CN106946569B - Ceramic electrode material and element for biomedical research and clinical application - Google Patents
Ceramic electrode material and element for biomedical research and clinical application Download PDFInfo
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Abstract
The invention relates to a ferroelectric ceramic material with high dielectric constant and low loss and a dielectric element prepared by the same, wherein the chemical composition of the ferroelectric ceramic material conforms to the chemical general formula (1-x) Pb (Mg)1/3Nb2/3)O3‑xPb1‑yLi0.5yNa0.5yTi1‑yNbyO3Wherein x is more than or equal to 0.072 and less than or equal to 0.120, y is more than or equal to 0 and less than or equal to 0.06, and x and y are mole numbers. The ferroelectric ceramic material is prepared by selecting proper composite doping modified ions and utilizing the traditional electronic ceramic preparation process. Correspondingly, the invention also provides a ferroelectric ceramic material prepared by the preparation method, and the ceramic material has the characteristics of high dielectric constant and low loss and is suitable for manufacturing a capacitor electrode for conducting alternating current. The material has good prospect in biomedical research and clinical application of applying an alternating current electric field.
Description
Technical Field
The invention belongs to the technical field of functional ceramic materials, and particularly relates to a dielectric ceramic material for a capacitor and a preparation method thereof.
Background
Biomedical research shows that under The action of an alternating current electric field, if a proper electric field frequency is selected, The electric field can selectively promote partial cell rotation due to charged ions in cells [ The Journal of membrane biology, vol.67, pp13-26,1982 ]. This is because, under the action of an external electric field, charged ions undergo local short-range migration, and an electric field-induced electric dipole is generated in the cell, and the electric dipole can rotate under the action of the external field, rotating together with the cell.
The electric moment direction of a single electric dipole is from negative charge to positive charge, and when the direction of an external electric field is perpendicular to the electric moment direction of the electric dipole, the electric field can most effectively induce the electric dipole to rotate. The electric field along the x-x direction in fig. 1 can more effectively induce dipole rotation in the figure. Conversely, since the electric field along the y-y direction is parallel to the electric dipole direction, the electric field can change the length of the dipole, but does not contribute to the rotation of the electric dipole.
Figure 2 illustrates differently oriented electrical dipoles within a carrier. In order to increase the rotating effect for the electric dipoles with different orientations, at least two pairs of electrodes perpendicular to each other (along the x direction and along the y direction in fig. 2) should be applied, and the two pairs of electrodes are sequentially energized by intermittent loading to induce the maximum amount of electric dipole rotation.
In biomedical and clinical applications in particular, if an electric field is applied directly to the human body using metal electrodes, migration of charged mineral ions within the human body's cells occurs under the effect of a conducted current, resulting in a change in the concentration of ions within 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 ceramic 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.
Biomedical experiments have shown that the growth of specific abnormal cells can be effectively inhibited by applying alternating voltage through insulated capacitor electrodes at specific alternating frequency [ Cancer Research, vol.64, pp3288-3295,2004; PNAS, vol.104, pp10152-10157,2007 ].
Figure 3 illustrates a parallel plate capacitor with three dielectric layers. Wherein S1 and S2 are metal plates of the capacitor. A, B and C are three layers of dielectric material layers which are parallel to each other. And the electric field intensity distribution of each layer A, B, C is inversely proportional to the dielectric constant of each dielectric layer [ general physics, advanced school teaching materials, second volume, 5 th edition, engineering conservation, Youth code of Jiang, page 123 ]. If A is chosen, the dielectric constant of the C two layers is much greater than that of the B layer. The electric field formed in the capacitor by the applied voltage V can be concentrated mainly in the B layer having a small dielectric constant, while the electric field in both a and C layers is very small. Thus, in the circuit of fig. 3, the two layers a and C have the same effect as two capacitor electrodes. 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 is effective in inhibiting tumor cell growth in animals and humans [ PNAS, vol.104, pp10152-10157,2007 ]. The treatment effect can be further optimized by applying voltage to two pairs of electrodes in a bidirectional vertical mode and supplying power to the two pairs of electrodes in sequence in an intermittent voltage application mode [ 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 with high dielectric constant. Partially relaxed ferroelectric ceramics based on the PMN-PT system are preferred dielectric materials. [ Journal of the American Ceramic Society, vol.82, pp797-818,1999]. In order to obtain PMN-PT ceramic material with perovskite structure, MgNb which is synthesized in advance is required2O6Is used as a precursor, and then is mixed with other raw materials to synthesize the specific component of the PMN-PT with the perovskite structure. [ Materials research bulletin, vol.17, pp1245-1250,1982; journal of the American Ceramic Society, vol.82, pp797-818,1999]。
Disclosure of Invention
The invention provides a preparation method of a ferroelectric ceramic material, and the ceramic material and an element prepared by the method.
According to an aspect of the present invention, there is provided a method for preparing a ferroelectric ceramic material, the method comprising the steps of:
1) synthesized by adopting a two-step solid phase method
(1-x)Pb(Mg1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3
The two-step solid phase process comprises:
1-1) with MgO, Nb2O5Is used as 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，Li2CO3,Na2CO3As raw material, the temperature is kept at 825-855 ℃ for 4 hours, and (1-x) Pb (Mg) is synthesized1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3The powder, wherein x is more than or equal to 0.072 and less than or equal to 0.120, y is more than or equal to 0 and less than or equal to 0.06, and x and y are mole numbers;
2) for the synthesized in the step 1)
(1-x)Pb(Mg1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3
Finely grinding the powder, adding a binder for granulation after fine grinding, and performing compression molding to obtain a biscuit;
3) performing plastic removal to remove organic substances in the biscuit;
4) and sintering the biscuit to obtain the ferroelectric ceramic material.
According to a specific embodiment of the present invention, the step 1-1) is specifically:
with MgO, Nb2O5As raw material, according to MgNb2O6The materials are mixed by a wet ball milling method after being proportioned according to the stoichiometric ratio;
drying the mixed material;
the MgNb is synthesized by heat preservation for 2 hours at the temperature of 1000 to 1200 DEG C2O6。
According to another embodiment of the present invention, the step 1-2) is specifically:
with MgNb2O6，Pb3O4，TiO2，Nb2O5，Li2CO3,Na2CO3As raw material, according to (1-x) Pb (Mg)1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3The materials are mixed by a wet ball milling method after being proportioned according to the stoichiometric ratio;
drying the mixed material;
keeping the temperature for 4 hours at 825-855 ℃ to obtain
(1-x)Pb(Mg1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3Powder body
Wherein x is more than or equal to 0.072 and less than or equal to 0.120, y is more than or equal to 0 and less than or equal to 0.06, and x and y are mole numbers;
according to another embodiment of the invention, in the step 2), the mass ratio of the ceramic powder, the grinding ball and the deionized water is as follows:
ceramic powder: grinding balls: deionized water 1: (1.8-2): (0.6-0.8).
According to another embodiment of the present invention, the fine grinding time is 24 to 48 hours.
According to yet another embodiment of the present invention, the grinding balls are zirconia balls.
According to still another embodiment of the present invention, in the step 2), the binder used is PVA;
the addition amount of the binder is 5-8% of the mass of the ceramic powder.
According to another embodiment of the invention, in the step 3), the temperature of the plastic discharging is 500-600 ℃, and the heat preservation time is 2-3 hours.
According to another embodiment of the present invention, the step 4) is specifically:
and putting the biscuit into a crucible for closed sintering, wherein the sintering temperature is 1180-1250 ℃, the heating rate is 2-5 ℃/min, and the heat preservation time is l-3 hours.
According to another aspect of the present invention, there is provided a ferroelectric ceramic material having a chemical composition corresponding to the general chemical formula (1-x) Pb (Mg)1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3,
Wherein x is more than or equal to 0.072 and less than or equal to 0.120, y is more than or equal to 0 and less than or equal to 0.06, and x and y are mole numbers;
the ferroelectric ceramic material is prepared by the preparation method provided by any one of the preceding claims.
According to one embodiment of the present invention, the ferroelectric ceramic material is capable of being sintered at 1180 ℃ to 1250 ℃.
According to another embodiment of the present invention, the ferroelectric ceramic material has a relative dielectric constant of more than 12000 and a dielectric loss of less than 0.05 at a frequency of 100Hz to 1MHz at room temperature.
Two parallel ceramic plates may form a pair of capacitor electrodes, as shown in fig. 3, and electrode plate a, and electrode plate C are connected to an external voltage source through metal plates S1, S2 on their outer sides. Through two mutually parallel capacitor electrode pieces, an alternating current electric field can be applied to different carriers B containing electric dipoles through the capacitor electrodes.
In order to increase the rotation effect for the electric dipoles with different orientations, as shown in fig. 2, two pairs of electrodes perpendicular to each other in the X and Y directions may be added, and the two pairs of electrodes are sequentially powered by an intermittent power-up manner, so as to induce the maximum number of electric dipoles to participate in rotation under the action of the electric field.
In biomedical research and clinical experiments, ceramic wafers can be fired into different shapes according to the body types of animals for experiments and the shapes of different parts of human bodies of patients, so that ceramic electrode elements are conveniently fixed, and an external alternating current electric field is ensured to be more effectively applied to specific experimental parts through a capacitive electrode.
In biomedical research, the electric field applied by the capacitive electrode can be used for researching the influence of different electric field strengths and frequencies on different cell growth in an animal body by adjusting the electric field strength and the frequencies. In clinical experiments, the electric field applied by the capacitive electrode can be used for researching the influence of different electric field strengths and frequencies on different cell growths in a human body by adjusting the electric field strength and the frequencies.
According to the preparation method of the ferroelectric ceramic material and the element, the dielectric ceramic material with high dielectric constant and low dielectric loss and the corresponding capacitor element are obtained by optimizing the doping element and the proportion and optimizing the specific operation of each step of the preparation method, and the preparation method makes excellent contribution to the preparation of capacitor electrodes 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 shows that the rotation effect of a single electric dipole is different under the action of electric fields in different directions;
FIG. 2 is a graph showing the improvement in the rotational efficiency of randomly oriented electric dipoles by applying an electric field intermittently in either the X or Y direction in sequence using two pairs of electrodes oriented perpendicular to each other;
FIG. 3 shows that an alternating voltage V can apply an electric field to a carrier B through the capacitor electrodes A and C which are conducted in an alternating current;
fig. 4 shows an XRD spectrum of a ferroelectric ceramic material prepared by the method for preparing a ferroelectric ceramic material according to the present invention;
fig. 5 is a diagram showing a room temperature hysteresis loop of a ferroelectric ceramic material prepared by the method for preparing a ferroelectric ceramic material according to the present invention.
FIG. 6 is an XRD spectrum of another ferroelectric ceramic material prepared by the method for preparing a ferroelectric ceramic material according to the present invention;
fig. 7 is a diagram showing a room temperature hysteresis loop of another ferroelectric ceramic material prepared by the method for preparing a ferroelectric ceramic material according to the present invention.
The same or similar reference numbers in the drawings identify the same or similar elements.
Detailed Description
The following disclosure provides many different embodiments, or examples, for implementing different features of the invention. To simplify the disclosure of the present invention, the components and arrangements of specific examples are described below. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. It should be noted that the components illustrated in the figures are not necessarily drawn to scale. Descriptions of well-known components and processing techniques and procedures are omitted so as to not unnecessarily limit the invention.
The preparation method of the ferroelectric ceramic material provided by the invention comprises the following steps:
Synthesis of (1-x) Pb (Mg) by two-step solid phase method1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3
The two-step solid phase process comprises:
with MgO, Nb2O5Is used as 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 ℃ to 1200 DEG C2O6. More preferably, the MgNb is obtained by heat preservation at the temperature of 1150 DEG C2O6The quality is better.
Preparing MgNb2O6Then, MgNb is added2O6，Pb3O4,TiO2,Nb2O5，Li2CO3,Na2CO3As raw material, the temperature is kept at 825-855 ℃ for 4 hours, and (1-x) Pb (Mg) is synthesized1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3The powder, wherein x is more than or equal to 0.072 and less than or equal to 0.120, y is more than or equal to 0 and less than or equal to 0.06, and x and y are mole numbers;
the second step solid phase method specifically comprises the following steps: firstly, MgNb is added2O6，Pb3O4，TiO2，Pb3O4,TiO2,Li2CO3,Na2CO3As raw material, according to (1-x) Pb (Mg)1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3Proportioning according to the stoichiometric ratio of (A); then, mixing materials by adopting a wet ball milling method; drying the mixed material; finally, the temperature is kept for 4 hours at 825-855 ℃ to obtain (1-x) Pb (Mg)1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3Powder; wherein x is more than or equal to 0.072 and less than or equal to 0.120, y is more than or equal to 0 and less than or equal to 0.06, and x and y are mole numbers. x is preferably 0.08, y is preferably 0.04, and the obtained powder has higher quality.
Step 2
Synthesis of (1-x) Pb (Mg)1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3And (3) after the powder is obtained, finely grinding the powder synthesized in the step (1), adding a binder for granulation, and performing compression molding to obtain a biscuit. Preferably, the binder used is PVA. The addition amount of the binder is 5-8% of the mass of the ceramic powder, such as: 5%, 6% or 8%. When the particle size of the ceramic powder particles is larger, the addition amount of the binder is smaller, and when the particle size of the ceramic powder particles is smaller, the addition amount of the binder is larger.
Preferably, wet ball milling is adopted when fine milling is carried out on the powder, wherein the mass ratio of the ceramic powder to the milling balls to the deionized water is as follows: ceramic powder: grinding balls: deionized water 1: (1.8-2): (0.6-0.8). In order to obtain a powder having a more suitable particle size, it is preferable that the ratio of the ceramic powder: grinding balls: deionized water 1: 1.8: 0.6.
preferably, the fine grinding time is 24-48 hours. For example: 24 hours, 36 hours or 48 hours.
Preferably, the grinding balls are zirconia balls, and it is more preferable to perform a fine grinding operation on the synthesized ceramic powder.
Step 3
And (4) performing plastic removal, and removing organic substances in the biscuit. Preferably, the temperature of the plastic discharge is 500-600 ℃, for example: 500 ℃, 550 ℃ or 600 ℃. The heat preservation time required in the plastic removing process is 2-3 hours, and preferably 2.5 hours.
Step 4
And sintering the biscuit to obtain the ferroelectric ceramic material. Further: and putting the biscuit into a crucible for closed sintering, wherein the sintering temperature is 1180-1250 ℃, for example: 1180 ℃, 1225 ℃ or 1250 ℃. The heating rate is 2 ℃/min to 5 ℃/min, for example: 2 ℃/min, 3 ℃/min or 5 ℃/min. The holding time is l to 3 hours, for example: 1 hour, 2 hours or 3 hours.
The invention also provides a ferroelectric ceramic material prepared by the preparation method provided by the invention, and the chemical components of the ferroelectric ceramic material conform to the chemical general formula (1-x) Pb (Mg)1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3Wherein x is more than or equal to 0.072 and less than or equal to 0.120, y is more than or equal to 0 and less than or equal to 0.06, and x and y are mole numbers;
preferably, the ferroelectric ceramic material is capable of sintering at 1180 ℃ to 1250 ℃, for example: 1180 ℃, 1225 ℃ or 1250 ℃. Under the condition of room temperature, when the frequency is in the frequency range of 100Hz to 1MHz, the relative dielectric constant of the ferroelectric ceramic material is more than 12000, and the dielectric loss is less than 0.05.
Two parallel ceramic plates can form a pair of capacitor electrodes. As shown in fig. 3, electrode tab a, and electrode tab C are connected to an external voltage source through metal plates S1, S2 on their outer sides. Through two mutually parallel capacitor electrode pieces, an alternating current electric field can be applied to different carriers B containing electric dipoles through the capacitor electrodes.
In order to increase the rotation efficiency of electric dipoles with different orientations, two pairs of electrodes which are perpendicular in two directions can be added, and the two pairs of electrodes are sequentially powered by an intermittent power-up mode to induce the maximum number of electric dipoles to participate in rotation under the action of an electric field.
In biomedical research and clinical experiments, according to the body types of animals for experiments and the shapes of different parts of human bodies of patients, ceramic plates can be fired into different shapes, ceramic electrode elements are convenient to fix, and an external alternating current electric field is guaranteed to be more effectively applied to specific experimental parts through capacitive electrodes.
In biomedical research, the electric field applied by the capacitive electrode can be used for researching the influence of different electric field strengths and frequencies on different cell growth in an animal body by adjusting the electric field strength and the frequencies. In clinical experiments, the electric field applied by the capacitive electrode can be used for researching the influence of different electric field strengths and frequencies on different cell growths in a human body by adjusting the electric field strength and the frequencies.
The technical solution provided by the present invention is further illustrated by two specific examples.
Example i:
the ferroelectric ceramic material comprises the following components:
0.89Pb(Mg1/3Nb2/3)O3-0.11Pb0.96Li0.02Na0.02Ti0.96Nb0.04O3
first, two-step solid phase synthesis:
0.89Pb(Mg1/3Nb2/3)O3-0.11Pb0.96Li0.02Na0.02Ti0.96Nb0.04O3
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 0.89Pb (Mg)1/3Nb2/3)O3-0.11Pb0.96Li0.02Na0.02Ti0.96Nb0.04O3
To 0.89Pb (Mg)1/3Nb2/3)O3-0.11Pb0.96Li0.02Na0.02Ti0.96Nb0.04O3MgNb required for calculating chemical formula composition2O6，Pb3O4，TiO2，Nb2O5，Li2CO3,Na2CO3The 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: 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.
The mixed raw materials are kept at the temperature of 830-850 ℃ for 4 hours for synthesis
0.89Pb(Mg1/3Nb2/3)O3-0.11Pb0.96Li0.02Na0.02Ti0.96Nb0.04O3。
Second, for 0.89Pb (Mg)1/3Nb2/3)O3-0.11Pb0.96Li0.02Na0.02Ti0.96Nb0.04O3And finely grinding the powder, wherein the mass ratio of the raw materials to the grinding balls to the deionized water is as follows:
raw materials: grinding balls: deionized water 1: 2: 0.6;
discharging and drying after 24 hours of wet fine grinding;
drying, sieving, preferably 40 mesh sieving.
Adding PVA with the mass of 5-8% of that of the ceramic powder for granulation, and pressing and molding the powder under the pressure of 150 MPa.
Thirdly, the biscuit which is formed by pressing is kept at the temperature of 500-600 ℃ for 1-3 hours, organic substances in the biscuit are removed, and the plastic removal rate is not more than 3 ℃/min.
Fourthly, placing the sample after plastic removal into an alumina crucible for closed sintering, covering the green body with ceramic powder with the same components in order to prevent the volatilization of lead components, covering a grinding opening cover, raising the temperature to 1225 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2 hours, and cooling along with the furnace to obtain the ceramic material sample.
And fifthly, grinding, cleaning and drying the sintered ceramic material, and testing the phase structure of the material by XRD. The test results are shown in FIG. 4. The phase structure of the ferroelectric ceramic material of the present invention is a perovskite structure.
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. The silver firing condition is 650 ℃ and the temperature is kept for 30 minutes, and the ferroelectric ceramic sample covered with the electrode is obtained.
Seventhly, the sintered ceramic of the invention is subjected to dielectric property and ferroelectric property test under a strong field. The dielectric properties were measured by a precision impedance analyzer (Agilent 4294A, product of Agilent Inc. USA), and refer to Table 1. The ferroelectric properties were measured using a TF Analyzer 2000 hysteresis loop measuring instrument from AIxACCT, Germany. Fig. 5 is a measured ceramic hysteresis loop. In the frequency range of 100Hz to 1MHz, the ferroelectric ceramic material of the invention has a relative dielectric constant of more than 12000 and a dielectric loss of less than 0.05 at room temperature. The sample was not broken down by applying an alternating current field of 50 KV/cm.
Eighth, two parallel ceramic sheets may constitute a pair of capacitor electrodes, as shown in fig. 3, and an alternating electric field may be applied to different carriers including electric dipoles through the capacitors.
Table 1: relative permittivity and dielectric loss of the sample of example 1 at room temperature (25 degrees C.)
| Testing frequency | 100Hz | 1kHz | 10kHz | 100kHz | 1MHz |
| Relative dielectric constant | 13047 | 12985 | 12730 | 12441 | 12071 |
| Dielectric loss | 0.0133 | 0.0138 | 0.0169 | 0.0259 | 0.0316 |
Example 2:
the ferroelectric ceramic material comprises the following components:
0.92Pb(Mg1/3Nb2/3)O3-0.08Pb0.96Li0.02Na0.02Ti0.96Nb0.04O3
the preparation method of example l was repeated according to the above formulation of the ferroelectric ceramic composition, and the obtained green body was sintered at 1235 ℃ and heat-preserved for 2 hours.
The ceramic samples were subjected to structural testing, see fig. 6. The structure of the ceramic is perovskite structure.
Then, the ceramic sheet was subjected to dielectric property and ferroelectric property tests with reference to table 2 and fig. 7. In the frequency range of 100Hz to 1MHz, the ferroelectric ceramic material of the invention has a relative dielectric constant of more than 12000 and a dielectric loss of less than 0.05 at room temperature. The sample was not broken down at an operating electric field of 50 kV/cm.
Two parallel ceramic plates may form a pair of capacitor electrodes, as shown in fig. 3, through which an alternating electric field may be applied to different carriers comprising electric dipoles.
Table 2: relative permittivity and dielectric loss of the sample of example 2 at room temperature (25 degrees C.)
| Testing frequency | 100Hz | 1kHz | 10kHz | 100kHz | 1MHz |
| Relative dielectric constant | 14293 | 14207 | 13831 | 13474 | 12858 |
| Dielectric loss | 0.0142 | 0.0144 | 0.0198 | 0.0247 | 0.0379 |
The invention selects proper doping modification and adjusts proper Mg/Nb/Ti ratio, and obtains the ferroelectric ceramic material which can be sintered at 1200-1250 ℃ by utilizing a two-step synthesis method. 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. For other examples, one of ordinary skill in the art will readily appreciate that the order of the process steps may be varied while maintaining the scope of the present invention.
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 (10)
1. A ferroelectric ceramic material, characterized in that the chemical composition of the ferroelectric ceramic material conforms to the general chemical formula (1-x) Pb (Mg)1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3Powder, wherein x is more than or equal to 0.072 and less than or equal to 0.120, y is more than 0 and less than or equal to 0.06, and x and y are mole numbers; it is prepared through the following steps
1) Synthesizing (1-x) Pb (Mg) by solid phase method1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3,
The solid phase synthesis is specifically completed by two steps
(1-x)Pb(Mg1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3(ii) a The two-step solid phase process comprises:
1-1) with MgO, Nb2O5Is used as 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，Li2CO3,Na2CO3As raw materials, keeping the temperature for 4 hours at 825-855 ℃, and synthesizing
(1-x)Pb(Mg1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3
Wherein x is more than or equal to 0.072 and less than or equal to 0.120, y is more than 0 and less than or equal to 0.06, and x and y are mole numbers;
2) for the synthesized in the step 1)
(1-x)Pb(Mg1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3Finely grinding the powder, adding a binder for granulation, and performing compression molding to obtain a biscuit;
3) performing plastic removal to remove organic substances in the biscuit;
4) sintering the biscuit to obtain a ferroelectric ceramic material;
the step 4) is specifically as follows:
and putting the biscuit into a crucible for closed sintering, wherein the sintering temperature is 1180-1250 ℃, the heating rate is 2-5 ℃ per minute, and the heat preservation time is 2-3 hours.
2. A ferroelectric ceramic material according to claim 1, characterized in that said step 1-1) is in particular:
with MgO, Nb2O5As raw material, according to MgNb2O6The materials are mixed by a wet ball milling method after being proportioned according to the stoichiometric ratio;
drying the mixed materials;
the MgNb is synthesized by heat preservation for 2 hours at the temperature of 1000 to 1200 DEG C2O6。
3. A ferroelectric ceramic material according to claim 1, characterized in that said steps 1-2) are in particular:
with MgNb2O6，Pb3O4，TiO2，Nb2O5，Li2CO3,Na2CO3As raw material, according to (1-x) Pb (Mg)1/3Nb2/3)O3-xPb1- yLi0.5yNa0.5yTi1-yNbyO3The materials are mixed by a wet ball milling method after being proportioned according to the stoichiometric ratio;
drying the mixed materials;
keeping the temperature for 4 hours at 825-855 ℃ to obtain
(1-x)Pb(Mg1/3Nb2/3)O3-xPb1-yLi0.5yNa0.5yTi1-yNbyO3Powder body
Wherein x is more than or equal to 0.072 and less than or equal to 0.120, y is more than 0 and less than or equal to 0.06, and x and y are mole numbers.
4. A ferroelectric ceramic material as in any one of claims 1-2, wherein in step 2), the mass ratio of the ceramic powder, the grinding balls, and the deionized water is as follows:
ceramic powder: grinding balls: deionized water 1: (1.8-2): (0.6-0.8).
5. The ferroelectric ceramic material according to claim 1, wherein the fine grinding time is 24 to 48 hours.
6. The ferroelectric ceramic material of claim 4, wherein the grinding balls are zirconia balls.
7. A ferroelectric ceramic material according to claim 1, characterized in that in said step 2) the binder used is PVA; the addition amount of the binder is 5-8% of the mass of the ceramic powder.
8. The ferroelectric ceramic material as set forth in claim 1, wherein in said step 3), the temperature of said plastic discharge is 500 ℃ to 600 ℃ and the holding time is 2 to 3 hours.
9. Use of the ferroelectric ceramic material as claimed in claim 1 as a capacitor electrode.
10. Use of the ferroelectric ceramic material of claim 1 for the manufacture of a medical device.
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