CN113636840B - Ceramic thick film of ceramic electrode for electric field treatment of tumor and preparation method thereof - Google Patents

Ceramic thick film of ceramic electrode for electric field treatment of tumor and preparation method thereof Download PDF

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CN113636840B
CN113636840B CN202111200498.2A CN202111200498A CN113636840B CN 113636840 B CN113636840 B CN 113636840B CN 202111200498 A CN202111200498 A CN 202111200498A CN 113636840 B CN113636840 B CN 113636840B
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thick film
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CN113636840A (en
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张建义
刘胜军
段红杰
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HEBEI PUNI MEDICAL TECHNOLOGY CO.,LTD.
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Abstract

The invention relates to a ceramic thick film of a ceramic electrode for electric field tumor treatment and a preparation method thereof, wherein the preparation method comprises the following steps: synthesis of (1-x) Pb (Mg) by two-step solid phase method1/ 3Nb2/3)O3‑xPb1‑ySr0.5yNa0.25ySm0.25yTiO3Powder, wherein x is more than or equal to 0.055 and less than or equal to 0.135, y is more than or equal to 0 and less than or equal to 0.03, and x and y are mole numbers; preparing casting slurry by utilizing the synthesized powder: adding a proper amount of solvent and dispersant into the powder, and finely grinding for 24 hours; adding a plasticizer, ball-milling for 15 minutes, adding a binder, and continuously ball-milling for 24 hours; carrying out tape casting on the slurry to obtain a tape casting film green body; laminating the cast film green blank, pressurizing, and then performing plastic discharge to obtain a biscuit; and sintering the biscuit to obtain the ceramic thick film material. The ceramic thick film material has high dielectric constant and low loss, and is suitable for making capacitor electrodes for conducting alternating current.

Description

Ceramic thick film of ceramic electrode for electric field treatment of tumor and preparation method thereof
Technical Field
The invention belongs to the technical field of functional ceramic materials, and particularly relates to a ceramic thick film of a ceramic electrode for electric field tumor treatment and a preparation method thereof.
Background
Biomedical experiments have demonstrated that the application of alternating voltage can effectively inhibit the growth of specific abnormal cells at specific alternating frequency [ Cancer Research, vol.64, pp3288-3295, 2004; PNAS, vol.104, pp10152-10157, 2007 ]. If an electric field is applied to a human body directly using a metal electrode, charged mineral ions in human cells migrate under the action of a conduction current, resulting in a change in the ion concentration in the cells, which is harmful to the human body [ PNAS, vol.104, pp10152-10157, 2007 ]. In addition, because high conduction current is directly related to the life safety of human bodies, the metal electrodes are used for applying electric fields to carry out medical research and treatment, the voltage cannot be too high, and the applied voltage is limited.
According to the physical principle, the pure capacitor is insulated for conducting current and is conducted for an alternating current electric field, so that in the experiment of clinically applying alternating voltage, if the insulated capacitor is used as an electrode to apply the alternating voltage, the conducting current in a human body can be avoided, and the side effect of the conducting current on cells is avoided. In addition, in general treatment, an electric field applied to a human body through the capacitive electrode is localized, and only the localized region is subjected to the electric field. Due to the insulating nature of the capacitor, no current is conducted through the body region to which the electric field is applied. Compared with a metal conductor electrode, the insulated capacitor electrode has higher safety.
Based on the above principle, there have been cases of applying an alternating current electric field by using an insulated capacitor electrode to perform biomedical and clinical experiments in foreign countries. Their preferred dielectric material is a ferroelectric ceramic material of the PMN-PT (lead magnesium niobate titanate material system) family, which corresponds to a relative dielectric constant greater than 5000. At a specific electric field frequency, the electric field can effectively inhibit tumor cell growth in animals and humans [ PNAS, vol.104, pp10152-10157, 2007 ].
Since the capacitive reactance of the capacitor is inversely proportional to the dielectric constant of the capacitor material [ electrotechnical, pamphlet, electronic technology, fifth edition, Qin-Zenghuang edition, page 108 ], the capacitive reactance of the capacitor made of the dielectric material with high dielectric constant is smaller. In addition, materials with high dielectric losses can generate heat under an electric field. Therefore, the material with high dielectric constant and low loss is adopted, so that the electric field can be more effectively applied to the human body part which directly needs to be researched or treated through the capacitor electrode plate with low capacitive reactance. Based on the application background, it is very urgent to find a suitable capacitor electrode made of a material with high dielectric constant to meet the requirements of domestic biomedical research or clinical application.
In general, ferroelectric materials have a high dielectric constant. PMN-PT (lead magnesium niobate-lead titanate material system) of perovskite structure is a relaxor ferroelectric material having a high dielectric constant or high piezoelectric coefficient. In order to obtain PMN-PT ceramic material with perovskite structure, MgNb which is synthesized in advance is required2O6As a precursor, then with other precursorsMixing the raw Materials, and synthesizing to obtain the specific component of PMN-PT with perovskite structure [ Materials Research Bulletin, vol.17, pp1245-1250, 1982; Journal of the American Ceramic Society, vol.82, pp797-818, 1999]。
A relaxor ferroelectric material based on a component in a PMN-PT system in MPB (quasi-isomorphous phase boundary) has excellent piezoelectric properties [ Journal of the American Ceramic Society, vol.82, pp797-818, 1999, Nature Materials, vol.17, pp349-354, 2018; Science, vol.364, pp264-268, 2019 ]. A great deal of research based on a PMN-PT system focuses on the components of an MPB phase boundary, and researches and develops piezoelectric materials. For materials for dielectric capacitance applications, the corresponding composition needs to deviate from the MPB phase boundary, and relatively little investigation is needed. In addition, compared with a bulk material, the dielectric thick film has the advantages of integration, miniaturization, homogenization and the like. It is necessary to study the preparation method of the ferroelectric thick film material to meet the use requirement.
Disclosure of Invention
The invention provides a ceramic thick film of a ceramic electrode for treating tumors by an electric field and a preparation method thereof.
According to one aspect of the present invention, there is provided a method for preparing a ceramic thick film for a ceramic electrode for electric field treatment of tumor, the method comprising the steps of:
1) synthesis of (1-x) Pb (Mg) by two-step solid phase method1/3Nb2/3)O3-xPb1-ySr0.5yNa0.25ySm0.25yTiO3Wherein x is more than or equal to 0.055 and less than or equal to 0.135, y is more than or equal to 0 and less than or equal to 0.03, and x and y are mole numbers:
1-1) with MgO, Nb2O5Is used as a raw material, and is thermally insulated for 2 hours at the temperature of 1000-1200 ℃ to synthesize MgNb2O6；
1-2) with MgNb2O6，Pb3O4，TiO2，Nb2O5，Na2CO3，SrCO3，Sm2O3As raw material, keeping the temperature at 815-865 ℃ for 4 hours to synthesize (1-x) Pb (Mg)1/3Nb2/3)O3-xPb1-ySr0.5yNa0.25ySm0.25yTiO3Powder, wherein x is more than or equal to 0.055 and less than or equal to 0.135, y is more than or equal to 0 and less than or equal to 0.03, and x and y are mole numbers;
mixing materials by adopting a wet ball milling method in the step 1-2), wherein the mass ratio of the ceramic powder, the milling balls and the deionized water is as follows: grinding balls: deionized water = 1: 2: 0.7, mixing and ball milling for 6 hours;
2) preparing casting slurry by using the powder synthesized in the step 1):
2-1) in (1-x) Pb (Mg)1/3Nb2/3)O3-xPb1-ySr0.5yNa0.25ySm0.25yTiO3Adding a proper amount of solvent and dispersant into the powder, and finely grinding for 24 hours;
2-2) adding a plasticizer, ball-milling for 15 minutes, then adding a binder, and continuously ball-milling for 24 hours;
wherein the solvent is ethanol and toluene in a mass ratio of 2: 3, mixing the dispersant and the plasticizer, wherein the dispersant is triethyl phosphate, the binder is polyvinyl butyral, and the plasticizer is the mixture of polyethylene glycol and dibutyl phthalate; the mass ratio of the powder, the solvent, the dispersant, the binder, the polyethylene glycol and the dibutyl phthalate is 22%: 65.8%: 0.2%: 2%: 2.5%: 7.5 percent;
2-3) carrying out tape casting on the slurry to obtain a tape casting film green body;
2-4) laminating the casting film green blank, pressurizing, then performing plastic removal, and removing organic substances in the casting film green blank to obtain a biscuit;
2-5) sintering the biscuit to obtain the ceramic thick film material.
According to an embodiment of the present invention, in the step 1-2), the grinding balls are zirconia balls.
According to one embodiment of the invention, in the step 2-4), the temperature of plastic discharge is 500-600 ℃, and the heat preservation time is 3 hours.
According to another embodiment of the invention, in the step 2-5), the sintering temperature is 1150-1250 ℃, the heating rate is 2-3 ℃/min, and the holding time is 2 hours.
According to another aspect of the present invention, there is provided a ceramic thick film for a ceramic electrode for electric field treatment of tumor, which is prepared by the aforementioned preparation method.
According to another embodiment of the invention, under room temperature, when the frequency is in the frequency range of 1 kHz-1 MHz, the relative dielectric constant of the ceramic thick film is more than 20000, and the dielectric loss is less than 0.04.
According to another aspect of the invention, there is provided a use of a ceramic material for a ceramic electrode for electric field treatment of a tumour in a capacitive electrode.
According to the ceramic thick film of the ceramic electrode for treating tumors by the electric field and the preparation method thereof, the ceramic thick film material with high dielectric constant, low dielectric loss and dielectric property is obtained by optimizing the doping element and the proportion and optimizing the specific operation of each step of the preparation method, and the ceramic thick film material makes excellent contribution to the preparation of the capacitor electrode required by biomedical research and clinical application. The preparation method provided by the invention is simple and feasible, is suitable for large-area popularization and use, and has good application prospect.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments made with reference to the following drawings:
FIG. 1 is an XRD pattern of a ceramic thick film material prepared by the ceramic thick film preparation method of a ceramic electrode for electric field tumor treatment provided by the invention;
FIG. 2 is a graph showing a hysteresis loop of a ceramic thick film material prepared by the method for preparing a ceramic thick film of a ceramic electrode for tumor electric field treatment according to the present invention;
FIG. 3 is an XRD pattern of another ceramic thick film material prepared by the ceramic thick film preparation method of the ceramic electrode for tumor electric field treatment provided by the invention;
FIG. 4 shows a pattern of a ferroelectric hysteresis loop of another ceramic thick film material prepared by the method for preparing a ceramic thick film of a ceramic electrode for tumor electric field treatment provided by the invention.
Detailed Description
The following disclosure provides many different embodiments, or examples, for implementing different features of the invention.
The invention provides a preparation method of a ceramic thick film of a ceramic electrode for electric field tumor treatment, wherein the ceramic thick film has ferroelectric property, and the method comprises the following steps:
step S101:
synthesis of (1-x) Pb (Mg) by two-step solid phase method1/3Nb2/3)O3-xPb1-ySr0.5yNa0.25ySm0.25yTiO3(ii) a Wherein x is more than or equal to 0.055 and less than or equal to 0.135, y is more than or equal to 0 and less than or equal to 0.03, and x and y are mole numbers.
The two-step solid phase process comprises:
the first step is as follows: with MgO, Nb2O5Is used as a raw material, and is thermally insulated for 2 hours at the temperature of 1000-1200 ℃ to synthesize MgNb2O6. Further, the raw materials of MgO and Nb are selected2O5Then, it is required to follow MgNb2O6The stoichiometric ratio of (A) is used for proportioning; then, mixing the raw materials by adopting a wet ball milling method; after mixing, drying the mixed material; finally, the MgNb is synthesized by heat preservation for 2 hours at the temperature of 1000-1200 DEG C2O6. More preferably, the MgNb is obtained by heat preservation at the temperature of 1150 DEG C2O6The quality is better.
The second step is that: preparing MgNb2O6Then, MgNb is added2O6，Pb3O4，TiO2，Nb2O5，Na2CO3，SrCO3，Sm2O3As raw material, keeping the temperature at 815-865 ℃ for 4 hours to synthesize (1-x) Pb (Mg)1/3Nb2/3)O3-xPb1- ySr0.5yNa0.25ySm0.25yTiO3Wherein x is more than or equal to 0.055 and less than or equal to 0.135, y is more than or equal to 0 and less than or equal to 0.03, and x and y are mole numbers.
Mixing materials by adopting a wet ball milling method, wherein the mass ratio of the ceramic powder, the milling balls and the deionized water is as follows:
ceramic powder: grinding balls: deionized water = 1: 2: 0.7, mixing and ball milling for 6 hours.
Preferably, the grinding balls are zirconia balls, and the powder is more suitable for ball milling operation.
Step S102:
and preparing the casting slurry by utilizing the synthesized powder. Firstly, (1-x) Pb (Mg)1/3Nb2/3)O3-xPb1- ySr0.5yNa0.25ySm0.25yTiO3Adding a proper amount of solvent and dispersant into the powder, and finely grinding for 24 hours; then adding plasticizer and ball milling for 15 minutes, then adding binder and continuing ball milling for 24 hours. After the ball milling is finished, removing bubbles for 25 minutes by using a vacuum method to obtain casting slurry, then, obtaining a casting film green body by using slurry casting molding, wherein the casting film green body with a specific shape can be obtained by firstly obtaining a casting film by using the slurry casting molding, and then cutting and the like on the casting film.
Preferably, the solvent is ethanol and toluene in a mass ratio of 2: 3, mixing; the dispersant is triethyl phosphate; the binder is polyvinyl butyral; the plasticizer is a mixture of polyethylene glycol and dibutyl phthalate.
Preferably, the mass ratio of the powder, the solvent, the dispersant, the binder, the polyethylene glycol and the dibutyl phthalate is 22%: 65.8%: 0.2%: 2%: 2.5%: 7.5 percent.
Step S103:
and laminating the cast film green blank (generally laminating the green blank to 10 layers), pressurizing by 3-5 MPa, and releasing pressure after 30 minutes of pressure maintaining. And then performing plastic removal, and removing organic substances in the cast film green blank to obtain a biscuit. The temperature of the discharged plastic is 500-600 ℃, and the heat preservation time is 3 hours.
And sintering the biscuit after plastic removal to obtain the ceramic thick film material. The sintering temperature is 1150-1250 ℃, the heating rate is 2-3 ℃/min, and the heat preservation time is 2 hours.
The technical solution provided by the present invention is further illustrated by two specific examples.
Example i:
the ferroelectric material comprises the following components: 0.88Pb (Mg)1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3，
First, two-step solid phase synthesis:
0.88Pb(Mg1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3，
first step of synthesizing MgNb2O6According to MgNb2O6MgO, Nb required for calculating chemical formula composition2O5Raw materials.
Mixing materials by adopting a wet ball milling method, wherein the mass ratio of the raw materials, the milling balls and the deionized water is as follows:
raw materials: grinding balls: deionized water = 1: 1.5: 0.8;
mixing for 6-8 hours to uniformly mix all the components.
Drying, and sieving after drying. The above mixed raw materials are preferably sieved with a 30-mesh sieve.
The mixed raw materials are insulated for 2 hours at the temperature of 1000-1200 ℃ to synthesize MgNb2O6；
Second step synthesis of 0.88Pb (Mg)1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3；
To obtain 0.88Pb (Mg)1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3MgNb required for calculating the chemical formula composition of2O6，Pb3O4，TiO2，Li2CO3，Na2CO3，SrCO3，Sm2O3The raw materials of (1).
Mixing materials by adopting a wet ball milling method, wherein the mass ratio of the raw materials, the milling balls and the deionized water is as follows:
raw materials: grinding balls: deionized water = 1: 2: 0.7;
mixing for 6-8 hours to uniformly mix all the components.
And drying, and sieving. The above mixed raw materials are preferably sieved with a 30-mesh sieve.
The mixed raw materials are kept at the temperature of 830-850 ℃ for 4 hours for synthesis
0.88Pb(Mg1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3。
Secondly, preparing casting slurry by utilizing the synthesized powder.
First at 0.88Pb (Mg)1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3 Adding a proper amount of solvent and dispersant into the powder, and finely grinding for 24 hours; then adding plasticizer and ball milling for 15 minutes, then adding binder and continuing ball milling for 24 hours. And after the ball milling is finished, removing bubbles for 25 minutes by using a vacuum method to obtain casting slurry.
Wherein the solvent is ethanol and toluene in a mass ratio of 2: 3, mixing; the dispersant is triethyl phosphate; the binder is polyvinyl butyral; the plasticizer is the mixture of polyethylene glycol and dibutyl phthalate;
wherein the mass ratio of the powder, the solvent, the dispersant, the binder, the polyethylene glycol and the dibutyl phthalate is 22 percent: 65.8%: 0.2%: 2%: 2.5%: 7.5 percent.
Thirdly, the slurry is cast to obtain a casting film green body.
Fourthly, stacking 10 layers of the casting film green blanks, pressurizing by 5 MPa, maintaining for 30 minutes, then releasing pressure, then preserving the temperature at 525 ℃ for 3 hours, removing plastic, and removing organic substances in the casting film green blanks to obtain biscuit;
fifthly, the biscuit is placed into an alumina crucible to be sintered in a closed manner, the biscuit is covered by ceramic powder with the same components, a grinding opening cover is covered, the temperature is increased to 1220 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 2 hours, and a ceramic material sample is obtained after furnace cooling.
And sixthly, grinding and flattening the sintered material, cleaning, drying, screen-printing silver paste, drying again, and putting into a box-type electric furnace for silver burning. The silver firing condition is 650 ℃ and the temperature is kept for 30 minutes, and the ceramic thick film sample covered with the electrode is obtained. The material phase structure was tested using XRD. The test results are shown in FIG. 1. The phase structure of the ceramic thick film material is a perovskite structure.
Seventhly, the dielectric property and the ferroelectric property under a strong field are tested on the sintered ceramic thick film sample. The dielectric properties were measured by a precision impedance analyzer (Agilent 4294A, product of Agilent Inc. USA), and refer to Table 1.
Figure 728858DEST_PATH_IMAGE001
In the frequency range of 1kHz to 1MHz, the relative dielectric constant of the ferroelectric ceramic material of the invention is more than 20000 at room temperature, and the dielectric loss is less than 0.04. The ferroelectric properties were measured using a TF Analyzer 2000 hysteresis loop measuring instrument from AIxACCT, Germany. Fig. 2 is a measured hysteresis loop of the ceramic thick film. The sample was not broken down by applying an alternating current field of 1 Hz at 90 KV/cm.
Example 2:
the ferroelectric material comprises the following components: 0.90Pb (Mg)1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3，
First, two-step solid phase synthesis:
0.90Pb(Mg1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3，
first step of synthesizing MgNb2O6According to MgNb2O6MgO, Nb required for calculating chemical formula composition2O5Raw materials.
Mixing materials by adopting a wet ball milling method, wherein the mass ratio of the raw materials, the milling balls and the deionized water is as follows:
raw materials: grinding balls: deionized water = 1: 1.5: 0.8;
mixing for 6-8 hours to uniformly mix all the components.
Drying, and sieving after drying. The above mixed raw materials are preferably sieved with a 30-mesh sieve.
The mixed raw materials are insulated for 2 hours at the temperature of 1000-1200 ℃ to synthesize MgNb2O6；
Second step synthesis of 0.90Pb (Mg)1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3；
To 0.90Pb (Mg)1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3MgNb required for calculating the chemical formula composition of2O6，Pb3O4，TiO2，Li2CO3，Na2CO3，SrCO3，Sm2O3The raw materials of (1).
Mixing materials by adopting a wet ball milling method, wherein the mass ratio of the raw materials, the milling balls and the deionized water is as follows:
raw materials: grinding balls: deionized water = 1: 2: 0.7;
mixing for 6-8 hours to uniformly mix all the components.
And drying, and sieving. The above mixed raw materials are preferably sieved with a 30-mesh sieve.
The mixed raw materials are kept at the temperature of 830-850 ℃ for 4 hours for synthesis
0.90Pb(Mg1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3。
Secondly, preparing casting slurry by utilizing the synthesized powder.
First at 0.90Pb (Mg)1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3Adding a proper amount of solvent and dispersant into the powder, and finely grinding for 24 hours; secondly, adding a plasticizerBall milling is carried out for 15 minutes, then the binder is added, and ball milling is continued for 24 hours. And after the ball milling is finished, removing bubbles for 25 minutes by using a vacuum method to obtain casting slurry.
Wherein the solvent is ethanol and toluene in a mass ratio of 2: 3, mixing; the dispersant is triethyl phosphate; the binder is polyvinyl butyral; the plasticizer is the mixture of polyethylene glycol and dibutyl phthalate;
wherein the mass ratio of the powder, the solvent, the dispersant, the binder, the polyethylene glycol and the dibutyl phthalate is 22 percent: 65.8%: 0.2%: 2%: 2.5%: 7.5 percent.
Thirdly, the slurry is cast to obtain a casting film green body.
Fourthly, stacking 10 layers of the casting film green blanks, pressurizing by 5 MPa, maintaining for 30 minutes, then releasing pressure, then preserving the temperature at 525 ℃ for 3 hours, removing plastic, and removing organic substances in the casting film green blanks to obtain biscuit.
Fifthly, the biscuit is placed into an alumina crucible to be sintered in a closed manner, the biscuit is covered by ceramic powder with the same components, a grinding opening cover is covered, the temperature is increased to 1220 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 2 hours, and a ceramic material sample is obtained after furnace cooling.
And sixthly, grinding and flattening the sintered material, cleaning, drying, screen-printing silver paste, drying again, and putting into a box-type electric furnace for silver burning. The silver firing condition is 650 ℃ and the temperature is kept for 30 minutes, and the ceramic thick film sample covered with the electrode is obtained. The material phase structure was tested using XRD. The test results are shown in FIG. 3. The phase structure of the ceramic thick film material is a perovskite structure.
Seventhly, the dielectric property and the ferroelectric property under a strong field are tested on the sintered ceramic thick film sample. The dielectric properties were measured by a precision impedance analyzer (Agilent 4294A, product of Agilent Inc., USA), see Table 2.
Figure 879217DEST_PATH_IMAGE002
In the frequency range of 1kHz to 1MHz, the relative dielectric constant of the ferroelectric ceramic material of the invention is more than 20000 at room temperature, and the dielectric loss is less than 0.04. Fig. 4 shows the measured hysteresis loop of the ceramic. The sample was not broken down by applying an alternating current field of 75 kV/cm at 1 Hz.
Comparative example 1:
the ferroelectric material comprises the following components: 0.88Pb (Mg)1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3，
Firstly, synthesizing by a solid phase method:
0.88Pb(Mg1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3；
first step of synthesizing MgNb2O6: with MgO, Nb2O5Is used as a raw material, and is thermally insulated for 2 hours at the temperature of 1000-1200 ℃ to synthesize MgNb2O6，；
Adopting a wet ball milling method for mixing materials, wherein the raw materials, the grinding balls and the deionized water are prepared from the following raw materials in mass: grinding balls: deionized water = 1: 1.5: 0.8; mixing for 6-8 hours to uniformly mix all the components. And drying, and sieving. The above mixed raw materials are preferably sieved with a 30-mesh sieve.
Second step synthesis of 0.88Pb (Mg)1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3：
With MgNb2O6，Pb3O4，TiO2，Nb2O5，Na2CO3，SrCO3，Sm2O3As raw material, the temperature is kept at 830-850 ℃ for 4 hours, and 0.88Pb (Mg) is synthesized1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3；
Adopting a wet ball milling method for mixing materials, wherein the raw materials, the grinding balls and the deionized water are prepared from the following raw materials in mass: grinding balls: deionized water = 1: 2: 0.7; mixing for 6-8 hours to uniformly mix all the components. Then, go intoDrying, and sieving. Sieving the mixed raw materials with a 30-mesh sieve preferably, and keeping the temperature of the mixed raw materials at 830-850 ℃ for 4 hours to synthesize 0.88Pb (Mg)1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3And (3) powder.
Secondly, the synthesized compound in the step 1)
0.88Pb(Mg1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3And (3) finely grinding the powder, adding a binder for granulation after fine grinding for 24 hours, and performing compression molding to obtain a biscuit.
Thirdly, the biscuit which is formed by pressing is kept at 650 ℃ for 2 hours, organic substances in the biscuit are removed, and the plastic removal rate does not exceed 3 ℃/min.
Fourthly, placing the sample after plastic removal into an alumina crucible for closed sintering, covering the blank with powder with the same components in order to prevent the volatilization of lead components, covering a grinding opening cover, raising the temperature to 1235-1250 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2 hours, and cooling along with the furnace to obtain compact finished ceramics.
Fifthly, grinding, cleaning and drying the sintered finished product. And an upper electrode for testing the dielectric property and the ferroelectric loop. The dielectric constant can only reach 15000, the dielectric loss is 0.045, and the highest bearing electric field of the ferroelectric loop test is only 60 kV/cm. Compared with the ceramic thick film material, the prepared ceramic block has lower dielectric constant and lower breakdown field strength.
Comparative example 2:
the ferroelectric material comprises the following components: 0.88Pb (Mg)1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3，
First, two-step solid phase synthesis:
0.88Pb(Mg1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3，
first step of synthesizing MgNb2O6According to MgNb2O6MgO, Nb required for calculating chemical formula composition2O5Raw materials.
Mixing materials by adopting a wet ball milling method, wherein the mass ratio of the raw materials, the milling balls and the deionized water is as follows:
raw materials: grinding balls: deionized water = 1: 1.5: 0.8;
mixing for 6-8 hours to uniformly mix all the components.
Drying, and sieving after drying. The above mixed raw materials are preferably sieved with a 30-mesh sieve.
The mixed raw materials are insulated for 2 hours at the temperature of 1000-1200 ℃ to synthesize MgNb2O6；
Second step synthesis of 0.88Pb (Mg)1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3；
To obtain 0.88Pb (Mg)1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3MgNb required for calculating the chemical formula composition of2O6，Pb3O4，TiO2，Li2CO3，Na2CO3，SrCO3，Sm2O3The raw materials of (1).
Mixing materials by adopting a wet ball milling method, wherein the mass ratio of the raw materials, the milling balls and the deionized water is as follows:
raw materials: grinding balls: deionized water = 1: 2: 0.7;
mixing for 6-8 hours to uniformly mix all the components.
And drying, and sieving. The above mixed raw materials are preferably sieved with a 30-mesh sieve.
The mixed raw materials are kept at the temperature of 830-850 ℃ for 4 hours for synthesis
0.88Pb(Mg1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3。
Secondly, preparing casting slurry by utilizing the synthesized powder.
First at 0.88Pb (Mg)1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3 Adding a proper amount of solvent and dispersant into the powder, and finely grinding for 24 hours; then adding plasticizer and ball milling for 15 minutes, then adding binder and continuing ball milling for 24 hours. And after the ball milling is finished, removing bubbles for 25 minutes by using a vacuum method to obtain casting slurry.
Wherein the solvent is ethanol and toluene in a mass ratio of 2: 3, mixing; the dispersant is triethyl phosphate; the binder is polyvinyl butyral; the plasticizer is a mixture of polyethylene glycol and dibutyl phthalate.
Wherein the mass ratio of the powder, the solvent, the dispersant, the binder, the polyethylene glycol and the dibutyl phthalate is 32 percent: 55.8%: 0.2%: 2%: 2.5%: 7.5 percent.
Thirdly, the slurry is cast to obtain a casting film green body.
Fourthly, stacking 10 layers of the casting film green blanks, pressurizing by 5 MPa, maintaining for 30 minutes, then releasing pressure, then preserving the temperature at 525 ℃ for 3 hours, removing plastic, and removing organic substances in the casting film green blanks to obtain biscuit.
Fifthly, the biscuit is placed into an alumina crucible to be sintered in a closed manner, the biscuit is covered by ceramic powder with the same components, a grinding opening cover is covered, the temperature is increased to 1220 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 2 hours, and a ceramic material sample is obtained after furnace cooling.
And sixthly, grinding the sintered ceramic material, cleaning, drying, screen-printing silver paste, drying again, and putting into a box-type electric furnace for silver burning. And (3) keeping the temperature at 650 ℃ for 30 minutes under the silver firing condition to obtain a ceramic thick film sample coated with the electrode.
The slurry formed in the preparation process has poor fluidity, is difficult to demould and is easy to crack.
Comparative example 3:
the ferroelectric material comprises the following components: 0.88Pb (Mg)1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3，
First, two-step solid phase synthesis:
0.88Pb(Mg1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3，
first step of synthesizing MgNb2O6According to MgNb2O6MgO, Nb required for calculating chemical formula composition2O5Raw materials.
Mixing materials by adopting a wet ball milling method, wherein the mass ratio of the raw materials, the milling balls and the deionized water is as follows:
raw materials: grinding balls: deionized water = 1: 1.5: 0.8;
mixing for 6-8 hours to uniformly mix all the components.
Drying, and sieving after drying. The above mixed raw materials are preferably sieved with a 30-mesh sieve.
The mixed raw materials are insulated for 2 hours at the temperature of 1000-1200 ℃ to synthesize MgNb2O6；
Second step synthesis of 0.88Pb (Mg)1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3；
To obtain 0.88Pb (Mg)1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3MgNb required for calculating the chemical formula composition of2O6，Pb3O4，TiO2，Li2CO3，Na2CO3，SrCO3，Sm2O3The raw materials of (1).
Mixing materials by adopting a wet ball milling method, wherein the mass ratio of the raw materials, the milling balls and the deionized water is as follows:
raw materials: grinding balls: deionized water = 1: 2: 0.7;
mixing for 6-8 hours to uniformly mix all the components.
And drying, and sieving. The above mixed raw materials are preferably sieved with a 30-mesh sieve.
The mixed raw materials are kept at the temperature of 830-850 ℃ for 4 hours for synthesis
0.88Pb(Mg1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3。
Secondly, preparing casting slurry by utilizing the synthesized powder.
First at 0.88Pb (Mg)1/3Nb2/3)O3-0.12Pb0.98Sr0.01Na0.005Sm0.005TiO3 Adding a proper amount of solvent and dispersant into the powder, and finely grinding for 24 hours; then adding plasticizer and ball milling for 15 minutes, then adding binder and continuing ball milling for 24 hours. And after the ball milling is finished, removing bubbles for 25 minutes by using a vacuum method to obtain casting slurry. .
Wherein the solvent is ethanol and toluene in a mass ratio of 2: 3, mixing; the dispersant is triethyl phosphate; the binder is polyvinyl butyral; the plasticizer is the mixture of polyethylene glycol and dibutyl phthalate;
wherein the mass ratio of the powder, the solvent, the dispersant, the binder, the polyethylene glycol and the dibutyl phthalate is 15 percent: 72.88%: 0.2%: 2%: 2.5%: 7.5 percent.
Thirdly, the slurry is cast to obtain a casting film green body.
Fourthly, stacking 10 layers of the casting film green blanks, pressurizing by 5 MPa, maintaining for 30 minutes, then releasing pressure, then preserving the temperature at 525 ℃ for 3 hours, removing plastic, and removing organic substances in the casting film green blanks to obtain biscuit.
Fifthly, the biscuit is placed into an alumina crucible to be sintered in a closed manner, the biscuit is covered by ceramic powder with the same components, a grinding opening cover is covered, the temperature is increased to 1220 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 2 hours, and a ceramic material sample is obtained after furnace cooling.
And sixthly, grinding the sintered ceramic material, cleaning, drying, screen-printing silver paste, drying again, and putting into a box-type electric furnace for silver burning. And (3) keeping the temperature at 650 ℃ for 30 minutes under the silver firing condition to obtain a ceramic thick film sample coated with the electrode.
The slurry formed in the preparation process has good fluidity, but the thick film has pores on the surface, the toughness of the thick film is poor, and the demoulding is difficult.
Comparative example 4:
the ferroelectric material comprises the following components: 0.90Pb (Mg)1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3，
First, two-step solid phase synthesis:
0.90Pb(Mg1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3，
first step of synthesizing MgNb2O6According to MgNb2O6MgO, Nb required for calculating chemical formula composition2O5Raw materials.
Mixing materials by adopting a wet ball milling method, wherein the mass ratio of the raw materials, the milling balls and the deionized water is as follows:
raw materials: grinding balls: deionized water = 1: 1.5: 0.8;
mixing for 6-8 hours to uniformly mix all the components.
Drying, and sieving after drying. The above mixed raw materials are preferably sieved with a 30-mesh sieve.
The mixed raw materials are insulated for 2 hours at the temperature of 1000-1200 ℃ to synthesize MgNb2O6；
Second step synthesis of 0.90Pb (Mg)1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3；
To 0.90Pb (Mg)1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3MgNb required for calculating the chemical formula composition of2O6，Pb3O4，TiO2，Li2CO3，Na2CO3，SrCO3，Sm2O3The raw materials of (1).
Mixing materials by adopting a wet ball milling method, wherein the mass ratio of the raw materials, the milling balls and the deionized water is as follows:
raw materials: grinding balls: deionized water = 1: 2: 0.7;
mixing for 6-8 hours to uniformly mix all the components.
And drying, and sieving. The above mixed raw materials are preferably sieved with a 30-mesh sieve.
The mixed raw materials are kept at the temperature of 830-850 ℃ for 4 hours for synthesis
0.90Pb(Mg1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3。
Secondly, preparing casting slurry by utilizing the synthesized powder.
First at 0.90Pb (Mg)1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3Adding a proper amount of solvent and dispersant into the powder, and finely grinding for 24 hours; then adding plasticizer and ball milling for 15 minutes, then adding binder and continuing ball milling for 24 hours. And after the ball milling is finished, removing bubbles for 25 minutes by using a vacuum method to obtain casting slurry.
Wherein the solvent is ethanol and toluene in a mass ratio of 2: 3, mixing; the dispersant is triethyl phosphate; the binder is polyvinyl butyral; the plasticizer is the mixture of polyethylene glycol and dibutyl phthalate;
wherein the mass ratio of the powder, the solvent, the dispersant, the binder, the polyethylene glycol and the dibutyl phthalate is 22 percent: 65.8%: 0.1%: 2.1%: 2.5%: 7.5 percent.
Thirdly, carrying out tape casting on the slurry to obtain a tape casting film green body;
fourthly, stacking 10 layers of the casting film green blanks, pressurizing by 5 MPa, maintaining for 30 minutes, then releasing pressure, then preserving the temperature at 525 ℃ for 3 hours, removing plastic, and removing organic substances in the casting film green blanks to obtain biscuit;
fifthly, the biscuit is placed into an alumina crucible to be sintered in a closed manner, the biscuit is covered by ceramic powder with the same components, a grinding opening cover is covered, the temperature is increased to 1220 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 2 hours, and a ceramic material sample is obtained after furnace cooling.
And sixthly, grinding the sintered ceramic material, cleaning, drying, screen-printing silver paste, drying again, and putting into a box-type electric furnace for silver burning. And (3) keeping the temperature at 650 ℃ for 30 minutes under the silver firing condition to obtain a ceramic thick film sample coated with the electrode.
The obtained thick film has small particles and pores on the surface. The toughness of the thick film is poor, and the demoulding is difficult.
Comparative example 5:
the ferroelectric material comprises the following components: 0.90Pb (Mg)1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3，
First, two-step solid phase synthesis:
0.90Pb(Mg1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3，
first step of synthesizing MgNb2O6According to MgNb2O6MgO, Nb required for calculating chemical formula composition2O5Raw materials.
Mixing materials by adopting a wet ball milling method, wherein the mass ratio of the raw materials, the milling balls and the deionized water is as follows:
raw materials: grinding balls: deionized water = 1: 1.5: 0.8;
mixing for 6-8 hours to uniformly mix all the components.
Drying, and sieving after drying. The above mixed raw materials are preferably sieved with a 30-mesh sieve.
The mixed raw materials are insulated for 2 hours at the temperature of 1000-1200 ℃ to synthesize MgNb2O6；
Second step synthesis of 0.90Pb (Mg)1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3；
To 0.90Pb (Mg)1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3MgNb required for calculating the chemical formula composition of2O6，Pb3O4，TiO2，Li2CO3，Na2CO3，SrCO3，Sm2O3The raw materials of (1).
Mixing materials by adopting a wet ball milling method, wherein the mass ratio of the raw materials, the milling balls and the deionized water is as follows:
raw materials: grinding balls: deionized water = 1: 2: 0.7;
mixing for 6-8 hours to uniformly mix all the components.
And drying, and sieving. The above mixed raw materials are preferably sieved with a 30-mesh sieve.
The mixed raw materials are kept at the temperature of 830-850 ℃ for 4 hours for synthesis
0.90Pb(Mg1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3。
Secondly, preparing casting slurry by utilizing the synthesized powder.
First at 0.90Pb (Mg)1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3Adding a proper amount of solvent and dispersant into the powder, and finely grinding for 24 hours; then adding plasticizer and ball milling for 15 minutes, then adding binder and continuing ball milling for 24 hours. And after the ball milling is finished, removing bubbles for 25 minutes by using a vacuum method to obtain casting slurry.
Wherein the solvent is ethanol and toluene in a mass ratio of 2: 3, mixing; the dispersant is triethyl phosphate; the binder is polyvinyl butyral; the plasticizer is the mixture of polyethylene glycol and dibutyl phthalate;
wherein the mass ratio of the powder, the solvent, the dispersant, the binder, the polyethylene glycol and the dibutyl phthalate is 22 percent: 65.8%: 0.2%: 2%: 1.5%: 8.5 percent.
Thirdly, the slurry is cast to obtain a casting film green body.
Fourthly, stacking 10 layers of the casting film green blanks, pressurizing by 5 MPa, maintaining for 30 minutes, then releasing pressure, then preserving the temperature at 525 ℃ for 3 hours, removing plastic, and removing organic substances in the casting film green blanks to obtain biscuit;
fifthly, the biscuit is placed into an alumina crucible to be sintered in a closed manner, the biscuit is covered by ceramic powder with the same components, a grinding opening cover is covered, the temperature is increased to 1220 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 2 hours, and a ceramic material sample is obtained after furnace cooling.
And sixthly, grinding the sintered ceramic material, cleaning, drying, screen-printing silver paste, drying again, and putting into a box-type electric furnace for silver burning. And (3) keeping the temperature at 650 ℃ for 30 minutes under the silver firing condition to obtain a ceramic thick film sample coated with the electrode.
The obtained film has microcrack on the surface, general plastic toughness, difficult demoulding and easy cracking.
Comparative example 6:
the ferroelectric material comprises the following components: 0.90Pb (Mg)1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3，
First, two-step solid phase synthesis:
0.90Pb(Mg1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3，
first step of synthesizing MgNb2O6According to MgNb2O6MgO, Nb required for calculating chemical formula composition2O5Raw materials.
Mixing materials by adopting a wet ball milling method, wherein the mass ratio of the raw materials, the milling balls and the deionized water is as follows:
raw materials: grinding balls: deionized water = 1: 1.5: 0.8;
mixing for 6-8 hours to uniformly mix all the components.
Drying, and sieving after drying. The above mixed raw materials are preferably sieved with a 30-mesh sieve.
The mixed raw materials are insulated for 2 hours at the temperature of 1000-1200 ℃ to synthesize MgNb2O6；
Second step synthesis of 0.90Pb (Mg)1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3；
To 0.90Pb (Mg)1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3MgNb required for calculating the chemical formula composition of2O6，Pb3O4，TiO2，Li2CO3，Na2CO3，SrCO3，Sm2O3The raw materials of (1).
Mixing materials by adopting a wet ball milling method, wherein the mass ratio of the raw materials, the milling balls and the deionized water is as follows:
raw materials: grinding balls: deionized water = 1: 2: 0.7;
mixing for 6-8 hours to uniformly mix all the components.
And drying, and sieving. The above mixed raw materials are preferably sieved with a 30-mesh sieve.
The mixed raw materials are kept at the temperature of 830-850 ℃ for 4 hours for synthesis
0.90Pb(Mg1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3。
Secondly, preparing casting slurry by utilizing the synthesized powder.
First at 0.90Pb (Mg)1/3Nb2/3)O3-0.10Pb0.99Sr0.005Na0.0025Sm0.0025TiO3Adding a proper amount of solvent and dispersant into the powder, and finely grinding for 24 hours; then adding plasticizer and ball milling for 15 minutes, then adding binder and continuing ball milling for 24 hours. And after the ball milling is finished, removing bubbles for 25 minutes by using a vacuum method to obtain casting slurry.
Wherein the solvent is ethanol and toluene in a mass ratio of 2: 3, mixing; the dispersant is triethyl phosphate; the binder is polyvinyl butyral; the plasticizer is the mixture of polyethylene glycol and dibutyl phthalate;
wherein the mass ratio of the powder, the solvent, the dispersant, the binder, the polyethylene glycol and the dibutyl phthalate is 22 percent: 65.8%: 0.2%: 2%: 3.5%: 6.5 percent.
Thirdly, the slurry is cast to obtain a casting film green body.
Fourthly, stacking 10 layers of the casting film green blanks, pressurizing by 5 MPa, maintaining for 30 minutes, then releasing pressure, then preserving the temperature at 525 ℃ for 3 hours, removing plastic, and removing organic substances in the casting film green blanks to obtain biscuit;
fifthly, the biscuit is placed into an alumina crucible to be sintered in a closed manner, the biscuit is covered by ceramic powder with the same components, a grinding opening cover is covered, the temperature is increased to 1220 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 2 hours, and a ceramic material sample is obtained after furnace cooling.
And sixthly, grinding the sintered ceramic material, cleaning, drying, screen-printing silver paste, drying again, and putting into a box-type electric furnace for silver burning. And (3) keeping the temperature at 650 ℃ for 30 minutes under the silver firing condition to obtain a ceramic thick film sample coated with the electrode.
The obtained film has uniform surface, but has poor plastic toughness, difficult demoulding and easy cracking.
In addition, the ceramic material (1-x) Pb (Mg) is prepared by adopting the ceramic material disclosed by the Chinese invention patent with the publication number of CN106946569B1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yO3Compared with the ceramic thick film obtained by subsequent tape casting, the ceramic thick film obtained by the invention has better performance.
The invention can obtain the ferroelectric thick film ceramic material by selecting proper doping modification, utilizing a two-step synthesis method, tape casting and sintering. The material has the characteristics of high dielectric constant and low dielectric loss, can be used for manufacturing insulated capacitor electrodes, and has a good application prospect.
Although the present invention has been described in detail with respect to the exemplary embodiments and advantages thereof, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention as defined by the appended claims.
Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed, that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Claims (7)

1. A preparation method of a ceramic thick film of a ceramic electrode for electric field treatment of tumors is characterized by comprising the following steps:
1) synthesis of (1-x) Pb (Mg) by two-step solid phase method1/3Nb2/3)O3-xPb1-ySr0.5yNa0.25ySm0.25yTiO3Wherein x is more than or equal to 0.055 and less than or equal to 0.135 and 0<y is less than or equal to 0.03, and x and y are mole numbers:
1-1) with MgO, Nb2O5Is used as a raw material, and is thermally insulated for 2 hours at the temperature of 1000-1200 ℃ to synthesize MgNb2O6；
1-2) with MgNb2O6，Pb3O4，TiO2，Nb2O5，Na2CO3，SrCO3，Sm2O3As raw material, keeping the temperature at 815-865 ℃ for 4 hours to synthesize (1-x) Pb (Mg)1/3Nb2/3)O3-xPb1-ySr0.5yNa0.25ySm0.25yTiO3Powder, wherein x is more than or equal to 0.055 and less than or equal to 0.135 and 0<y is less than or equal to 0.03, and x and y are mole numbers;
mixing materials by adopting a wet ball milling method in the step 1-2), wherein the mass ratio of the ceramic powder, the milling balls and the deionized water is as follows: grinding balls: deionized water = 1: 2: 0.7, mixing and ball milling for 6 hours;
2) preparing casting slurry by using the powder synthesized in the step 1):
2-1) in (1-x) Pb (Mg)1/3Nb2/3)O3-xPb1-ySr0.5yNa0.25ySm0.25yTiO3Adding a proper amount of solvent and dispersant into the powder, and finely grinding for 24 hours;
2-2) adding a plasticizer, ball-milling for 15 minutes, then adding a binder, and continuously ball-milling for 24 hours;
wherein the solvent is ethanol and toluene in a mass ratio of 2: 3, mixing the dispersant and the plasticizer, wherein the dispersant is triethyl phosphate, the binder is polyvinyl butyral, and the plasticizer is the mixture of polyethylene glycol and dibutyl phthalate; the mass ratio of the powder, the solvent, the dispersant, the binder, the polyethylene glycol and the dibutyl phthalate is 22%: 65.8%: 0.2%: 2%: 2.5%: 7.5 percent;
2-3) carrying out tape casting on the slurry to obtain a tape casting film green body;
2-4) laminating the casting film green blank, pressurizing, then discharging plastic, and removing organic substances in the casting film green blank to obtain a biscuit;
2-5) sintering the biscuit to obtain the ceramic thick film material.
2. The method for preparing a ceramic thick film of a ceramic electrode for electric field treatment of tumor according to claim 1, wherein in step 1-2), the grinding ball is a zirconia ball.
3. The method for preparing a ceramic thick film of a ceramic electrode for electric field therapy of tumor according to claim 1, wherein in the step 2-4), the temperature of plastic discharge is 500 ℃ to 600 ℃, and the holding time is 3 hours.
4. The method for preparing a ceramic thick film of a ceramic electrode for electric field therapy of tumor according to claim 1, wherein in the step 2-5), the sintering temperature is 1150-1250 ℃, the heating rate is 2-3 ℃/min, and the holding time is 2 hours.
5. A ceramic thick film of a ceramic electrode for electric field treatment of tumors prepared by the method of any one of claims 1-4.
6. The ceramic thick film of a ceramic electrode for electric field therapy of tumor according to claim 5, wherein the relative dielectric constant of the ceramic thick film is more than 20000 and the dielectric loss is less than 0.04 at room temperature when the frequency is in the frequency range of 1 kHz-1 MHz.
7. Use of the ceramic thick film of the ceramic electrode for electric field treatment of tumors according to claim 5 in a capacitive electrode.
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