CN113024245A - High-breakdown-strength dielectric ceramic material and preparation method thereof - Google Patents

High-breakdown-strength dielectric ceramic material and preparation method thereof Download PDF

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CN113024245A
CN113024245A CN202110379857.9A CN202110379857A CN113024245A CN 113024245 A CN113024245 A CN 113024245A CN 202110379857 A CN202110379857 A CN 202110379857A CN 113024245 A CN113024245 A CN 113024245A
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张志杰
李政东
钟明峰
徐威
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South China University of Technology SCUT
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Abstract

A dielectric ceramic material with high breakdown strength and a preparation method thereof. The dielectric ceramic material has high breakdown strength, and the preparation method comprises the following steps: 1) according to the chemical formula aTiO2‑bSiO2‑cAl2O3‑xCa3(PO4)2Weighing raw materials according to the proportion of the reagents; 2) and adding the weighed reagent into deionized water and zirconia ball milling beads for ball milling, and then adding PVA (polyvinyl alcohol) and performing spray drying on the slurry. Pressing the obtained mixed raw material into a die with the diameter of 15mm under 30MPa to obtain a cylindrical green blank with the thickness of 0.5 mm; 3) discharging the adhesive of the prepared cylindrical green body, and sintering at 1200-1300 ℃ to obtain the fired ceramic wafer. The dielectric ceramic material has high breakdown strength, simple preparation process and good dielectric constantThe method has the advantages of low production cost, no lead and environmental protection, and has wide application prospect in a high-voltage solid-state pulse power system.

Description

High-breakdown-strength dielectric ceramic material and preparation method thereof
Technical Field
The invention relates to the field of materials, in particular to the field of high-performance dielectric ceramic materials, and specifically relates to a dielectric ceramic material with high breakdown strength and a preparation method thereof. The invention belongs to the field of inorganic material dielectric ceramics and preparation thereof, and provides a titanium dioxide-based dielectric ceramic material with high breakdown strength and a preparation method thereof, which have wide application prospect.
Background
The pulse power system has wide application in life, can be applied to laser drive, dielectric wall accelerator, microwave source generator, fusion, electromagnetic rail gun and other drives, and has the main working principle that all stored electric energy is released to a load instantly when needed after long-time charging. The performance of a pulse power system depends to a large extent on the performance of the pulse forming line. The pulse forming line is an important component of a pulse power system and plays a major role including storing energy released by a previous stage and compressing a pulse width. As can be seen from the effect of the pulse-forming wire, the pulse-forming wire material needs to have a high energy storage density and a moderate dielectric constant. In order to meet the requirement of high energy storage density, the dielectric material is required to have higher breakdown strength and higher dielectric constant in order to obtain higher energy storage density according to a calculation formula of the energy storage density. However, it has been found that it is difficult to simultaneously improve the breakdown strength and the dielectric constant. Considering that the breakdown strength has a large influence on the energy storage density, and the operating condition of the pulse forming line needs to withstand a high voltage to prevent breakdown, a greater breakthrough is needed in the operation of improving the breakdown strength.
According to the performance requirements of the pulse forming line, the dielectric material with high dielectric breakdown strength, medium dielectric constant and low dielectric loss has wide application prospect in a high-voltage solid-state pulse power system.
Materials that currently have potential applications in this area include polymeric materials, glass-ceramic materials, and dielectric-ceramic materials. The polymer dielectric material has high breakdown strength and certain flexibility, and plays an important role in certain specific occasions. However, the polymer dielectric material has the problems of low dielectric constant, poor temperature stability, easy aging and the like, and the use of the polymer dielectric material is limited. The glass ceramic material has the advantages of high breakdown strength and dielectric constant, fast charge-discharge response, high thermal stability and the like, but has certain dielectric relaxation and high dielectric loss, and can generate a large amount of heat in the using process to cause the failure of a device.
Compared with other two types of dielectric materials, the dielectric ceramic has stable higher dielectric constant and lower dielectric loss, has smaller change in wider temperature and frequency range, but generally has lower breakdown strength so as not to meet the requirements of practical application. Therefore, the development of a dielectric ceramic system which has high breakdown strength, moderate dielectric constant and low dielectric loss has wide application prospect.
TiO2The dielectric ceramic is a typical linear dielectric ceramic, has a relatively high dielectric constant of about 110 at room temperature, has the advantages of stable frequency characteristic, low temperature change rate, high voltage linearity stability, high charge and discharge efficiency and the like, and has great potential in the field of energy storage dielectrics. But its low breakdown strength limits its use. Thus, TiO enhancement2The improvement of the dielectric ceramic breakdown strength has very important significance.
Patent CN107473734B discloses a linear dielectric ceramic system with high breakdown strength: the dielectric ceramic with excellent electrical properties is prepared by adopting a traditional solid phase method. However, in the development of practical applications in certain fields of application, there is still a need for dielectric ceramic materials having a higher breakdown strength. The invention aims to provide a dielectric ceramic system with higher breakdown strength so as to meet the actual requirement.
Disclosure of Invention
The invention aims to provide a dielectric ceramic material with high breakdown strength and a preparation method thereof; aTiO designed by the invention2-bSiO2-cAl2O3-xCa3(PO4)2A ceramic system havingThe dielectric property is excellent, the breakdown strength is high, and the application prospect in a nanosecond-level high-gradient pulse power supply system is wide.
The technical scheme adopted by the invention is as follows:
a dielectric ceramic having a high breakdown strength, the maximum value of which can be up to 90.8 kV/mm. The preparation method of the dielectric ceramic material with high breakdown strength comprises the following steps:
1) during the preparation process, according to the chemical formula aTiO2-bSiO2-cAl2O3-xCa3(PO4)2The raw materials are weighed according to the proportion of the reagents. Wherein the raw material comprises reagent grade rutile type TiO2(99％)，α-Al2O3(99％)，Ca3(PO4)2(99%) and SiO2(99％)；
2) And adding the weighed reagent into deionized water and zirconia ball milling beads for ball milling, and then adding PVA (polyvinyl alcohol) and performing spray drying on the slurry. Pressing the obtained mixed raw material into a die with the diameter of 15mm under 30MPa to obtain a cylindrical green blank with the thickness of 0.5 mm;
3) discharging the prepared adhesive of the cylindrical green body, and sintering at 1200-1300 ℃ to obtain a fired ceramic wafer;
preferably, the proportions a, b, c and x of the raw materials of the reagents in the step 1) are mass ratios, wherein a is more than or equal to 3 and less than or equal to 6, b is more than or equal to 0 and less than or equal to 2, c is more than 0 and less than or equal to 2, and x is more than 0 and less than or equal to 4.
Preferably, the mass ratio of the reagent, the water and the ball milling beads in the step 2) is 1.0 (1.5-2.0): (3.0-4.0).
Preferably, the rotating speed of the ball mill in the ball milling process in the step 2) is 300-500 r/min, and the ball milling time is 8-14 h.
Preferably, the PVA added in the step 2) has a concentration of 2-5 wt% and an addition amount of 30-80 ml.
Preferably, the cylindrical green body in the step 3) is subjected to heat preservation at 600-800 ℃ for 120-180 min in the sintering process to discharge the binder.
Preferably, the rate of temperature rise of the cylindrical green blank in the step 3) is 6-8 ℃/min.
Preferably, the cylindrical green body in the step 3) is sintered at the temperature of 1200-1300 ℃ for 60-180 min.
The dielectric ceramic material with high breakdown strength prepared by the preparation method provided by the invention has the maximum dielectric breakdown strength of 90.8 kV/mm.
Compared with the prior art, the invention has the beneficial effects that:
1) the dielectric ceramic with high breakdown strength is prepared by a solid-phase reaction method, and has the characteristics of lead-free environmental protection, simple process, low cost and the like;
2) the invention significantly changes the crystalline phase composition and the microstructure of the material by regulating and controlling the proportion of the dielectric ceramic raw materials, thereby greatly improving the TiO content2Breakdown properties of the base dielectric ceramic.
Drawings
FIG. 1 shows aTiO compounds of examples 1 to 52-bSiO2-cAl2O3-xCa3(PO4)2XRD pattern of the base dielectric ceramic.
FIG. 2 shows aTiO compounds of examples 1 to 52-bSiO2-cAl2O3-xCa3(PO4)2A cross-sectional SEM image of the base dielectric ceramic, wherein (a) x is 0.33, (b) x is 0.66, (c) x is 0.99, (d) x is 1.32, and (e) x is 1.65.
FIG. 3 shows aTiO compounds of examples 1 to 52-bSiO2-cAl2O3-xCa3(PO4)2The dielectric constant and dielectric loss of the base dielectric ceramic are plotted against frequency.
FIG. 4 shows aTiO compounds of examples 1 to 52-bSiO2-cAl2O3-xCa3(PO4)2Breakdown Strength (E) of the base dielectric ceramicb) Weibull plot of (c).
FIG. 5 shows aTiO of comparative examples 1 to 42-bSiO2-cAl2O3-xCa3(PO4)2XRD pattern of the base dielectric ceramic.
FIG. 6 shows aTiO of comparative examples 1 to 42-bSiO2-cAl2O3-xCa3(PO4)2The dielectric constant and dielectric loss of the base dielectric ceramic are plotted against frequency.
FIG. 7 shows aTiO of comparative examples 1 to 42-bSiO2-cAl2O3-xCa3(PO4)2Breakdown Strength (E) of the base dielectric ceramicb) Weibull plot of (c).
Detailed Description
In order to make the present invention easier to understand, the present invention will be further explained and illustrated with reference to specific examples, but the present invention is not limited thereto.
Example 1
A dielectric ceramic material with high breakdown strength is prepared by the following steps:
1) according to the chemical formula aTiO2-bSiO2-cAl2O3-xCa3(PO4)2Weighing rutile TiO according to the proportion of the reagents2(99％)，α-Al2O3(99％)，Ca3(PO4)2(99%) and SiO2(99%), where a is 4.13, b is 1, c is 1.19, and x is 0.33;
2) adding the weighed reagent into deionized water and zirconia ball milling beads for ball milling, then adding 60ml of PVA with the concentration of 5 wt% and then carrying out spray drying on the slurry. Pressing the obtained mixed raw material into a die with the diameter of 15mm under 30MPa to obtain a cylindrical green blank with the thickness of 0.5 mm;
3) discharging the prepared adhesive of the cylindrical green body, and sintering at 1260 ℃ to obtain a sintered ceramic wafer;
prepared aTiO2-bSiO2-cAl2O3-xCa3(PO4)2The XRD pattern of the base ceramic is shown in figure 1; a cross-sectional SEM of this fraction is shown in fig. 2 a; the dielectric spectrum of this composition is shown in FIG. 3; the weibull distribution of the breakdown strength of this composition is shown in fig. 4. As can be seen by XRD pattern analysis, aTiO2-bSiO2-cAl2O3-xCa3(PO4)2The crystal phase composition of the base ceramic is obviously regulated and controlled. According to the sectional SEM image, the grain size of the component is relatively uniform, and other crystal phases which are different from TiO in morphology can be observed in the sectional SEM2And (4) crystal grains. According to the dielectric spectrum, the dielectric constant of the composition is 35.3, and the dielectric loss is 0.0018. According to the Weber distribution diagram of the breakdown strength, the breakdown strength values of the component are distributed more intensively, and the breakdown strength value is improved to 55.9 kV/mm.
Example 2
A dielectric ceramic material with high breakdown strength is prepared by the following steps:
1) according to the chemical formula aTiO2-bSiO2-cAl2O3-xCa3(PO4)2Weighing rutile TiO according to the proportion of the reagents2(99％)，α-Al2O3(99％)，Ca3(PO4)2(99%) and SiO2(99%), where a is 4.13, b is 1, c is 1.19, and x is 0.66;
2) adding the weighed reagent into deionized water and zirconia ball milling beads for ball milling, then adding 60ml of PVA with the concentration of 5 wt% and then carrying out spray drying on the slurry. Pressing the obtained mixed raw material into a die with the diameter of 15mm under 30MPa to obtain a cylindrical green blank with the thickness of 0.5 mm;
3) keeping the prepared cylindrical green body at 600 ℃ for 120min to discharge the adhesive, and then sintering at 1260 ℃ to obtain a sintered ceramic wafer;
prepared aTiO2-bSiO2-cAl2O3-xCa3(PO4)2Base ceramic XRD is shown in fig. 1; the cross-sectional SEM is shown as b in FIG. 2; the dielectric spectrum of this composition is shown in FIG. 3; the weber distribution of the breakdown strength is shown in fig. 4. According to the analysis of XRD pattern, aTiO2-bSiO2-cAl2O3-xCa3(PO4)2The crystal phase composition of the base ceramic is obviously regulated and controlled. According to the SEM image of the section, the composition isThe grain size is relatively uniform, and other crystal phases which appear in the section SEM and have different morphologies from TiO2And (4) crystal grains. According to the dielectric spectrum, the dielectric constant of the composition is 32.3, and the dielectric loss is 0.0013. According to the Weber distribution diagram of the breakdown strength, the breakdown strength values of the component are distributed more intensively, and the breakdown strength value is improved to 73.1 kV/mm.
Example 3
A dielectric ceramic material with high breakdown strength is prepared by the following steps:
1) according to the chemical formula aTiO2-bSiO2-cAl2O3-xCa3(PO4)2Weighing rutile TiO according to the proportion of the reagents2(99％)，α-Al2O3(99％)，Ca3(PO4)2(99%) and SiO2(99%), where a is 4.13, b is 1, c is 1.19, and x is 0.99;
2) adding the weighed reagent into deionized water and zirconia ball milling beads for ball milling, then adding 60ml of PVA with the concentration of 5 wt% and then carrying out spray drying on the slurry. Pressing the obtained mixed raw material into a die with the diameter of 15mm under 30MPa to obtain a cylindrical green blank with the thickness of 0.5 mm;
3) discharging the prepared adhesive of the cylindrical green body, and sintering at 1250 ℃ to obtain a sintered ceramic plate;
prepared aTiO2-bSiO2-cAl2O3-xCa3(PO4)2The XRD pattern of the base ceramic is shown in figure 1; a cross-sectional SEM of this fraction is shown in fig. 2 c; the dielectric spectrum of this composition is shown in FIG. 3; the weibull distribution of the breakdown strength of this composition is shown in fig. 4. As can be seen by XRD pattern analysis, aTiO2-bSiO2-cAl2O3-xCa3(PO4)2The crystal phase composition of the base ceramic is obviously regulated and controlled. According to the sectional SEM image, the grain size of the component is relatively uniform, and other crystal phases which are different from TiO in morphology can be observed in the sectional SEM2And (4) crystal grains. According to the dielectric spectrum, theThe dielectric constant of the composition was 27.1 and the dielectric loss was 0.0031. According to the Weber distribution diagram of the breakdown strength, the breakdown strength values of the component are distributed more intensively, and the breakdown strength value is improved to 74.7 kV/mm.
Example 4
A dielectric ceramic material with high breakdown strength is prepared by the following steps:
1) according to the chemical formula aTiO2-bSiO2-cAl2O3-xCa3(PO4)2Weighing rutile TiO according to the proportion of the reagents2(99％)，α-Al2O3(99％)，Ca3(PO4)2(99%) and SiO2(99%), wherein a is 4.13, b is 1, c is 1.19, and x is 1.32;
2) adding the weighed reagent into deionized water and zirconia ball milling beads for ball milling, then adding 60ml of PVA with the concentration of 5 wt% and then carrying out spray drying on the slurry. Pressing the obtained mixed raw material into a die with the diameter of 15mm under 30MPa to obtain a cylindrical green blank with the thickness of 0.5 mm;
3) discharging the prepared adhesive of the cylindrical green body, and sintering at 1250 ℃ to obtain a sintered ceramic plate;
prepared aTiO2-bSiO2-cAl2O3-xCa3(PO4)2Base ceramic XRD is shown in fig. 1; a cross-sectional SEM of this fraction is shown in fig. 2 d; the dielectric spectrum of this composition is shown in FIG. 3; the weibull distribution of the breakdown strength of this composition is shown in fig. 4. As can be seen by XRD pattern analysis, aTiO2-bSiO2-cAl2O3-xCa3(PO4)2The crystal phase composition of the base ceramic is obviously regulated and controlled. From the sectional SEM images, the grain size of the composition was relatively uniform, and other crystal phases appeared in the sectional SEM could be observed. The appearance of the crystalline phase in the component is different from that of TiO2Grains having a relatively rough surface, shape and size defined by the surrounding TiO2The space of the crystal grains. According to the dielectric spectrum, the dielectric constant of the composition is 26.8, and the dielectric loss is 0.0026. According to the Weber distribution diagram of the breakdown strength, the breakdown strength values of the component are distributed more intensively, and the breakdown strength value of the component is greatly improved to 90.8kV/mm after the crystal phase composition is regulated and controlled, and is obviously higher than other components.
Example 5
A dielectric ceramic material with high breakdown strength is prepared by the following steps:
1) according to the chemical formula aTiO2-bSiO2-cAl2O3-xCa3(PO4)2Weighing rutile TiO according to the proportion of the reagents2(99％)，α-Al2O3(99％)，Ca3(PO4)2(99%) and SiO2(99%), where a is 4.13, b is 1, c is 1.19, and x is 1.65;
2) adding the weighed reagent into deionized water and zirconia ball milling beads for ball milling, then adding 60ml of PVA with the concentration of 5 wt% and then carrying out spray drying on the slurry. Pressing the obtained mixed raw material into a die with the diameter of 15mm under 30MPa to obtain a cylindrical green blank with the thickness of 0.5 mm;
3) discharging the prepared adhesive of the cylindrical green body, and sintering at 1240 ℃ to obtain a sintered ceramic wafer;
prepared aTiO2-bSiO2-cAl2O3-xCa3(PO4)2The XRD pattern of the base ceramic is shown in figure 1; a cross-sectional SEM of this fraction is shown in fig. 2 e; the dielectric spectrum of this composition is shown in FIG. 3; the weibull distribution of the breakdown strength of this composition is shown in fig. 4. As can be seen by XRD pattern analysis, aTiO2-bSiO2-cAl2O3-xCa3(PO4)2The crystal phase composition of the base ceramic is obviously regulated and controlled. According to the sectional SEM image, the grain size of the component is relatively uniform, and other crystal phases which are different from TiO in morphology can be observed in the sectional SEM2And (4) crystal grains. According to the dielectric spectrum, the dielectric constant of the composition is 25.8, and the dielectric loss is 0.0019. From the Weber distribution of the breakdown strength, the compositionThe distribution of the breakdown strength value is concentrated, and the breakdown strength value is improved to 73.9 kV/mm.
Comparative example 1
A dielectric ceramic material with high breakdown strength is prepared by the following steps:
1) according to the chemical formula aTiO2-bSiO2-cAl2O3-xCa3(PO4)2Weighing rutile TiO according to the proportion of the reagents2(99％)，α-Al2O3(99％)，Ca3(PO4)2(99%) and SiO2(99%), wherein a is 4.13, b is 1, c is 1.19, and x is 0;
2) adding the weighed reagent into deionized water and zirconia ball milling beads for ball milling, then adding 60ml of PVA with the concentration of 5 wt% and then carrying out spray drying on the slurry. Pressing the obtained mixed raw material into a die with the diameter of 15mm under 30MPa to obtain a cylindrical green blank with the thickness of 0.5 mm;
3) discharging the prepared adhesive of the cylindrical green body, and sintering at 1240 ℃ to obtain a sintered ceramic wafer;
prepared aTiO2-bSiO2-cAl2O3-xCa3(PO4)2The XRD pattern of the base ceramic is shown in figure 5; the dielectric spectrum of this composition is shown in fig. 6; the weibull distribution of the breakdown strength of this composition is shown in fig. 7. The aTiO prepared by the proportion can be known by XRD pattern analysis2-bSiO2-cAl2O3-xCa3(PO4)2Other crystal phases are generated in the base ceramic. From the dielectric spectrum, the dielectric constant of this composition was 46.5, and the dielectric loss was 0.0034. According to the Weber distribution diagram of the breakdown strength, the breakdown strength values of the component are distributed in a concentrated mode, and the breakdown strength value is 55.9 kV/mm.
Comparative example 2
A dielectric ceramic material with high breakdown strength is prepared by the following steps:
1) according to the chemical formula aTiO2-bSiO2-cAl2O3-xCa3(PO4)2Weighing rutile TiO according to the proportion of the reagents2(99％)，α-Al2O3(99％)，Ca3(PO4)2(99%) and SiO2(99%), wherein a is 4.13, b is 1, c is 1, and x is 1.20;
2) adding the weighed reagent into deionized water and zirconia ball milling beads for ball milling, then adding 60ml of PVA with the concentration of 5 wt% and then carrying out spray drying on the slurry. Pressing the obtained mixed raw material into a die with the diameter of 15mm under 30MPa to obtain a cylindrical green blank with the thickness of 0.5 mm;
3) discharging the prepared adhesive of the cylindrical green body, and sintering at 1240 ℃ to obtain a sintered ceramic wafer;
prepared aTiO2-bSiO2-cAl2O3-xCa3(PO4)2The XRD pattern of the base ceramic is shown in figure 5; the dielectric spectrum of this composition is shown in fig. 6; the weibull distribution of the breakdown strength of this composition is shown in fig. 7. The aTiO prepared by the proportion can be known by XRD pattern analysis2-bSiO2-cAl2O3-xCa3(PO4)2The crystal phase composition of the base ceramic is regulated and controlled. According to the dielectric spectrum, the dielectric constant of the composition is 36.5, and the dielectric loss is 0.0012. According to the Weber distribution diagram of the breakdown strength, the breakdown strength values of the component are distributed in a concentrated mode, and the breakdown strength value is 67.4 kV/mm.
Comparative example 3
A dielectric ceramic material with high breakdown strength is prepared by the following steps:
1) according to the chemical formula aTiO2-bSiO2-cAl2O3-xCa3(PO4)2Weighing rutile TiO according to the proportion of the reagents2(99％)，α-Al2O3(99％)，Ca3(PO4)2(99%) and SiO2(99%), wherein a is 4.13, b is 1, c is 1, and x is 1.32;
2) adding the weighed reagent into deionized water and zirconia ball milling beads for ball milling, then adding 60ml of PVA with the concentration of 5 wt% and then carrying out spray drying on the slurry. Pressing the obtained mixed raw material into a die with the diameter of 15mm under 30MPa to obtain a cylindrical green blank with the thickness of 0.5 mm;
3) discharging the prepared adhesive of the cylindrical green body, and sintering at 1240 ℃ to obtain a sintered ceramic wafer;
prepared aTiO2-bSiO2-cAl2O3-xCa3(PO4)2The XRD pattern of the base ceramic is shown in figure 5; the dielectric spectrum of this composition is shown in fig. 6; the weibull distribution of the breakdown strength of this composition is shown in fig. 7. The aTiO prepared by the proportion can be known by XRD pattern analysis2-bSiO2-cAl2O3-xCa3(PO4)2The crystal phase composition of the base ceramic has obvious regulation and control effects. From the dielectric spectrum, the dielectric constant of this composition was 35.6 and the dielectric loss was 0.0011. According to the Weber distribution diagram of the breakdown strength, the breakdown strength values of the component are distributed in a concentrated mode, and the breakdown strength value is 68.7 kV/mm.
Comparative example 4
A dielectric ceramic material with high breakdown strength is prepared by the following steps:
1) according to the chemical formula aTiO2-bSiO2-cAl2O3-xCa3(PO4)2Weighing rutile TiO according to the proportion of the reagents2(99％)，α-Al2O3(99％)，Ca3(PO4)2(99%) and SiO2(99%), wherein a is 4.13, b is 0.5, c is 0.67, and x is 0.99;
2) adding the weighed reagent into deionized water and zirconia ball milling beads for ball milling, then adding 60ml of PVA with the concentration of 5 wt% and then carrying out spray drying on the slurry. Pressing the obtained mixed raw material into a die with the diameter of 15mm under 30MPa to obtain a cylindrical green blank with the thickness of 0.5 mm;
3) discharging the prepared adhesive of the cylindrical green body, and sintering at 1240 ℃ to obtain a sintered ceramic wafer;
prepared aTiO2-bSiO2-cAl2O3-xCa3(PO4)2The XRD pattern of the base ceramic is shown in figure 5; the dielectric spectrum of this composition is shown in fig. 6; the weibull distribution of the breakdown strength of this composition is shown in fig. 7. The aTiO prepared by the proportion can be known by XRD pattern analysis2-bSiO2-cAl2O3-xCa3(PO4)2The crystal phase composition of the base ceramic has obvious regulation and control effects. According to the dielectric spectrum, the dielectric constant of the composition is 52.6, and the dielectric loss is 0.0012. According to the Weber distribution diagram of the breakdown strength, the distribution of the breakdown strength values of the system is concentrated, and the breakdown strength value is 60.6 kV/mm.
Comparative example 5
A dielectric ceramic material with high breakdown strength is prepared by the following steps:
1) according to the chemical formula aTiO2-bSiO2-cAl2O3-xCa3(PO4)2Weighing rutile TiO according to the proportion of the reagents2(99％)，α-Al2O3(99％)，Ca3(PO4)2(99%) and SiO2(99%), wherein a is 4.13, b is 1, c is 0.67, and x is 0.99;
2) adding the weighed reagent into deionized water and zirconia ball milling beads for ball milling, then adding 60ml of PVA with the concentration of 5 wt% and then carrying out spray drying on the slurry. Pressing the obtained mixed raw material into a die with the diameter of 15mm under 30MPa to obtain a cylindrical green blank with the thickness of 0.5 mm;
3) discharging the prepared adhesive of the cylindrical green body, and sintering at 1240 ℃ to obtain a sintered ceramic wafer;
the aTiO prepared by changing the proportion of the components2-bSiO2-cAl2O3-xCa3(PO4)2The crystal phase composition of the base ceramic is regulated. aTiO prepared by the component2-bSiO2-cAl2O3-xCa3(PO4)2The dielectric constant of the base ceramic was 30.5, and the dielectric loss was 0.0034. The breakdown strength value of this component was 70.3 kV/mm.
Comparative example 6
A dielectric ceramic material with high breakdown strength is prepared by the following steps:
1) according to the chemical formula aTiO2-bSiO2-cAl2O3-xCa3(PO4)2Weighing rutile TiO according to the proportion of the reagents2(99％)，α-Al2O3(99％)，Ca3(PO4)2(99%) and SiO2(99%), wherein a is 4.13, b is 1, c is 0.67, and x is 1.32;
2) adding the weighed reagent into deionized water and zirconia ball milling beads for ball milling, then adding 60ml of PVA with the concentration of 5 wt% and then carrying out spray drying on the slurry. Pressing the obtained mixed raw material into a die with the diameter of 15mm under 30MPa to obtain a cylindrical green blank with the thickness of 0.5 mm;
3) discharging the prepared adhesive of the cylindrical green body, and sintering at 1240 ℃ to obtain a sintered ceramic wafer;
the aTiO prepared by changing the proportion of the components2-bSiO2-cAl2O3-xCa3(PO4)2The crystal phase composition of the base ceramic is regulated. aTiO prepared by the component2-bSiO2-cAl2O3-xCa3(PO4)2The dielectric constant of the base ceramic was 27.9, and the dielectric loss was 0.0029. The breakdown strength value of this component was 45.8 kV/mm.
Performance testing
For aTiO of examples 1 to 5 and comparative examples 1 to 42-bSiO2-cAl2O3-xCa3(PO4)2The breakdown strength performance test was performed, and the test results are shown in the following table:
aTiO of examples 1 to 5 and comparative examples 1 to 42-bSiO2-cAl2O3-xCa3(PO4)2Results of performance test of
Figure BDA0003012521510000091
Note:
dielectric constant εrAnd dielectric loss tan δ: the dielectric constant and loss were measured at room temperature from 1kHz to 10MHz using a precision impedance analyzer (HP 4294A);
breakdown strength (E)b): . The breakdown strength (E) was measured at room temperature under direct current using a withstand voltage test apparatus (HT-100)b) And the sample is pushed forward at the rate of 1kV/s until the sample is subjected to the breakdown phenomenon. At least 10 specimens were tested per set of samples, each sample being sandwiched between two hemispherical electrodes, and the entire system being immersed in silicone oil to avoid flashover. The test results were analyzed using Weber's two-parameter distribution to obtain the average breakdown strength (E)b)。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a dielectric ceramic material with high breakdown strength is characterized by comprising the following steps: the preparation method comprises the following steps:
the method comprises the following steps: according to the chemical formula aTiO2-bSiO2-cAl2O3-xCa3(PO4)2Weighing raw materials in the ratio of the reagents, wherein the raw materials comprise reagent-grade rutile TiO2(99％)，α-Al2O3(99％)，Ca3(PO4)2(99%) and SiO2(99％)；
Step two: adding the weighed reagent into deionized water and zirconia ball milling beads for ball milling, then adding PVA (polyvinyl alcohol) and then carrying out spray drying on the slurry, and preparing the obtained mixed raw material into a cylindrical green body;
step three: and discharging the adhesive of the prepared cylindrical green body, and sintering to obtain the dielectric ceramic material with high breakdown strength.
2. The method of claim 1, wherein the high breakdown strength dielectric ceramic material is prepared by: the proportions a, b, c and x of the raw materials of the reagents are mass ratios, wherein a is more than or equal to 3 and less than or equal to 6, b is more than 0 and less than or equal to 2, c is more than 0 and less than or equal to 2, and x is more than 0 and less than or equal to 4.
3. The method of claim 1, wherein the high breakdown strength dielectric ceramic material is prepared by: in the ball milling process, the mass ratio of the weighed reagent to the weighed water to the weighed ball milling beads is 1.0 (1.5-2.0): (3.0-4.0).
4. The method of claim 1, wherein the high breakdown strength dielectric ceramic material is prepared by: in the ball milling process, the rotating speed of the ball mill is 300-500 r/min, and the ball milling time is 8-14 h.
5. The method of claim 1, wherein the high breakdown strength dielectric ceramic material is prepared by: PVA is added as a binder, wherein the concentration of the added PVA is 2-5 wt%, and the addition amount is 30-80 ml.
6. The method of claim 1, wherein the high breakdown strength dielectric ceramic material is prepared by: the concrete operation of discharging the adhesive of the prepared cylindrical green body is as follows: keeping the temperature at 600-800 ℃ for 120-180 min to discharge the binder.
7. The method of claim 1, wherein the high breakdown strength dielectric ceramic material is prepared by: and the heating rate in the sintering process is 6-8 ℃/min.
8. The method of claim 1, wherein the high breakdown strength dielectric ceramic material is prepared by: the sintering temperature is 1200-1300 ℃, and the sintering heat preservation time is 60-180 min.
9. The method of claim 1, wherein the high breakdown strength dielectric ceramic material is prepared by: in the second step, the obtained mixed raw materials are made into cylindrical green blanks, and the specific steps are as follows: a cylindrical green body having a thickness of 0.5mm was obtained by uniaxial pressing at 30MPa into a mold having a diameter of 15 mm.
10. The dielectric ceramic material with high breakdown strength prepared by the preparation method of any one of claims 1 to 9, wherein the dielectric ceramic material is characterized in that: the dielectric breakdown strength maximum value of the high-breakdown-strength dielectric ceramic material is 90.8 kV/mm.
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