CN108516826B - Sn-containing intermediate microwave dielectric ceramic material and preparation method thereof - Google Patents
Sn-containing intermediate microwave dielectric ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Sn-containing intermediate microwave dielectric ceramic material and a preparation method thereof, wherein the chemical formula of the Sn-containing intermediate microwave dielectric ceramic material is CoSnNb2O8And the chemical general formula of the substance is (1-x) CoSnNb2O8‑xZn1.01Nb2O6Wherein x is Zn1.01Nb2O6X is more than or equal to 0.40 and less than or equal to 0.60. The preparation method comprises the following steps: proportioning, ball milling, presintering synthesis, secondary ball milling, granulation, molding, viscosity discharging and sintering. The invention prepares a medium and low-loss microwave dielectric ceramic material by specific raw material composition and combining with a specific process, the material has low sintering temperature and the temperature coefficient of resonance frequency is close to zero, and can be widely applied to various dielectric resonators, filters and other devices.
Description
Technical Field
The invention belongs to the technical field of electronic information materials, and particularly relates to a Sn-containing intermediate microwave dielectric ceramic material and a preparation method thereof.
Background
With the rapid development of communication technology, the number of mobile phones and communication base stations is increasing day by day, and the transmission of data such as texts, pictures and videos by wireless communication is rapidly developed. As a key material of components such as filters, resonators and the like, microwave dielectric ceramics are the best dielectric material which is rapidly developed under the background, and the microwave dielectric ceramics have three requirements in use: suitable dielectric constant (. epsilon.)r) Low dielectric loss (or high quality factor Q x f) and temperature coefficient of resonance frequency as close to zero (| τ) as possiblefLess than or equal to 10 ppm/DEG C). But the single-phase microwave dielectric ceramics which can simultaneously meet the three performance parameter indexes are very few.
The technology development is different day by day and day, and is based on satellite communication and movementThe intermediate microwave dielectric ceramic material applied to the communication base station is widely concerned by researchers at home and abroad. The hot system studied in recent years is (Zr, Sn) TiO4Class and Ba (B)2+ 1/3B5 + 2/3)O3Type complex perovskite wherein B2+Is Mg, Ni, Co, Mn, Zn, Ca, etc., B5+Ta and Nb. Although these materials have ideal microwave dielectric properties, the sintering conditions are severe and the preparation process is complicated, such as Ba (Mg)1/3Ta2/3)O3The sintering temperature is as high as 1640 ℃, and even the densification can be realized only after heat preservation for dozens of hours, which are difficult to meet the development requirements of modern microwave communication devices on miniaturization and integration.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a Sn-containing intermediate microwave dielectric ceramic material and a preparation method thereof, wherein the material is made of CoSnNb2O8As a base material, Zn is added thereto1.01Nb2O6The medium and low-loss microwave dielectric ceramic material is prepared, the sintering temperature of the material is low, and the near-zero temperature coefficient of the resonant frequency meets the requirement of a microwave device on the temperature stability.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
an intermediate microwave dielectric ceramic material containing Sn and having a chemical formula of CoSnNb2O8。
An intermediate microwave medium ceramic material containing Sn is prepared from the said material and Zn1.01Nb2O6Prepared by compounding and has the chemical general formula of (1-x) CoSnNb2O8-xZn1.01Nb2O6Wherein x is Zn1.01Nb2O6X is more than or equal to 0.40 and less than or equal to 0.60.
Further, the Sn-containing intermediate microwave dielectric ceramic material has a chemical formula of 0.52CoSnNb2O8-0.48Zn1.01Nb2O6。
The preparation method of the Sn-containing intermediate microwave dielectric ceramic material comprises the following steps:
(1) preparing materials: according to CoSnNb respectively2O8、Zn1.01Nb2O6CoO, ZnO and Nb are weighed2O5And SnO2；
(2) Ball milling: ball-milling and mixing the raw materials weighed in the step (1) to obtain slurry;
(3) pre-sintering synthesis: drying, grinding and sieving the slurry obtained in the step (2), and calcining at 1050 ℃ and 950 ℃ for 4-6h to obtain CoSnNb2O8And Zn1.01Nb2O6；
(4) Secondary ball milling: mixing CoSnNb2O8And Zn1.01Nb2O6Mixing, and performing ball milling again to obtain slurry;
(5) and (3) granulation: drying, grinding and sieving the slurry obtained in the step (4) to obtain powder, then adding a binder into the powder, and uniformly mixing in a mortar to obtain powder;
(6) molding: pressing and molding the powder obtained in the step (5) under the condition of 8-12MPa to obtain a ceramic green body;
(7) removing viscosity: the ceramic green body is insulated for 4-6h at the temperature of 400-600 ℃, and the binder is discharged;
(8) and (3) sintering: sintering the green body after the binder removal at 1150-1200 ℃ for 4-6h in an air atmosphere to obtain the ceramic material.
Further, CoO, ZnO and Nb in the step (1)2O5And SnO2The purity of (A) is more than 99.9%.
Further, in the step (2) and the step (4), ethanol is used as a medium in the ball milling process, the ball milling rotation speed is 300-.
Further, in the step (2) and the step (4), the ball milling rotation speed is 350r/min, and the ball milling time is 6 h.
Further, in the step (3), the slurry obtained in the step (2) is dried, ground and sieved, and then calcined for 4 hours at 1100 ℃ and 1000 ℃ respectively.
Furthermore, the binder in the step (5) is 5-7 wt% of polyvinyl alcohol solution, and the addition amount of the binder accounts for 5-10% of the total mass of the powder.
Further, the binder in the step (5) is 5 wt% of polyvinyl alcohol solution, and the addition amount of the polyvinyl alcohol solution accounts for 8% of the total mass of the powder.
The Sn-containing intermediate microwave dielectric ceramic material and the preparation method thereof have the following beneficial effects:
(1) medium, low loss CoSnNb2O8(εr31.0, Q × f 43,000GHz) microwave dielectric ceramic has a low sintering temperature, but a high temperature coefficient of resonance frequency; and ZnNb2O6Respectively has a microwave dielectric property of epsilonr＝23.0，Q×f＝81,000GHz，τfAt-68 ppm/° C, when Zn is in excess of 0.01mol, at ∈rAnd τfOn the basis of small variation, Q × f can be increased to 120,000-. Therefore, the invention uses Zn1.01Nb2O6Improvement of CoSnNb as temperature compensation material2O8Temperature coefficient of resonant frequency.
(2) The invention relates to CoSnNb with positive and negative resonance frequency temperature coefficients2O8And Zn1.01Nb2O6The two-phase ceramic is compounded, and the medium and low-loss microwave dielectric ceramic material with stable temperature is prepared by a specific raw material ratio and a specific process. The material has low sintering temperature and simple preparation process, and can be widely used for manufacturing devices such as various dielectric resonators, filters and the like.
Detailed Description
In the invention, CoO, ZnO and Nb are used2O5And SnO2The method is a key step for preparing a product meeting the proportioning requirement on the premise of fully reacting the raw materials by ball milling; pre-sintering synthesis after ball milling, which aims to pre-react raw materials to form a required main crystal phase, wherein the synthesis temperature and the heat preservation time have great influence on the formation of the main crystal phase in the process, the powder has higher surface activity after pre-sintering, the growth of crystal grains and the improvement of density in the sintering process are facilitated, the post-sintering shrinkage rate of a sample can be reduced through the pre-sintering, and the generation of the material due to overlarge deformation is avoidedCracks and closed pores; mixing the powder obtained after pre-sintering according to a ratio, and carrying out secondary ball milling to uniformly mix all the substances and simultaneously achieve the purpose of refining the powder; after the powder is sieved, a proper amount of binder is added and uniformly mixed with the powder to improve the compactness of a green body, the mixture is granulated and then is pressed and formed, the binder is fully discharged at high temperature, and finally sintering is carried out, wherein the sintering temperature and the sintering time of the mixture can influence the crystal structure and the micro-morphology of the material, and further influence the microwave dielectric property of the obtained ceramic. The microwave dielectric ceramic material with small temperature coefficient of resonant frequency, dielectric constant of 28.1-30.9 and quality factor of 53023-87840GHz can be obtained at a lower sintering temperature, and can be widely used for manufacturing various dielectric substrates, resonators, filters and other devices, and can meet the technical requirements of mobile communication, satellite communication and the like.
The present invention will be further described with reference to the following examples.
Example 1
An intermediate microwave dielectric ceramic material containing Sn and having a chemical formula of 0.58CoSnNb2O8-0.42Zn1.01Nb2O6。
The preparation method of the Sn-containing intermediate microwave dielectric ceramic material comprises the following steps:
(1) preparing materials: according to CoSnNb respectively2O8、Zn1.01Nb2O6CoO, ZnO and Nb are weighed2O5And SnO2(ii) a Among them, CoO, ZnO and Nb2O5And SnO2The purity of (A) is more than 99.9%;
(2) ball milling: taking ethanol as a medium, and performing ball milling and mixing on the raw materials weighed in the step (1) to obtain slurry; wherein the weight ratio of the raw materials and ethanol in the step (1) is 1:1, the ball milling speed is 300r/min, and the ball milling time is 7 h;
(3) pre-sintering synthesis: drying, grinding and sieving the slurry obtained in the step (2), and calcining the slurry at 1100 ℃ and 1000 ℃ for 4 hours respectively to obtain CoSnNb2O8And Zn1.01Nb2O6；
(4) Secondary ball milling: mixing CoSnNb2O8And Zn1.01Nb2O6Mixing, ball-milling again to obtain slurry, wherein the ball-milling process of the second time is the same as that of the step (2);
(5) and (3) granulation: drying, grinding and sieving the slurry obtained in the step (4) to obtain powder, then adding a binder into the powder, and uniformly mixing in a mortar to obtain powder; wherein the binder is 5 wt% of polyvinyl alcohol solution, and the addition amount of the binder accounts for 5% of the total mass of the powder;
(6) molding: pressing the powder obtained in the step (5) into a cylinder with the diameter of 10mm multiplied by 6mm under the pressure of 8MPa to obtain a ceramic green body;
(7) removing viscosity: preserving the temperature of the ceramic green body at 400 ℃ for 6h, and discharging the binder;
(8) and (3) sintering: sintering the green body after viscosity removal for 4h at 1175 ℃ in an air atmosphere to obtain the ceramic material.
Example 2
An intermediate microwave dielectric ceramic material containing Sn and having a chemical formula of 0.57CoSnNb2O8-0.43Zn1.01Nb2O6。
The preparation method of the Sn-containing intermediate microwave dielectric ceramic material comprises the following steps:
(1) preparing materials: according to CoSnNb respectively2O8、Zn1.01Nb2O6CoO, ZnO and Nb are weighed2O5And SnO2(ii) a Among them, CoO, ZnO and Nb2O5And SnO2The purity of (A) is more than 99.9%;
(2) ball milling: taking ethanol as a medium, and performing ball milling and mixing on the raw materials weighed in the step (1) to obtain slurry; wherein the weight ratio of the raw materials and ethanol in the step (1) is 1:1, the ball milling speed is 400r/min, and the ball milling time is 5 h;
(3) pre-sintering synthesis: drying, grinding and sieving the slurry obtained in the step (2), and calcining the slurry at 1100 ℃ and 1000 ℃ for 4 hours respectively to obtain CoSnNb2O8And Zn1.01Nb2O6；
(4) Secondary ball milling: mixing CoSnNb2O8And Zn1.01Nb2O6Mixing is carried outMixing, ball milling again to obtain slurry, wherein the ball milling process in the second time is the same as that in the step (2);
(5) and (3) granulation: drying, grinding and sieving the slurry obtained in the step (4) to obtain powder, then adding a binder into the powder, and uniformly mixing in a mortar to obtain powder; wherein the binder is 5 wt% of polyvinyl alcohol solution, and the addition amount of the binder accounts for 10% of the total mass of the powder;
(6) molding: pressing the powder obtained in the step (5) into a cylinder with the diameter of 10mm multiplied by 6mm under the pressure of 12MPa to obtain a ceramic green body;
(7) removing viscosity: preserving the temperature of the ceramic green body at 600 ℃ for 4h, and discharging the binder;
(8) and (3) sintering: and sintering the green body subjected to viscosity removal for 6 hours at 1175 ℃ in an air atmosphere to obtain the ceramic material.
Example 3
An intermediate microwave dielectric ceramic material containing Sn and having a chemical formula of 0.52CoSnNb2O8-0.48Zn1.01Nb2O6。
The preparation method of the Sn-containing intermediate microwave dielectric ceramic material comprises the following steps:
(1) preparing materials: according to CoSnNb respectively2O8、Zn1.01Nb2O6CoO, ZnO and Nb are weighed2O5And SnO2(ii) a Among them, CoO, ZnO and Nb2O5And SnO2The purity of (A) is more than 99.9%;
(2) ball milling: taking ethanol as a medium, and performing ball milling and mixing on the raw materials weighed in the step (1) to obtain slurry; wherein the weight ratio of the raw materials and ethanol in the step (1) is 1:1, the ball milling speed is 350r/min, and the ball milling time is 6 hours;
(3) pre-sintering synthesis: drying, grinding and sieving the slurry obtained in the step (2), and calcining the slurry at 1100 ℃ and 1000 ℃ for 4 hours respectively to obtain CoSnNb2O8And Zn1.01Nb2O6；
(4) Secondary ball milling: mixing CoSnNb2O8And Zn1.01Nb2O6Mixing, ball milling again to obtain slurry, ball milling for the second time and the ball milling in the step (2)The ball milling process is the same;
(5) and (3) granulation: drying, grinding and sieving the slurry obtained in the step (4) to obtain powder, then adding a binder into the powder, and uniformly mixing in a mortar to obtain powder; wherein the binder is 5 wt% of polyvinyl alcohol solution, and the addition amount of the binder accounts for 6% of the total mass of the powder;
(6) molding: pressing the powder obtained in the step (5) into a cylinder with the diameter of 10mm multiplied by 6mm under the pressure of 10MPa to obtain a ceramic green body;
(7) removing viscosity: preserving the temperature of the ceramic green body at 500 ℃ for 4h, and discharging the binder;
(8) and (3) sintering: sintering the green body after viscosity removal for 4h at 1175 ℃ in an air atmosphere to obtain the ceramic material.
Example 4
An intermediate microwave dielectric ceramic material containing Sn and having a chemical formula of 0.52CoSnNb2O8-0.48Zn1.01Nb2O6。
The preparation method of the Sn-containing intermediate microwave dielectric ceramic material comprises the following steps:
(1) preparing materials: according to CoSnNb respectively2O8、Zn1.01Nb2O6CoO, ZnO and Nb are weighed2O5And SnO2(ii) a Among them, CoO, ZnO and Nb2O5And SnO2The purity of (A) is more than 99.9%;
(2) ball milling: taking ethanol as a medium, and performing ball milling and mixing on the raw materials weighed in the step (1) to obtain slurry; wherein the weight ratio of the raw materials and ethanol in the step (1) is 1:1, the ball milling speed is 320r/min, and the ball milling time is 6.5 h;
(3) pre-sintering synthesis: drying, grinding and sieving the slurry obtained in the step (2), and calcining the slurry at 1100 ℃ and 1000 ℃ for 4 hours respectively to obtain CoSnNb2O8And Zn1.01Nb2O6；
(4) Secondary ball milling: mixing CoSnNb2O8And Zn1.01Nb2O6Mixing, ball-milling again to obtain slurry, wherein the ball-milling process of the second time is the same as that of the step (2);
(5) and (3) granulation: drying, grinding and sieving the slurry obtained in the step (4) to obtain powder, then adding a binder into the powder, and uniformly mixing in a mortar to obtain powder; wherein the binder is 5 wt% of polyvinyl alcohol solution, and the addition amount of the binder accounts for 7% of the total mass of the powder;
(6) molding: pressing the powder obtained in the step (5) into a cylinder with the diameter of 10mm multiplied by 6mm under the pressure of 10MPa to obtain a ceramic green body;
(7) removing viscosity: preserving the temperature of the ceramic green body at 450 ℃ for 5h, and discharging the binder;
(8) and (3) sintering: sintering the green body after the viscosity removal at 1200 ℃ for 4h in an air atmosphere to obtain the ceramic material.
Example 5
An intermediate microwave dielectric ceramic material containing Sn and having a chemical formula of 0.45CoSnNb2O8-0.55Zn1.01Nb2O6。
The preparation method of the Sn-containing intermediate microwave dielectric ceramic material comprises the following steps:
(1) preparing materials: according to CoSnNb respectively2O8、Zn1.01Nb2O6CoO, ZnO and Nb are weighed2O5And SnO2(ii) a Among them, CoO, ZnO and Nb2O5And SnO2The purity of (A) is more than 99.9%;
(2) ball milling: taking ethanol as a medium, and performing ball milling and mixing on the raw materials weighed in the step (1) to obtain slurry; wherein the weight ratio of the raw materials and ethanol in the step (1) is 1:1, the ball milling speed is 380r/min, and the ball milling time is 5.5 h;
(3) pre-sintering synthesis: drying, grinding and sieving the slurry obtained in the step (2), and calcining the slurry at 1100 ℃ and 1000 ℃ for 4 hours respectively to obtain CoSnNb2O8And Zn1.01Nb2O6；
(4) Secondary ball milling: mixing CoSnNb2O8And Zn1.01Nb2O6Mixing, ball-milling again to obtain slurry, wherein the ball-milling process of the second time is the same as that of the step (2);
(5) and (3) granulation: drying, grinding and sieving the slurry obtained in the step (4) to obtain powder, then adding a binder into the powder, and uniformly mixing in a mortar to obtain powder; wherein the binder is 5 wt% of polyvinyl alcohol solution, and the addition amount of the binder accounts for 8% of the total mass of the powder;
(6) molding: pressing the powder obtained in the step (5) into a cylinder with the diameter of 10mm multiplied by 6mm under the pressure of 10MPa to obtain a ceramic green body;
(7) removing viscosity: preserving the temperature of the ceramic green body at 550 ℃ for 4.5h, and discharging the binder;
(8) and (3) sintering: sintering the green body after viscosity removal for 4h at 1175 ℃ in an air atmosphere to obtain the ceramic material.
Example 6
An intermediate microwave dielectric ceramic material containing Sn and having a chemical formula of 0.40CoSnNb2O8-0.60Zn1.01Nb2O6。
The preparation method of the Sn-containing intermediate microwave dielectric ceramic material comprises the following steps:
(1) preparing materials: according to CoSnNb respectively2O8、Zn1.01Nb2O6CoO, ZnO and Nb are weighed2O5And SnO2(ii) a Among them, CoO, ZnO and Nb2O5And SnO2The purity of (A) is more than 99.9%;
(2) ball milling: taking ethanol as a medium, and performing ball milling and mixing on the raw materials weighed in the step (1) to obtain slurry; wherein the weight ratio of the raw materials and ethanol in the step (1) is 1:1, the ball milling speed is 360r/min, and the ball milling time is 6.5 h;
(3) pre-sintering synthesis: drying, grinding and sieving the slurry obtained in the step (2), and calcining the slurry at 1100 ℃ and 1000 ℃ for 4 hours respectively to obtain CoSnNb2O8And Zn1.01Nb2O6；
(4) Secondary ball milling: mixing CoSnNb2O8And Zn1.01Nb2O6Mixing, ball-milling again to obtain slurry, wherein the ball-milling process of the second time is the same as that of the step (2);
(5) and (3) granulation: drying, grinding and sieving the slurry obtained in the step (4) to obtain powder, then adding a binder into the powder, and uniformly mixing in a mortar to obtain powder; wherein the binder is 5 wt% of polyvinyl alcohol solution, and the addition amount of the binder accounts for 9% of the total mass of the powder;
(6) molding: pressing the powder obtained in the step (5) into a cylinder with the diameter of 10mm multiplied by 6mm under the pressure of 10MPa to obtain a ceramic green body;
(7) removing viscosity: preserving the temperature of the ceramic green body at 500 ℃ for 5h, and discharging the binder;
(8) and (3) sintering: and sintering the green body subjected to viscosity discharging for 5 hours at 1150 ℃ in an air atmosphere to obtain the ceramic material.
The Sn-containing intermediate microwave dielectric ceramic material prepared in the examples 1 to 6 is subjected to microwave dielectric property test, and the microwave dielectric property is evaluated by a cylindrical dielectric resonator method, wherein epsilon isr、Q×f、τfThe results are shown in Table 1.
TABLE 1 results of performance parameters for Sn containing intermediate microwave dielectric ceramic materials prepared in various examples
Claims (8)
1. The Sn-containing intermediate microwave dielectric ceramic material is characterized by comprising CoSnNb2O8And Zn1.01Nb2O6Prepared by compounding and has the chemical general formula of (1-x) CoSnNb2O8-xZn1.01Nb2O6Wherein x is Zn1.01Nb2O6X is more than or equal to 0.40 and less than or equal to 0.60;
the Sn-containing intermediate microwave dielectric ceramic material is prepared by the following method:
(1) preparing materials: according to CoSnNb respectively2O8、Zn1.01Nb2O6CoO, ZnO and Nb are weighed2O5And SnO2；
(2) Ball milling: ball-milling and mixing the raw materials weighed in the step (1) to obtain slurry;
(3) pre-sintering synthesis: drying, grinding and sieving the slurry obtained in the step (2), and calcining at 1050 ℃ and 950 ℃ for 4-6h to obtain CoSnNb2O8And Zn1.01Nb2O6；
(4) Secondary ball milling: mixing CoSnNb2O8And Zn1.01Nb2O6Mixing, and performing ball milling again to obtain slurry;
(5) and (3) granulation: drying, grinding and sieving the slurry obtained in the step (4) to obtain powder, then adding a binder into the powder, and uniformly mixing in a mortar to obtain powder;
(6) molding: pressing and molding the powder obtained in the step (5) under the condition of 8-12MPa to obtain a ceramic green body;
(7) removing viscosity: the ceramic green body is insulated for 4-6h at the temperature of 400-600 ℃, and the binder is discharged;
(8) and (3) sintering: sintering the green body after the binder removal at 1150-1200 ℃ for 4-6h in an air atmosphere to obtain the ceramic material.
2. The Sn containing intermediate microwave dielectric ceramic material of claim 1 wherein the chemical formula is 0.52CoSnNb2O8-0.48Zn1.01Nb2O6。
3. The Sn-containing intermediate microwave dielectric ceramic material as claimed in claim 1 or 2, wherein CoO, ZnO and Nb in step (1)2O5And SnO2The purity of (A) is more than 99.9%.
4. The Sn-containing intermediate microwave dielectric ceramic material as claimed in claim 1 or 2, wherein in the step (2) and the step (4), ethanol is used as a medium in the ball milling process, the ball milling rotation speed is 300-400r/min, and the ball milling time is 5-7 h.
5. The Sn-containing intermediate microwave dielectric ceramic material as claimed in claim 1 or 2, wherein in the step (2) and the step (4), the ball milling rotation speed is 350r/min, and the ball milling time is 6 h.
6. The Sn-containing intermediate microwave dielectric ceramic material of claim 1 or 2, wherein the slurry obtained in step (2) is dried, ground, sieved and calcined at 1100 ℃ and 1000 ℃ for 4 hours in step (3).
7. The Sn-containing intermediate microwave dielectric ceramic material as claimed in claim 1 or 2, wherein the binder in the step (5) is 5-7 wt% of polyvinyl alcohol solution, and the addition amount of the polyvinyl alcohol solution accounts for 5-10% of the total mass of the powder.
8. The Sn-containing intermediate microwave dielectric ceramic material as claimed in claim 7, wherein the binder in the step (5) is 5 wt% polyvinyl alcohol solution, and the addition amount thereof is 8% of the total mass of the powder.
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| CN110698194B (en) * | 2019-11-06 | 2022-05-06 | 苏州博恩希普新材料科技有限公司 | Microwave dielectric ceramic with layered structure and preparation method thereof |
| CN111170734B (en) * | 2020-01-07 | 2022-04-01 | 山东国瓷功能材料股份有限公司 | Two-phase composite microwave dielectric ceramic material for filter and preparation method thereof |
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| CN114804867B (en) * | 2022-04-29 | 2023-04-07 | 厦门松元电子股份有限公司 | Ceramic dielectric material suitable for hot-pressing sintering, ceramic device and preparation method thereof |
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