol or acrylic resin or a mixture of the polyvinyl alcohol and the acrylic resin, the plasticizer is polyethylene glycol or acrylic resin or a mixture of the polyethylene glycol and the acrylic resin, and the dispersant is carboxylic acid ammonium salt.
10. The method of claim 8, wherein the temperature rising rate of the step S4 gel discharging process is less than 10 ℃/hr, and the temperature rising rate of the step S5 sintering process is 150-200 ℃/hr.
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