CN107473734B - Linear dielectric ceramic with high electric strength resistance and preparation method thereof - Google Patents

Linear dielectric ceramic with high electric strength resistance and preparation method thereof Download PDF

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CN107473734B
CN107473734B CN201710851674.6A CN201710851674A CN107473734B CN 107473734 B CN107473734 B CN 107473734B CN 201710851674 A CN201710851674 A CN 201710851674A CN 107473734 B CN107473734 B CN 107473734B
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CN107473734A (en
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陈莹
黄叶
李鑫
董显林
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to a linear dielectric ceramic with high electric strength resistance and a preparation method thereof, wherein the chemical composition of the linear dielectric ceramic comprises aCaO-bMgO-cAl according to the mode of converting into oxides2O3‑dSiO2-eTiO-xMO, wherein a, b, c, d, e,x is mass percent, a is more than or equal to 0.03 and less than or equal to 0.12, b is more than or equal to 0.02 and less than or equal to 0.10, c is more than or equal to 0.25 and less than or equal to 0.40, d is more than or equal to 0.05 and less than or equal to 0.25, e is more than or equal to 0.40 and less than or equal to 0.60, and satisfies a + b + c + d + e =1, and x is more than 0 and less; the metal oxide MO is MnO2、CeO2、Nb2O5、La2O3、Ni2O3And ZrO2At least one of (1). The invention adopts the traditional solid phase method preparation process, is simple, has low sintering temperature and is suitable for industrial large-scale production.

Description

Linear dielectric ceramic with high electric strength resistance and preparation method thereof
Technical Field
The invention relates to a linear dielectric ceramic with high electric strength resistance and a preparation method thereof, in particular to CaO-MgO-Al2O3-SiO2-TiO2an-MO dielectric ceramic and a preparation method thereof, belonging to the technical field of electronic ceramic materials.
Background
In 1994, E. L. Neau first proposed the concept of solid-state repetitive frequency pulse technology, if solid-state materials were used instead of liquids, the physical length of the pulse-forming lines could be significantly reduced, the requirements and maintenance costs for auxiliary systems could be greatly reduced, the mobility of the equipment could be improved, making the device airborne and satellite-borne possible.
Solid media can be generally classified into organic, glass-ceramic, and ceramic. The organic matter generally has very high electric strength (more than or equal to 100kV/mm), but the dielectric constant of the organic matter is very small (3-5), the dielectric loss is very large, and the dielectric property obviously changes along with the temperature and the frequency. Although the electric strength and the dielectric constant of the glass ceramic are relatively high, the problems of poor stability of dielectric property and mechanical property, low actual energy storage density caused by interface polarization and the like exist. Ceramics generally have a relatively suitable dielectric constant, but relatively low electrical strength, such as typical TiO2The dielectric constant of the ceramic at normal temperature is 90, but the electric strength of the ceramic is only 25kV/mm, so that the ceramic can not meet the requirement of practical application. Therefore, the research and development of the dielectric ceramic system with high electric strength resistance, moderate dielectric constant, low dielectric loss and good dielectric property along with temperature and frequency stability has important scientific significance and wide application prospect.
The patent with the publication number of CN103664162B discloses a dielectric ceramic system with high electric strength, which adopts the traditional solid phase method, the electric strength of the ceramic can reach 53kV/mm, and the ceramic system has excellent electrical properties. However, in practical application development, a ceramic material with higher electric strength is required, and the high electric strength not only determines the final acceleration field strength and the high-voltage bearing capacity of an application device, but also determines the working stability and the service life of the device.
Disclosure of Invention
The invention aims to meet the requirement of application development and aims to provide a dielectric ceramic material which is reliably used at high voltage and a preparation method thereof.
In one aspect, the present invention provides a linear dielectric ceramic having high dielectric strength, the chemical composition of which comprises aCaO-bMgO in terms of oxide-cAl2O3-dSiO2-eTiO-xMO, wherein a, b, c, d, e, x are mass percentages, a is 0.03 ≤ 0.12, b is 0.02 ≤ 0.10, c is 0.25 ≤ 0.40, d is 0.05 ≤ 0.25, e is 0.40 ≤ 0.60 and satisfies a + b + c + d + e ═ 1, x is 0 < 0 ≤ 0.025;
the metal oxide MO is MnO2、CeO2、Nb2O5、La2O3、Ni2O3And ZrO2At least one of (1).
The invention is in the state of aCaO-bMgO-cAl2O3-dSiO2-eTiO2The system dielectric ceramic is modified by selecting a metal oxide MO (for example, MnO) with a high energy gap capable of reducing sintering temperature (fluxing action)2、CeO2、Nb2O5、La2O3、Ni2O3And ZrO2Etc.) as doping assistant, can make aCaO-bMgO-cAl2O3-dSiO2-eTiO2The system medium ceramic forms a liquid phase in the subsequent sintering process, the sintering temperature is reduced (about 50 ℃), the porosity is reduced to improve the compactness of the ceramic, so that the electric strength resistance of the medium ceramic material is improved, and the addition of MO can promote cordierite Mg2Al4Si5O18Phase, anorthite CaAl2Si2O8Formation of phases and formation of new substances, e.g. NiAl2O4. The composite phase of cordierite and anorthite can effectively reduce the pores and microcracks of the ceramic and inhibit the growth of the ceramic grains; NiAl2O4Has excellent thermal shock resistance and mechanical property, thereby improving the mechanical property of the ceramic. MO is a metal oxide having a high forbidden band width and having a fluxing action. A small amount of metal oxide MO is added to form a liquid phase, so that the sintering temperature of the original components is reduced, the porosity is reduced, and the compactness of the ceramic is improved, thereby improving the electric strength of the ceramic. If the doping content of MO is too much, the crystallization temperature of each phase will be obviously different, resulting in abnormal growth of some phase grains, uneven distribution of each phase, and air holes, and reducing the electric strength of the ceramic, soThere is an optimum range for the amount of MO to be added.
Further, it is preferable that when the metal oxide MO is MnO2When x is more than 0 and less than or equal to 0.025;
when the metal oxide MO is CeO2When x is more than 0 and less than or equal to 0.02;
when the metal oxide MO is Nb2O5When x is more than 0 and less than or equal to 0.015;
when the metal oxide MO is L a2O3When x is more than 0 and less than or equal to 0.015;
when the metal oxide MO is Ni2O3When x is more than 0 and less than or equal to 0025;
when the metal oxide MO is ZrO2When x is more than 0 and less than or equal to 0.025.
In the invention, the electric strength of the linear dielectric ceramic can be 51.64-82.06 kV/mm.
The invention also provides a preparation method for preparing the linear dielectric ceramic, which comprises the following steps:
weighing a Ca source, a Mg source, an Al source, a Si source and a Ti source according to the chemical compositions, and carrying out ball milling or mixing and calcining on the weighed materials to synthesize ceramic powder; adding an M source and a binder, mixing, pressing into a biscuit, removing plastic and sintering to obtain the linear dielectric ceramic. In the invention, the calcination synthesis is carried out firstly to decompose carbonate or organic salt in a Ca source, a Mg source, an Al source, a Si source and a Ti source and carry out a primary reaction to form an oxide composite phase, and then an M source is added to optimize and design the phase composition in the composite phase so as to achieve the purpose of designing the components; directly mixing all the raw materials together may not obtain the target product or the obtained target product has poor performance.
Preferably, the calcination synthesis temperature is 900-1100 ℃, and the time is 2-4 hours.
Further, preferably, the Ca source is CaO or CaCO3And CaTiO3The Mg source is MgO or/and MgCO3The Al source is Al2O3The Si source is SiO2The Ti source is CaTiO3Or/and TiO2And the M source is oxide or carbonate of metal M.
Preferably, the temperature of the plastic discharge is 600-800 ℃ and the time is 1-3 hours.
Preferably, the binder is at least one of polyvinyl alcohol, polyvinyl butyral, phenolic resin and the like, and the addition amount of the binder is preferably 2-7 wt% of the total mass of the raw material powder.
Preferably, the sintering temperature is 1220-1300 ℃ and the sintering time is 2-6 hours.
Preferably, the forming mode of the blank body is dry pressing, and the pressure of the dry pressing is preferably 180-300 MPa.
The invention has the following beneficial effects:
CaO-MgO-Al2O3-SiO2-TiO2The material system is modified, so that the sintering temperature can be obviously reduced, the electric strength can be improved, the electric strength can reach 82.06kV/mm, the electric strength is 1.6 times of the electric strength of the original component, the change rate of the dielectric constant is less than 5% in the temperature range of-50-150 ℃, and the ceramic material system is a linear dielectric ceramic material system with high electric strength and important application value. The material has moderate dielectric constant, high electric strength, low dielectric loss and good environmental adaptability, and can obviously improve the output power, the service life and the stability of a pulse power device. The invention adopts the traditional solid phase method preparation process, is simple, has low sintering temperature and is suitable for industrial large-scale production.
Drawings
FIG. 1 is a graph showing the change of dielectric constant and dielectric loss with frequency of a dielectric ceramic prepared in comparative example 1 of the present invention;
FIG. 2 is a graph showing the change of dielectric constant and dielectric loss with temperature of the dielectric ceramic prepared in comparative example 1 of the present invention;
FIG. 3 is a graph showing the change of dielectric constant and dielectric loss with frequency of the dielectric ceramic prepared in example 2 of the present invention;
FIG. 4 is a graph showing the change of dielectric constant and dielectric loss with temperature of the dielectric ceramic prepared in example 2 of the present invention;
FIG. 5 is a graph showing the dielectric constant and dielectric loss as a function of frequency for the dielectric ceramic prepared in example 5 of the present invention;
FIG. 6 is a graph showing the change of dielectric constant and dielectric loss with temperature of the dielectric ceramic prepared in example 5 of the present invention;
FIG. 7 is a graph showing the dielectric constant and dielectric loss as a function of frequency for the dielectric ceramic prepared in example 8 of the present invention;
FIG. 8 is a graph showing the change of dielectric constant and dielectric loss with temperature of the dielectric ceramic prepared in example 8 of the present invention;
FIG. 9 is a graph showing the dielectric constant and dielectric loss as a function of frequency for the dielectric ceramic prepared in example 11 of the present invention;
FIG. 10 is a graph showing the change of dielectric constant and dielectric loss with temperature of the dielectric ceramic prepared in example 11 of the present invention;
FIG. 11 is a graph showing the dielectric constant and dielectric loss as a function of frequency for the dielectric ceramic prepared in example 14 of the present invention;
FIG. 12 is a graph showing the change of dielectric constant and dielectric loss with temperature of the dielectric ceramic prepared in example 14 of the present invention;
FIG. 13 is a SEM cross-section of a dielectric ceramic prepared in example 17 of the present invention;
FIG. 14 is a graph showing the dielectric constant and dielectric loss as a function of frequency for the dielectric ceramic prepared in example 17 of the present invention;
FIG. 15 is a graph showing the change of dielectric constant and dielectric loss with temperature of a dielectric ceramic prepared in example 17 of the present invention;
FIG. 16 is an XRD pattern of the dielectric ceramics prepared in comparative example 1 and example 17 of the present invention;
FIG. 17 is a Weibull distribution plot of the electrical strength resistance of the dielectric ceramics prepared in comparative example 1 and examples 2, 5, 8, 11, 14, 17 of the present invention;
FIG. 18 is a SEM image of a cross section of a dielectric ceramic prepared in comparative example 7 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the invention, the linear dielectric ceramic with high electric strength resistance is foldedThe oxide-calculated mode has the following composition formula: aCaO-bMgO-cAl2O3-dSiO2-eTiO2-xMO. Wherein MO represents a metal oxide, which may be MnO2、CeO2、Nb2O5、La2O3、Ni2O3、ZrO2One or more of them. a. b, c, d, e and x are mass percent, and satisfy the condition that a + b + c + d + e is 1, a is more than or equal to 0.03 and less than or equal to 0.12, b is more than or equal to 0.02 and less than or equal to 0.10, c is more than or equal to 0.25 and less than or equal to 0.40, d is more than or equal to 0.05 and less than or equal to 0.25, e is more than or equal to 0.40 and less than or equal to 0.60, and x is more than 0 and less.
The method has the advantages of lead-free environmental protection, low cost, simple preparation process and the like. The following is an exemplary description of the preparation method of the dielectric ceramic with high electric strength provided by the present invention.
aCaO-bMgO-cAl2O3-dSiO2-eTiO2And preparing system medium ceramic powder. Specifically, the Ca source, Mg source, Al source, Si source and Ti source are mixed so as to be aCaO-bMgO-cAl2O3-dSiO2-eTiO2Mixing the composition formula of the system dielectric ceramic, and calcining at 900-1100 ℃ for 2-4 hours to obtain the aCaO-bMgO-cAl2O3-dSiO2-eTiO2System medium ceramic powder. The Ca source can be CaO, CaCO3And CaTiO3One kind of (1). The Mg source can be MgO or/and MgCO3. The Al source may be Al2O3. The Si source may be SiO2. The Ti source can be CaTiO3Or/and TiO2。
As an example, with CaCO3Or CaTiO3MgO or MgCO3，Al2O3，SiO2，TiO2Mixing the raw materials according to the mass ratio, ball-milling and uniformly mixing the mixed raw materials, drying and calcining (the calcining temperature is 900-1100 ℃ and the calcining time is 2 hours) to obtain aCaO-bMgO-cAl2O3-dSiO2-eTiO2System medium ceramic powder. Wherein the ball milling process adopts zirconia balls and deionized water as ball milling media, the ball milling time is 6-24 hours, and the granularity d is prepared50Is a mixed powder of 0.5 to 3 μm.
aCaO-bMgO-cAl was added as described above2O3-dSiO2-eTiO2The system medium ceramic powder, metal oxide MO (or carbonate of M) and a binder are mixed and sieved to prepare a green body. The metal oxide MO is mixed with CaO, MgO and Al2O3、SiO2、TiO2The total mass of (i.e., the total mass of all of the Ca source, Mg source, Al source, Si source, and Ti source in terms of oxides, or aCaO-bMgO-cAl2O3-dSiO2-eTiO2Mass of the system medium ceramic powder) can be x: 1, wherein x is more than 0 and less than or equal to 0.025. When the metal oxide MO is MnO2When x is more than 0 and less than or equal to 0.025. When the metal oxide MO is CeO2When x is more than 0 and less than or equal to 0.02. When the metal oxide MO is Nb2O5When x is more than 0 and less than or equal to 0.015, when the metal oxide MO is L a2O3When x is more than 0 and less than or equal to 0.015. When the metal oxide MO is Ni2O3When x is more than 0 and less than or equal to 0.025. When the metal oxide MO is ZrO2When x is more than 0 and less than or equal to 0.025. The aCaO-bMgO-cAl2O3-dSiO2-eTiO2The grain size of the system medium ceramic powder can be 0.5-3 μm. The particle size of the metal oxide MO may be 0.5-2 μm. The forming mode of the blank body can be dry pressing forming and the like. The pressure of the dry pressing molding can be 180-300 MPa. The binder may be at least one of polyvinyl alcohol, polyvinyl butyral, phenol resin, and the like. The addition amount of the binder can be 2-7 wt% of the total mass of the raw material powder, and preferably 5-7 wt%.
As an example, take the above-mentioned aCaO-bMgO-cAl2O3-dSiO2-eTiO2Adding MO with different mass into system medium ceramic powder, performing wet ball milling, drying, adding a binder, uniformly mixing, sieving, and pressing under the pressure of 180-300 MPa to prepare a biscuit. Wherein the ball milling process uses zirconia balls and deionized water as ball milling media, the ball milling time is 6-24 hours, and the particle size d is prepared50Is a mixed powder of 0.5 to 3 μm. The binder is 7% polyvinyl alcohol (PVA) solution. The adhesiveThe addition amount of the caking agent is 5-7% of the total mass of the powder.
And (5) plastic removal of the blank. And (3) carrying out heat preservation treatment on the obtained biscuit (blank) at a certain temperature to remove organic matters in the biscuit. The plastic discharging temperature range is 600-800 ℃, and the heat preservation time is 1-3 hours.
Sintering the biscuit at the temperature of 1220-1300 ℃, and then cooling to room temperature (25 ℃) to obtain the high-electric-strength linear dielectric ceramic. The heat preservation time of the high-temperature sintering can be 2-6 hours.
According to the invention, the traditional solid-phase preparation process is adopted, the electric strength of the ceramic system can reach 82.06kV/mm, the dielectric constant is adjustable between 20 and 30, and the frequency and temperature stability of the dielectric constant are good. The method has important application value in the fields of high-voltage power supplies, high-power pulse systems, common-cavity antennas, particle beam inertial confinement fusion, electron beam accelerators, strong X-ray systems and the like.
The linear dielectric ceramic has the electric strength of 51.64-82.06 kV/mm measured by an SD-DC 200kV direct-current high-voltage generator. The invention adopts an E4980A precision impedance analyzer to measure the dielectric constant and the dielectric loss of the linear dielectric ceramic.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Comparative example 1 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2(1) Calculating the required CaCO according to the components of the dielectric ceramic material3，MgO，Al2O3，SiO2，TiO2Mass, using deionized waterAnd zirconia balls are used as ball milling media, and the ball milling media comprise the following materials: ball: ball-milling for 24 hours by using deionized water in a mass ratio of 1:3:3, drying, sieving by using a 40-mesh sieve, and keeping the obtained powder at 1100 ℃ for 2 hours at a heating rate of 2 ℃/min to obtain the synthesized dielectric ceramic powder;
(2) the synthesized ceramic powder is prepared by the following steps: ball: ball milling for 24 hours by the mass ratio of deionized water to 1:3:1.6, discharging, drying, and sieving by a 40-mesh sieve to obtain the granularity d50The particle size was 1.6 μm. Adding 5 wt% of polyvinyl alcohol (PVA) into the obtained powder for granulation, and then pressing ceramic biscuit with diameter of 13mm under the pressure of 180 MPa;
(3) keeping the ceramic biscuit obtained in the step (2) at 800 ℃ for 2 hours, removing organic matters in the biscuit, and raising the temperature at 2 ℃/min;
(4) placing the sample after plastic removal on an alumina plate, heating to 1280 ℃ at the heating rate of 2 ℃/min, preserving the heat for 4 hours, and naturally cooling to room temperature (25 ℃) to obtain a ceramic sample;
(5) and (3) grinding the two sides of the obtained ceramic sample to 0.5mm, then ultrasonically cleaning, drying, performing screen printing on silver paste, drying again, and preserving heat at 750 ℃ for 30 minutes to obtain the dielectric ceramic sample coated with the electrode.
FIG. 1 is a dielectric spectrum of the dielectric ceramic prepared in comparative example 1, and it can be seen that the dielectric constant of the dielectric ceramic is stabilized at about 27.2 and the dielectric loss at room temperature is about 0.0024 in the range of 1kHz to 10 MHz. FIG. 2 is a dielectric thermogram of the dielectric ceramic prepared in this comparative example 1, and it can be seen from the graph that the dielectric constant of the dielectric ceramic slightly decreases with increasing temperature and the dielectric loss slightly increases with increasing temperature, but still is less than 0.004, in the range of-55 deg.C to 150 deg.C.
Example 1 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.01CeO2
(1) Calculating the required CaCO according to the components of the dielectric ceramic material3，MgO，Al2O3，SiO2，TiO2The mass is that deionized water and zirconia balls are adopted as ball milling mediaTaking care: ball: ball-milling for 24 hours by using deionized water in a mass ratio of 1:3:3, drying, sieving by using a 40-mesh sieve, and keeping the obtained powder at 1100 ℃ for 2 hours at a heating rate of 2 ℃/min to obtain the synthesized dielectric ceramic powder;
(2) adding CeO2Proportioning according to a stoichiometric ratio, adding the mixture into the ceramic powder synthesized in the step (1), and mixing the materials according to the ratio: ball: ball milling for 24 hours by the mass ratio of deionized water to 1:3:1.6, discharging, drying, and sieving by a 40-mesh sieve to obtain the granularity d50The particle size was 1.5. mu.m. Adding 5 wt% of polyvinyl alcohol (PVA) into the obtained powder for granulation, and then pressing ceramic biscuit with diameter of 13mm under the pressure of 180 MPa;
(3) keeping the ceramic biscuit obtained in the step (2) at 800 ℃ for 2 hours, removing organic matters in the biscuit, and raising the temperature at 2 ℃/min;
(4) placing the sample after plastic removal on an alumina plate, heating to 1260 ℃ at the heating rate of 2 ℃/min, preserving the heat for 4 hours, and naturally cooling to room temperature to obtain a ceramic sample;
(5) and (3) grinding the two sides of the obtained ceramic sample to 0.5mm, then ultrasonically cleaning, drying, screen-printing silver paste, drying again, preserving the heat at 750 ℃ for 30 minutes to obtain a dielectric ceramic sample coated with an electrode, and carrying out dielectric property test and electric strength test on the sample. The dielectric properties of the linear dielectric ceramics prepared in this example are shown in Table 1.
Example 2 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.015CeO2
With CaCO3，MgO，Al2O3，SiO2，TiO2，CeO2As a raw material, ceramics were prepared by the same process as in example 1, at a sintering temperature of 1250 ℃ for 4 hours.
FIG. 3 is a dielectric spectrum of the dielectric ceramic prepared in example 2, which shows that the dielectric constant of the dielectric ceramic is stabilized at about 26.7 and the dielectric loss at room temperature is about 0.0022 within the range of 1kHz to 10 MHz. FIG. 4 is a dielectric thermogram of the dielectric ceramic prepared in this example 2, and it can be seen that the dielectric constant of the dielectric ceramic slightly decreases with increasing temperature and the dielectric loss slightly increases with increasing temperature within the range of-55 deg.C to 150 deg.C, but still below 0.004.
Example 3 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.02CeO2
With CaCO3，MgO，Al2O3，SiO2，TiO2，CeO2As a raw material, ceramics were prepared by the same process as in example 1, at a sintering temperature of 1250 ℃ for 4 hours. The dielectric properties of the linear dielectric ceramics prepared in this example are shown in Table 1.
Example 4 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.005Nb2O5
With CaCO3，MgO，Al2O3，SiO2，TiO2，CeO2As a raw material, ceramics were prepared by the same process as in example 1, at a sintering temperature of 1250 ℃ for 4 hours. The dielectric properties of the linear dielectric ceramics prepared in this example are shown in Table 1.
Example 5 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.01Nb2O5
With CaCO3，MgO，Al2O3，SiO2，TiO2，Nb2O5Preparing ceramic by the same process as the example 1 with the sintering temperature of 1240 ℃ and the sintering time of 4 hours as raw materials;
FIG. 5 is a dielectric spectrum of the dielectric ceramic prepared in this example, which shows that the dielectric constant of the dielectric ceramic is stabilized at about 26.6 and the dielectric loss at room temperature is about 0.0021 in the range of 1kHz to 10 MHz. FIG. 6 is a dielectric thermogram of the dielectric ceramic prepared in this example, from which it can be seen that the dielectric constant of the dielectric ceramic slightly decreases with increasing temperature and the dielectric loss slightly increases with increasing temperature, but still below 0.004, in the range of-55 deg.C to 150 deg.C.
Example 6 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.015Nb2O5
With CaCO3，MgO，Al2O3，SiO2，TiO2，Nb2O5As a raw material, ceramics were prepared by the same process as in example 1, sintering temperature was 1240 ℃ and sintering time was 4 hours. The dielectric properties of the linear dielectric ceramics prepared in this example are shown in Table 1.
Example 7 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.005La2O3
With CaCO3，MgO，Al2O3，SiO2，TiO2，La2O3As a raw material, ceramics were prepared by the same process as in example 1 at 1260 ℃ for 4 hours. The dielectric properties of the linear dielectric ceramics prepared in this example are shown in Table 1.
Example 8 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.01La2O3
With CaCO3，MgO，Al2O3，SiO2，TiO2，La2O3As a raw material, a ceramic was prepared according to the same process as in example 1, with a sintering temperature of 1240 ℃.
FIG. 7 is a dielectric spectrum of the dielectric ceramic prepared in this example, which shows that the dielectric constant of the dielectric ceramic is stabilized at about 27.1 and the dielectric loss at room temperature is about 0.0023 within a range of 1kHz to 10 MHz. FIG. 8 is a dielectric thermogram of the dielectric ceramic prepared in this example, from which it can be seen that the dielectric constant of the dielectric ceramic slightly decreases with increasing temperature and the dielectric loss slightly increases with increasing temperature, but still below 0.004, in the range of-55 deg.C to 150 deg.C.
Example 9 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.015La2O3
With CaCO3，MgO，Al2O3，SiO2，TiO2，La2O3As a raw material, ceramics were prepared by the same process as in example 1, sintering temperature was 1240 ℃ and sintering time was 4 hours. The dielectric properties of the linear dielectric ceramics prepared in this example are shown in Table 1.
Example 10 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.01ZrO2
With CaCO3，MgO，Al2O3，SiO2，TiO2，ZrO2As a raw material, ceramics were prepared by the same process as in example 1, at a sintering temperature of 1250 ℃ for 4 hours. The dielectric properties of the linear dielectric ceramics prepared in this example are shown in Table 1.
Example 11 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.02ZrO2
With CaCO3，MgO，Al2O3，SiO2，TiO2，ZrO2As a raw material, ceramics were prepared by the same process as in example 1 at a sintering temperature of 1260 ℃.
FIG. 9 is a dielectric spectrum of the dielectric ceramic prepared in this example, and it can be seen that the dielectric constant of the dielectric ceramic is stabilized at about 27.6 and the dielectric loss at room temperature is about 0.0026 in the range of 1kHz to 10 MHz. FIG. 10 is a dielectric thermogram of the dielectric ceramic prepared in this example, and it can be seen that the dielectric constant of the dielectric ceramic slightly decreases with increasing temperature and the dielectric loss slightly increases with increasing temperature within the range of-50 deg.C to 150 deg.C, but still below 0.004.
Example 12 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.025ZrO2
With CaCO3，MgO，Al2O3，SiO2，TiO2，ZrO2As a raw material, ceramics were prepared by the same process as in example 1, sintering temperature was 1240 ℃ and sintering time was 4 hours. The dielectric properties of the linear dielectric ceramics prepared in this example are shown in Table 1.
Example 13 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.01MnO2
With CaCO3，MgO，Al2O3，SiO2，TiO2，MnO2As a raw material, ceramics were prepared by the same process as in example 1 at 1260 ℃ for 4 hours. The dielectric properties of the linear dielectric ceramics prepared in this example are shown in Table 1.
Example 14 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.02MnO2
With CaCO3，MgO，Al2O3，SiO2，TiO2，MnO2As a raw material, ceramics were prepared by the same process as in example 1, the sintering temperature was 1240 ℃ and the sintering temperature was 4 hours.
FIG. 11 is a dielectric spectrum of the dielectric ceramic prepared in this example, and it can be seen that the dielectric constant of the dielectric ceramic is stabilized at about 29.5 and the dielectric loss at room temperature is about 0.0021 within the range of 1kHz to 10 MHz. FIG. 12 is a dielectric thermogram of the dielectric ceramic prepared in this example, and it can be seen that the dielectric constant of the dielectric ceramic slightly decreases with increasing temperature and the dielectric loss slightly increases with increasing temperature in the range of-55 deg.C to 150 deg.C.
Example 15 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.025MnO2
With CaCO3，MgO，Al2O3，SiO2，TiO2，MnO2As a raw material, ceramics were prepared by the same process as in example 1, sintering temperature was 1240 ℃ and sintering time was 4 hours. The dielectric properties of the linear dielectric ceramics prepared in this example are shown in Table 1.
Example 16 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.01Ni2O3
With CaCO3，MgO，Al2O3，SiO2，TiO2，Ni2O3As a raw material, ceramics were prepared by the same process as in example 1, sintering temperature was 1240 ℃ and sintering time was 4 hours. The dielectric properties of the linear dielectric ceramics prepared in this example are shown in Table 1.
Example 17 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.02Ni2O3
With CaCO3，MgO，Al2O3，SiO2，TiO2，Ni2O3As a raw material, ceramics were prepared according to the same process as in example 1, with a sintering temperature of 1230 ℃.
Fig. 13 is a cross-sectional SEM image of the dielectric ceramic in this example, and it can be seen that the dielectric ceramic is dense, the phases are uniformly distributed, and a distinct liquid phase appears, which is a main reason for the significant improvement of the electric strength. FIG. 14 is a dielectric spectrum of the dielectric ceramic prepared in this example, which shows that the dielectric constant of the dielectric ceramic is stabilized at about 26 and the dielectric loss at room temperature is about 0.0021 in the range of 1kHz to 10 MHz. FIG. 15 is a dielectric thermogram of the ceramic prepared in this example, from which it can be seen that the dielectric constant of the dielectric ceramic slightly decreases with increasing temperature and the dielectric loss slightly increases with increasing temperature, but still below 0.004, in the range of-55 deg.C to 150 deg.C;
FIG. 16 is an XRD pattern of the dielectric ceramics prepared in comparative example 1 and example 17, from which it can be seen that the ceramics are multi-componentCo-existing phase of composite oxide, doped with Ni2O3Then, Ni2O3Can be mixed with Al2O3Reaction to produce NiAl2O4And (4) phase(s).
Example 18 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.025Ni2O3
With CaCO3，MgO，Al2O3，SiO2，TiO2，Ni2O3As a raw material, ceramics were prepared by the same process as in example 1, with a sintering temperature of 1230 ℃ and a sintering time of 4 hours. The dielectric properties of the linear dielectric ceramics prepared in this example are shown in Table 1.
FIG. 17 is a Weibull distribution diagram showing the electric strength of dielectric ceramics prepared in comparative example 1 and examples 2, 5, 8, 11, 14, 17 according to the present invention, from which it can be seen that the electric strength of dielectric ceramics prepared in comparative example 1 and examples 2, 5, 8, 11, 14, 17 is 50.55kV/mm, 53.88kV/mm, 55.61kV/mm, 57.37kV/mm, 65.31kV/mm, 71.46kV/mm, 82.06kV/mm, respectively.
Comparative example 2 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.03CeO2
With CaCO3，MgO，Al2O3，SiO2，TiO2，CeO2As a raw material, ceramics were prepared by the same process as in example 1, at a sintering temperature of 1250 ℃ for 4 hours. The dielectric properties of the linear dielectric ceramics prepared by the comparative example are shown in Table 1.
Comparative example 3 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.03Nb2O5
With CaCO3，MgO，Al2O3，SiO2，TiO2，Nb2O5As a raw material, ceramics were prepared by the same process as in example 1, sintering temperature was 1240 ℃ and sintering time was 4 hours. Comparative example stationThe dielectric properties of the prepared linear dielectric ceramic are shown in Table 1.
Comparative example 4 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.03La2O3
With CaCO3，MgO，Al2O3，SiO2，TiO2，La2O3As a raw material, ceramics were prepared by the same process as in example 1, sintering temperature was 1240 ℃ and sintering time was 4 hours. The dielectric properties of the linear dielectric ceramics prepared by the comparative example are shown in Table 1.
Comparative example 5 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.03ZrO2
With CaCO3，MgO，Al2O3，SiO2，TiO2，ZrO2As a raw material, ceramics were prepared by the same process as in example 1, sintering temperature was 1240 ℃ and sintering time was 4 hours. The dielectric properties of the linear dielectric ceramics prepared by the comparative example are shown in Table 1.
Comparative example 6 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.04MnO2
With CaCO3，MgO，Al2O3，SiO2，TiO2，MnO2As a raw material, ceramics were prepared by the same process as in example 1, sintering temperature was 1240 ℃ and sintering time was 4 hours. The dielectric properties of the linear dielectric ceramics prepared by the comparative example are shown in Table 1.
Comparative example 7 the linear dielectric ceramic material consists of: 0.08CaO-0.06MgO-0.31Al2O3-0.07SiO2-0.48TiO2-0.05Ni2O3
With CaCO3，MgO，Al2O3，SiO2，TiO2，Ni2O3As a raw material, ceramics were prepared by the same process as in example 1, the sintering temperature was 1230 deg.C, and firing was carried outThe knot time was 4 hours. The dielectric properties of the linear dielectric ceramics prepared by the comparative example are shown in Table 1. FIG. 18 is a SEM image of a cross section of the dielectric ceramic prepared in this comparative example 7, and it is understood that the dielectric ceramic has a distinct second phase and a liquid phase, and that an excessive second phase causes a deterioration in the microstructure of the dielectric ceramic, and distinct pores appear, resulting in an increase in loss, which is a main cause of a sharp decrease in the electric strength resistance.
Table 1 shows the dielectric properties of the dielectric ceramics prepared in comparative example 1 and examples 1 to 18:
Figure BDA0001412076740000111
Figure BDA0001412076740000121
the comprehensive experiment results show that: the high-electric-strength linear dielectric ceramic material prepared by the traditional solid phase method has the advantages that the electric strength can reach 82.06kV/mm, the dielectric constant is adjustable between 20 and 30, the dielectric loss at room temperature is lower than 0.003, the frequency and the temperature stability of the dielectric constant are good, and the high-electric-strength linear dielectric ceramic material is very suitable for being applied to the fields of high-voltage power supplies, high-power pulse systems, co-cavity antennas, particle beam inertial confinement fusion, electron beam accelerators, strong X-ray technologies and the like. In addition, the material disclosed by the invention has the advantages of lead-free environmental protection, simple preparation process and the like.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (7)

1. A linear dielectric ceramic with high electric strength resistance is characterized in that the chemical composition of the linear dielectric ceramic comprises aCaO-bMgO-cAl in a manner of being converted into oxides2O3-dSiO2-eTiO2-xMO, wherein MO is a metal oxide, a, b, c, d, e, x are mass percentages, a is 0.03 ≤ 0.12, b is 0.02 ≤ 0.10, c is 0.25 ≤ 0.40, d is 0.05 ≤ 0.25, e is 0.40 ≤ 0.60 and satisfies a + b + c + d + e = 1;
the metal oxide MO is MnO2、CeO2、Nb2O5、La2O3、Ni2O3And ZrO2At least one of;
when the metal oxide MO is MnO2When x is more than 0 and less than or equal to 0.025;
when the metal oxide MO is CeO2When x is more than 0 and less than or equal to 0.02;
when the metal oxide MO is Nb2O5When x is more than 0 and less than or equal to 0.015;
when the metal oxide MO is L a2O3When x is more than 0 and less than or equal to 0.015;
when the metal oxide MO is Ni2O3When x is more than 0 and less than or equal to 0.025;
when the metal oxide MO is ZrO2When x is more than 0 and less than or equal to 0.025;
the electric strength of the linear dielectric ceramic is 51.64-82.06 kV/mm.
2. A method of making a linear dielectric ceramic as claimed in claim 1, comprising:
weighing a Ca source, a Mg source, an Al source, a Si source and a Ti source according to the chemical compositions, and carrying out ball milling or mixing and calcining on the weighed materials to synthesize ceramic powder;
adding an M source and a binder, mixing, pressing into a biscuit, removing plastic and sintering to obtain the linear dielectric ceramic;
and after plastic removal, sintering the obtained blank to obtain the linear dielectric ceramic with high electric strength resistance.
3. The preparation method according to claim 2, wherein the calcination synthesis temperature is 900-1100 ℃ and the time is 2-4 hours.
4. The method according to claim 2, wherein the Ca source is CaO, CaCO3And CaTiO3The Mg source is MgO or/and MgCO3The Al source is Al2O3The Si source is SiO2The Ti source is CaTiO3Or/and TiO2And the M source is oxide or carbonate of metal M.
5. The preparation method according to claim 2, wherein the temperature of the plastic discharge is 600-800 ℃ for 1-3 hours.
6. The preparation method according to claim 2, wherein the binder is at least one of polyvinyl alcohol, polyvinyl butyral and phenol resin, and the amount of the binder added is 2 to 7wt% of the total mass of the raw material powder.
7. The method according to any one of claims 2 to 6, wherein the sintering temperature is 1220 to 1300 ℃ and the sintering time is 2 to 6 hours.
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