CN114394832B - Barium zirconate titanate based porcelain with stable dielectric temperature and preparation method thereof - Google Patents
Barium zirconate titanate based porcelain with stable dielectric temperature and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a barium zirconate titanate based porcelain with stable dielectric temperature and a preparation method thereof, and the barium zirconate titanate based porcelain comprises (Ba) 1‑x Gd x )(Ti 0.9 Zr 0.1 )O 3+x/2 MgO and ZnO; the preparation method comprises weighing (CH) by mol ratio 3 COO) 2 Ba、Gd(NO 3 ) 3 、C 16 H 36 O 4 Ti and Zr (NO) 3 ) 4 ·5H 2 And O, preparing main crystal phase nano powder by a sol-gel method, grinding and compression molding the main crystal phase nano powder, mgO and ZnO to prepare a sheet blank, and finally sintering to prepare the barium zirconate titanate-based porcelain. The invention leads the porcelain to have the characteristics of high dielectric constant and low dielectric loss through the synergistic action of the composite perovskite structure nano main crystal phase and the modifier, and leads the temperature change rate of the dielectric constant to be less than +/-15 percent due to the induction of dispersion phase change.
Description
Technical Field
The invention relates to electronic ceramic and a preparation method thereof, in particular to barium zirconate titanate based ceramic with stable dielectric temperature and a preparation method thereof.
Background
Barium titanate (BaTiO) 3 ) It is a good dielectric, piezoelectric and ferroelectric material, and can be extensively used for making electronic components of capacitor, PTC element and piezoelectric transducer, etc. However, the Curie point (about 120 ℃) is higher, and the dielectric constant at room temperature is only 1/6 of that at the Curie temperature, so that the application range of the dielectric material as a capacitor medium is greatly influenced.
Barium zirconate titanate [ Ba (Zr) x Ti 1-x )O 3 ]As barium titanate (BaTiO) 3 ) With barium zirconate (BaZrO) 3 ) The formed solid solution has the characteristics of high dielectricity, adjustable Curie temperature and the like, and is gradually one of research hotspots of ceramic dielectric materials due to the appearance of relaxation characteristics. However, the multiparameter synergy of the barium zirconate titanate-based ceramic with high dielectric constant, low loss and stable dielectric temperature is still one of the technical difficulties of the material as the X7R, Y V type capacitor dielectric material. Journal of electronic Components and materials 2016, volume 35, phase 3 2 O 3 Effect of doping on BZT-based ceramic Structure and dielectric Properties "article discloses a BaZr prepared by conventional solid phase method 0.1 Ti 0.9 O 3 +xGd 2 O 3 (x =0 to 0.70) ceramic having a dielectric constant as high as 4355, a dielectric loss of 0.031 and a dielectric constant having poor temperature stability. Journal of electronic Components and materials in "Ceria doped barium zirconate titanate ceramics" 2004, volume 23, no. 10Study of porcelain Properties and Structure "in the paper, there is disclosed CeO prepared by a solid phase method 2 Doped with Ba (Zr, ti) O 3 The ceramic has a room temperature dielectric constant as high as 7193, a temperature change rate of dielectric constant of-80.1 to +19.1%, and a room temperature dielectric loss of 0.0351. Journal of Applied Physics, volume 102, no. 8 of 2007 in "Dielectric properties and relaxor behavior of ray-earth (La, sm, eu, dy, Y) underlying barium zirconium titanate ceramics" a publication of the solid phase process of preparing (Ba 1-x Ln x )Zr 0.2 Ti 0.8-x/4 O 3 (x =0-0.04, ln = La, sm, eu, dy, Y) series ceramic materials in which the loss tangent at x =0.04, ln = La can be as low as 0.00005, but the room temperature dielectric constant is only 650.
Therefore, there is a need for a barium zirconate titanate based ceramic material having not only a high dielectric constant, but also low dielectric loss and high dielectric temperature stability.
Disclosure of Invention
The invention aims to: the first purpose of the invention is to provide barium zirconate titanate based porcelain with high dielectric constant, low dielectric loss and good dielectric temperature stability;
the second purpose of the invention is to provide a preparation method of the barium zirconate titanate-based porcelain.
The technical scheme is as follows: the barium zirconate titanate-based porcelain with stable dielectric temperature comprises the following components in percentage by mass:
(Ba 1-x Gd x )(Ti 0.9 Zr 0.1 )O 3+x/2 99.7-99.5wt％
MgO 0.15-0.25wt％
ZnO 0.15-0.25wt％；
wherein x =0.04-0.05.
The preparation method of the barium zirconate titanate-based porcelain with stable dielectric temperature comprises the following steps:
(1) Weighed in a molar ratio (1-x): x:0.9 3 COO) 2 Ba、Gd(NO 3 ) 3 、C 16 H 36 O 4 Ti and Zr (NO) 3 ) 4 ·5H 2 O; c is to be 16 H 36 O 4 Ti、C 2 H 5 OH or (CH) 2 OH) 2 、CH 3 Mixing and stirring COOH to obtain solution A; gd (NO) 3 ) 3 、(CH 3 COO) 2 Ba and Zr (NO) 3 ) 4 ·5H 2 Dissolving O in water to obtain solution B;
(2) Slowly dripping the solution B into the solution A, stirring, adjusting the pH value of the solution, and continuously stirring to obtain sol; putting the sol in a constant temperature environment to perform sol-gel conversion and aging; drying and calcining the aged gel to obtain main crystal phase powder;
(3) Adding MgO and ZnO into the main crystal phase powder according to mass percent, grinding, then carrying out compression molding to obtain a green body, and sintering the green body to obtain the barium zirconate titanate-based porcelain.
Wherein, in the step (1), the C 16 H 36 O 4 Ti、C 2 H 5 OH or (CH) 2 OH) 2 、CH 3 COOH are mixed according to a volume ratio of 1.
Wherein, in the step (1), gd (NO) is added 3 ) 3 、(CH 3 COO) 2 Ba and Zr (NO) 3 ) 4 ·5H 2 O is dissolved in water according to the ratio of the solute to the solvent substance being 1.
Wherein in the step (2), the pH value is 3.0-4.5.
Wherein, in the step (1), C is added 16 H 36 O 4 Ti、C 2 H 5 OH or (CH) 2 OH) 2 、CH 3 Mixing and stirring COOH for 0.5-1 h to obtain solution A; slowly dripping the solution B into the solution A, stirring for 1.5-2.5 h, and adjusting the pH value of the solution; stirring for 0.5-1 hr to obtain sol.
Wherein, in the step (2), the sol is placed in a constant-temperature water bath to generate sol-gel conversion; the constant temperature water bath temperature is 50-80 ℃, and the sol-gel conversion time is 20-50 min.
Wherein, in the step (2), the aging temperature is 20-25 ℃ and the aging time is 8-12 h.
In the step (2), the drying mode is drying, and the drying temperature is 80-100 ℃.
Wherein in the step (2), the calcining temperature is 750-1000 ℃, the temperature is kept for 2-3 h, and the heating rate is 4-5 ℃/min.
Wherein, the sintering process in the step (3) comprises the following steps: keeping the temperature at 1290-1370 ℃ for 1-4 h, wherein the heating rate is 4-5 ℃/min.
Has the advantages that: compared with the prior art, the invention has the following remarkable effects: 1. the porcelain is obtained by sol-gel method (Ba) 1-x Gd x )(Ti 0.9 Zr 0.1 )O 3+x/2 The main crystal phase nano powder is sintered under the action of the modifiers ZnO and MgO to obtain the micron polycrystalline ceramic, so that the ceramic has the characteristics of high dielectric constant and low dielectric loss, and the temperature stability of the dielectric constant of the ceramic is obviously improved due to the induction of dispersion phase change; 2. the capacitor dielectric material can meet the use requirements of a blocking circuit and a bypass circuit on the capacitor dielectric material, and has wide application prospects in the fields of automobiles, electronic appliances, medical treatment and the like.
Drawings
FIG. 1 is a transmission electron micrograph of barium zirconate titanate-based primary crystalline phase powder prepared in example 1 of the present invention;
FIG. 2 is a surface micro-topography of barium zirconate titanate-based porcelain prepared in example 1 in accordance with the present invention;
FIG. 3 is an X-ray diffraction pattern of barium zirconate titanate-based porcelain prepared in example 1 of the present invention.
Detailed Description
The present invention is described in further detail below.
Example 1
The main crystal phase powder of the porcelain has a chemical formula as follows: (Ba) 0.96 Gd 0.04 )(Ti 0.9 Zr 0.1 )O 3.02 ，x＝0.04。
The porcelain composition is shown in table 1 below:
TABLE 1 Components and amounts of example 1
| Components | Powder of main crystal phase | MgO | ZnO |
| Content/wt% | 99.6 | 0.2 | 0.2 |
The preparation method of the porcelain comprises the following steps:
(1) Weighed in a molar ratio of 0.96 3 COO) 2 Ba、Gd(NO 3 ) 3 、C 16 H 36 O 4 Ti and Zr (NO) 3 ) 4 ·5H 2 O; c is to be 16 H 36 O 4 Ti and C 2 H 5 OH and CH 3 Mixing and magnetically stirring COOH according to a volume ratio of 1; gd (NO) 3 ) 3 、(CH 3 COO) 2 Ba and Zr (NO) 3 ) 4 ·5H 2 Dissolving O in deionized water according to the mass ratio of solute to solvent being 1; slowly dripping the solution B into the solution A, stirring for 2 hours by magnetic force, and dripping CH 3 Adjusting the pH value of the solution to 4.0 by COOH, and continuously stirring for 0.5h to obtain sol; placing the sol in a 60 ℃ water bath kettle, keeping the temperature for 30min to perform sol-gel conversion, and aging at 25 ℃ for 12h; and drying the aged gel at 100 ℃, and calcining the gel at 1000 ℃ for 2h at the heating rate of 5 ℃/min to obtain the main crystal phase powder. As can be seen from fig. 1, the primary particles of the main crystal phase powder are in the nanometer order.
(2) Adding MgO and ZnO into the main crystal phase powder according to the mass fraction shown in Table 1, grinding for 1h in an agate mortar by a dry method, then carrying out compression molding to obtain a green body, placing the green body on a ceramic base plate dispersed with a zirconium dioxide padding, controlling the heating rate to be 5 ℃/min, heating to 1320 ℃, sintering and preserving heat for 2h to obtain a ceramic, and finally cooling to room temperature along with a furnace to obtain the barium zirconate titanate-based ceramic material. It can be seen from fig. 2 that the porcelain is dense and has a uniform particle size distribution, and the average grain size is in the order of micrometers. As can be seen from FIG. 3, the porcelain is a perovskite structure single-phase solid solution.
As can be seen from the performance test of the prepared ceramic material, the barium zirconate titanate-based ceramic material prepared in the embodiment has a room temperature dielectric constant of 3732, and a dielectric loss of 0.0211, a dielectric constant temperature change rate of +7.2 to-13.4% within a temperature range of-30 ℃ to 85 ℃.
Example 2
The main crystal phase powder of the porcelain has a chemical formula as follows: (Ba) 0.95 Gd 0.05 )(Ti 0.9 Zr 0.1 )O 3.025 ，x＝0.05。
The porcelain composition is shown in table 2 below:
TABLE 2 Components and amounts of example 2
| Components | Powder of main crystal phase | MgO | ZnO |
| Content/wt% | 99.6 | 0.2 | 0.2 |
The preparation method of the porcelain comprises the following steps:
(1) Weighed in a molar ratio of 0.95 3 COO) 2 Ba、Gd(NO 3 ) 3 、C 16 H 36 O 4 Ti and Zr (NO) 3 ) 4 ·5H 2 And O. C is to be 16 H 36 O 4 Ti and C 2 H 5 OH and CH 3 COOH was mixed at a volume ratio of 1. Gd (NO) 3 ) 3 、(CH 3 COO) 2 Ba and Zr (NO) 3 ) 4 ·5H 2 Dissolving O in deionized water according to the mass ratio of the solute to the solvent substance of 1. Slowly dripping the solution B into the solution A, stirring for 2 hours by magnetic force, and dripping CH 3 Adjusting the pH value of the solution to 4.0 by COOH, and continuously stirring for 0.5h to obtain sol. Placing the sol in a 60 ℃ water bath kettle, keeping the temperature for 30min to perform sol-gel conversion, and aging at 25 ℃ for 8h. And drying the aged gel at 100 ℃, and calcining the gel at 1000 ℃ for 2h at the heating rate of 5 ℃/min to obtain the main crystal phase powder.
(2) Adding MgO and ZnO into the main crystal phase powder according to the mass fraction shown in Table 2, grinding for 1h in an agate mortar by a dry method, then carrying out compression molding to obtain a green body, placing the green body on a ceramic base plate dispersed with a zirconium dioxide padding, controlling the heating rate to be 5 ℃/min, heating to 1320 ℃, sintering and preserving heat for 2h to obtain a ceramic, and finally cooling to room temperature along with a furnace to obtain the barium zirconate titanate-based ceramic material.
As can be seen from the performance test of the prepared porcelain, the barium zirconate titanate-based porcelain prepared in the embodiment has the room-temperature dielectric constant of 3194, the dielectric loss of 0.0179 and the temperature change rate of the dielectric constant of +10.0 to-7.6 percent within the range of-30 ℃ to 85 ℃.
Example 3
The main crystal phase powder of the porcelain has a chemical formula as follows: (Ba) 0.954 Gd 0.046 )(Ti 0.9 Zr 0.1 )O 3.023 ，x＝0.046。
The porcelain composition is shown in table 3 below:
table 3 components and amounts thereof of example 3
| Components | Powder of main crystal phase | MgO | ZnO |
| Content/wt% | 99.7 | 0.15 | 0.15 |
The preparation method of the porcelain comprises the following steps:
(1) Weighed in a molar ratio of 0.954 3 COO) 2 Ba、Gd(NO 3 ) 3 、C 16 H 36 O 4 Ti and Zr (NO) 3 ) 4 ·5H 2 And O. C is to be 16 H 36 O 4 Ti and C 2 H 5 OH and CH 3 COOH was mixed at a volume ratio of 1. Gd (NO) 3 ) 3 、(CH 3 COO) 2 Ba and Zr (NO) 3 ) 4 ·5H 2 Dissolving O in deionized water according to the mass ratio of the solute to the solvent substance of 1. Slowly dripping the solution B into the solution A, magnetically stirring for 2h, and dripping CH 3 Adjusting the pH value of the solution to 3.0 by COOH, and continuously stirring for 0.5h to obtain sol. Placing the sol in a 60 ℃ water bath kettle, keeping the temperature for 30min to perform sol-gel conversion, and aging at 25 ℃ for 10h. And drying the aged gel at 100 ℃, and calcining the gel at 1000 ℃ for 2h at the heating rate of 4 ℃/min to obtain the main crystal phase powder.
(2) Adding MgO and ZnO into the main crystal phase powder according to the mass fraction of Table 3, grinding for 1h in an agate mortar by a dry method, then carrying out compression molding to obtain a green body, placing the green body on a ceramic base plate dispersed with a zirconium dioxide padding, controlling the heating rate to be 4 ℃/min, heating to 1320 ℃, sintering and preserving heat for 2h to obtain a ceramic, and finally cooling to room temperature along with a furnace to obtain the barium zirconate titanate-based ceramic material.
As can be seen from the performance test of the prepared porcelain, the barium zirconate titanate-based porcelain prepared in the embodiment has the room-temperature dielectric constant of 3476 and the dielectric loss of 0.0192, and the temperature change rate of the dielectric constant is +8.9 to-10.6 percent within the range of-30 ℃ to 85 ℃.
Example 4
The main crystalline phase powder of the porcelain has a chemical formula as follows: (Ba) 0.96 Gd 0.04 )(Ti 0.9 Zr 0.1 )O 3.02 ，x＝0.04。
The porcelain composition is shown in table 4 below:
table 4 components and amounts thereof of example 4
| Components | Powder of main crystal phase | MgO | ZnO |
| Content/wt% | 99.7 | 0.15 | 0.15 |
The preparation method of the porcelain comprises the following steps:
(1) Weighed in a molar ratio of 0.96 3 COO) 2 Ba、Gd(NO 3 ) 3 、C 16 H 36 O 4 Ti and Zr (NO) 3 ) 4 ·5H 2 And O. C is to be 16 H 36 O 4 Ti and C 2 H 5 OH and CH 3 COOH was mixed at a volume ratio of 1. Gd (NO) 3 ) 3 、(CH 3 COO) 2 Ba and Zr (NO) 3 ) 4 ·5H 2 Dissolving O in deionized water according to the mass ratio of the solute to the solvent substance of 1. Slowly dripping the solution B into the solution A, magnetically stirring for 1.5h, and dripping CH 3 Adjusting the pH value of the solution to 3.0 by COOH, and continuously stirring for 0.5h to obtain sol. Placing the sol in a 50 ℃ water bath kettle, keeping the temperature for 20min to perform sol-gel conversion, and aging at 20 ℃ for 8h. And drying the aged gel at 80 ℃, and calcining the gel at 750 ℃ for 2h at the heating rate of 4 ℃/min to obtain main crystal phase powder.
(2) Adding MgO and ZnO into the main crystal phase powder according to the mass fraction in Table 4, grinding for 1h in an agate mortar by a dry method, then carrying out compression molding to obtain a green body, placing the green body on a ceramic base plate dispersed with a zirconium dioxide padding, controlling the heating rate to rise to 1290 ℃ at 4 ℃/min, sintering and preserving heat for 1h to form ceramic, and finally cooling to room temperature along with a furnace to obtain the barium zirconate titanate-based ceramic material.
As can be seen from the performance test of the prepared porcelain, the barium zirconate titanate-based porcelain prepared in the embodiment has the room-temperature dielectric constant of 3520, the dielectric loss of 0.0232, and the temperature change rate of the dielectric constant of +7.9 to-13.7 percent within the range of-30 to 85 ℃.
Example 5
The main crystal phase powder of the porcelain has a chemical formula as follows: (Ba) 0.95 Gd 0.05 )(Ti 0.9 Zr 0.1 )O 3.025 ，x＝0.05。
The porcelain composition is shown in table 5 below:
table 5 components and amounts thereof of example 5
| Components | Powder of main crystal phase | MgO | ZnO |
| Content/wt% | 99.5 | 0.25 | 0.25 |
The preparation method of the porcelain comprises the following steps:
(1) Weighed in a molar ratio of 0.95 3 COO) 2 Ba、Gd(NO 3 ) 3 、C 16 H 36 O 4 Ti and Zr (NO) 3 ) 4 ·5H 2 And O. C is to be 16 H 36 O 4 Ti and C 2 H 5 OH and CH 3 And mixing COOH in a volume ratio of 1. Gd (NO) 3 ) 3 、(CH 3 COO) 2 Ba and Zr (NO) 3 ) 4 ·5H 2 Dissolving O in deionized water according to the mass ratio of the solute to the solvent substance of 1. Slowly dripping the solution B into the solution A, stirring for 2.5h by magnetic force, and dripping CH 3 And adjusting the pH value of the solution to 4.5 by COOH, and continuously stirring for 1h to obtain the sol. Placing the sol in a water bath kettle at 80 deg.C, keeping the temperature for 50min to perform sol-gel conversion, and aging at 25 deg.C for 12h. And drying the aged gel at 100 ℃, and calcining the gel at 1000 ℃ for 3h at the heating rate of 5 ℃/min to obtain the main crystal phase powder.
(2) Adding MgO and ZnO into the main crystal phase powder according to the mass fraction of Table 5, grinding for 1.5h in an agate mortar by a dry method, then carrying out compression molding to obtain a green body, placing the green body on a ceramic backing plate dispersed with a zirconium dioxide padding, controlling the heating rate to rise to 1370 ℃ at 5 ℃/min, sintering and preserving the temperature for 4h to form ceramic, and finally cooling to room temperature along with a furnace to obtain the barium zirconate titanate-based ceramic material.
As can be seen from the performance test of the prepared porcelain, the barium zirconate titanate-based porcelain prepared in the embodiment has the room-temperature dielectric constant of 3274 and the dielectric loss of 0.0189, and the temperature change rate of the dielectric constant is +11.5 to-8.3 within the range of-30 ℃ to 85 ℃.
Example 6
The main crystalline phase powder of the porcelain has a chemical formula as follows: (Ba) 0.96 Gd 0.04 )(Ti 0.9 Zr 0.1 )O 3.02 ，x＝0.04。
The porcelain composition is shown in table 6 below:
table 6 components and amounts thereof of example 6
| Components | Powder of main crystal phase | MgO | ZnO |
| Content/wt% | 99.65 | 0.2 | 0.15 |
The preparation method of the porcelain comprises the following steps:
(1) Weighed in a molar ratio of 0.96 3 COO) 2 Ba、Gd(NO 3 ) 3 、C 16 H 36 O 4 Ti and Zr (NO) 3 ) 4 ·5H 2 And O. C is to be 16 H 36 O 4 Ti and (CH) 2 OH) 2 And CH 3 COOH was mixed at a volume ratio of 1. Gd (NO) 3 ) 3 、(CH 3 COO) 2 Ba and Zr (NO) 3 ) 4 ·5H 2 Dissolving O in deionized water according to the mass ratio of the solute to the solvent substance of 1. Slowly dripping the solution B into the solution A, magnetically stirring for 1.5h, and dripping CH 3 Adjusting the pH value of the solution to 3.0 by COOH, and continuously stirring for 0.5h to obtain the sol. Placing the sol in a 50 ℃ water bath kettle, keeping the temperature for 20min to perform sol-gel conversion, and aging at 20 ℃ for 8h. And drying the aged gel at 80 ℃, and calcining the gel at 750 ℃ for 2h at the heating rate of 4 ℃/min to obtain main crystal phase powder.
(2) Adding MgO and ZnO into the powder with the main crystal phase according to the mass fraction shown in the table 6, grinding for 1 hour in an agate mortar by a dry method, then carrying out compression molding to obtain a blank body, placing the blank body on a ceramic base plate dispersed with a zirconium dioxide padding, controlling the heating rate to rise to 1290 ℃ at a rate of 4 ℃/min, sintering and preserving heat for 1 hour to obtain ceramic, and finally cooling to room temperature along with a furnace to obtain the barium zirconate titanate-based ceramic material.
As can be seen from the performance test of the prepared porcelain, the barium zirconate titanate-based porcelain prepared in the embodiment has the room-temperature dielectric constant of 3190, the dielectric loss of 0.0176 and the temperature change rate of the dielectric constant of +10.9 to-14.1 percent within the range of-30 to 85 ℃.
Example 7
The main crystal phase powder of the porcelain has a chemical formula as follows: (Ba) 0.95 Gd 0.05 )(Ti 0.9 Zr 0.1 )O 3.025 ，x＝0.05。
The porcelain composition is shown in table 7 below:
table 7 components and amounts thereof of example 7
| Components | Powder of main crystal phase | MgO | ZnO |
| Content/wt% | 99.55 | 0.2 | 0.25 |
The preparation method of the porcelain comprises the following steps:
(1) And (c) are weighed according to a molar ratio of 0.95 3 COO) 2 Ba、Gd(NO 3 ) 3 、C 16 H 36 O 4 Ti and Zr (NO) 3 ) 4 ·5H 2 And O. C is to be 16 H 36 O 4 Ti and (CH) 2 OH) 2 And CH 3 COOH was mixed in a volume ratio of 1. Gd (NO) 3 ) 3 、(CH 3 COO) 2 Ba and Zr (NO) 3 ) 4 ·5H 2 Dissolving O in deionized water according to the mass ratio of the solute to the solvent substance of 1. Slowly dripping the solution B into the solution A, magnetically stirring for 1.5h, and dripping CH 3 Adjusting the pH value of the solution to 4.0 by COOH, and continuously stirring for 0.5h to obtain sol. Placing the sol in a 50 ℃ water bath kettle, keeping the temperature for 20min to perform sol-gel conversion, and aging at 20 ℃ for 10h. And drying the aged gel at 80 ℃, and calcining the gel at 1000 ℃ for 2h at the heating rate of 4 ℃/min to obtain the main crystal phase powder.
(2) Adding MgO and ZnO into the main crystal phase powder according to the mass fraction shown in Table 7, grinding for 1h in an agate mortar by a dry method, then carrying out compression molding to obtain a green body, placing the green body on a ceramic base plate dispersed with a zirconium dioxide padding, controlling the heating rate to rise to 1290 ℃ at 4 ℃/min, sintering and preserving heat for 2h to form ceramic, and finally cooling to room temperature along with a furnace to obtain the barium zirconate titanate-based ceramic material.
As can be seen from the performance test of the prepared porcelain, the barium zirconate titanate-based porcelain prepared in the embodiment has the room-temperature dielectric constant of 3234 and the dielectric loss of 0.0188, and the temperature change rate of the dielectric constant is +9.1 to-11.3 within the range of-30 ℃ to 85 ℃.
Claims (10)
1. The barium zirconate titanate-based porcelain with stable dielectric temperature is characterized by comprising the following components in percentage by mass:
(Ba 1-x Gd x )(Ti 0.9 Zr 0.1 )O 3+x/2 99.7-99.5wt%
MgO 0.15-0.25wt%
ZnO 0.15-0.25wt%；
wherein x =0.04-0.05;
the preparation method of the barium zirconate titanate-based porcelain with stable dielectric temperature comprises the following steps:
(1) Weighed in a molar ratio (1-x) x:0.9 (CH) 3 COO) 2 Ba、Gd(NO 3 ) 3 、C 16 H 36 O 4 Ti and Zr (NO) 3 ) 4 ·5H 2 O; c is to be 16 H 36 O 4 Ti、C 2 H 5 OH or (CH) 2 OH) 2 、CH 3 Mixing and stirring COOH to obtain solution A; gd (NO) 3 ) 3 、(CH 3 COO) 2 Ba and Zr (NO) 3 ) 4 ·5H 2 Dissolving O in water to obtain solution B;
(2) Slowly dripping the solution B into the solution A, stirring, adjusting the pH value of the solution, and continuously stirring to obtain sol; putting the sol in a constant temperature environment to perform sol-gel conversion and aging; drying and calcining the aged gel to obtain main crystal phase powder;
(3) Adding MgO and ZnO into the main crystal phase powder according to the mass percentage, grinding the powder, then carrying out compression molding to obtain a blank body, and sintering the blank body to obtain the barium zirconate titanate-based porcelain.
2. A method of preparing a dielectric temperature stable barium zirconate titanate-based porcelain according to claim 1, comprising the steps of:
(1) Weighed in a molar ratio (1-x) x:0.9 (CH) 3 COO) 2 Ba、Gd(NO 3 ) 3 、C 16 H 36 O 4 Ti and Zr (NO) 3 ) 4 ·5H 2 O; c is to be 16 H 36 O 4 Ti、C 2 H 5 OH or (CH) 2 OH) 2 、CH 3 Mixing and stirring COOH to obtain solution A; gd (NO) 3 ) 3 、(CH 3 COO) 2 Ba and Zr (NO) 3 ) 4 ·5H 2 Dissolving O in water to obtain solution B;
(2) Slowly dripping the solution B into the solution A, stirring, adjusting the pH value of the solution, and continuously stirring to obtain sol; putting the sol in a constant temperature environment to perform sol-gel conversion and aging; drying and calcining the aged gel to obtain main crystal phase powder;
(3) Adding MgO and ZnO into the main crystal phase powder according to mass percent, grinding, then carrying out compression molding to obtain a green body, and sintering the green body to obtain the barium zirconate titanate-based porcelain.
3. The method of claim 2, wherein in step (1), C is 16 H 36 O 4 Ti、C 2 H 5 OH or (CH) 2 OH) 2 、CH 3 And mixing COOH according to a volume ratio of 1.
4. The method for preparing dielectric temperature stable barium zirconate titanate-based porcelain according to claim 2, wherein Gd (NO) is added in step (1) 3 ) 3 、(CH 3 COO) 2 Ba and Zr (NO) 3 ) 4 ·5H 2 Dissolving O in water according to the ratio of the solute to the solvent substance being 1.
5. The method for preparing dielectric temperature stable barium zirconate titanate-based porcelain according to claim 2, wherein in the step (2), the pH value is 3.0 to 4.5.
6. The method for preparing dielectric temperature stable barium zirconate titanate-based porcelain according to claim 2, wherein in the step (2), the sol is placed in a constant-temperature water bath to cause sol-gel conversion; the constant-temperature water bath temperature is 50 to 80 ℃, and the sol-gel conversion time is 20 to 50min.
7. The method for preparing dielectric temperature stable barium zirconate titanate-based porcelain according to claim 2, wherein in the step (2), the aging temperature is 20 to 25 ℃ and the aging time is 8 to 12h.
8. The method for preparing the dielectric temperature stable barium zirconate titanate-based porcelain according to claim 2, wherein in the step (2), the drying is carried out in a drying mode, and the drying temperature is 80-100 ℃.
9. The method for preparing the dielectric temperature stable barium zirconate titanate-based ceramic material according to claim 2, wherein in the step (2), the calcining temperature is 750 to 1000 ℃, the heat preservation time is 2 to 3 hours, and the heating rate is 4~5 ℃/min.
10. The method for preparing dielectric temperature stable barium zirconate titanate-based porcelain according to claim 2, wherein the sintering process in the step (3) is as follows: keeping the temperature for 1 to 4 hours at the temperature of 1290 to 1370 ℃, wherein the heating rate is 4~5 ℃/min.
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