CN108911740B - Ferrotitanium strontium bismuth cobaltate ceramic material with multiferroic performance and five-layer layered structure and preparation method thereof - Google Patents
Ferrotitanium strontium bismuth cobaltate ceramic material with multiferroic performance and five-layer layered structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a ferrotitanium strontium bismuth cobaltate ceramic material with a five-layer layered structure and multiferroic performance and a preparation method thereof, wherein the method comprises the steps of mixing a titanium source, a strontium source, a bismuth source, an iron source and a cobalt source in a nitric acid solution according to a molar ratio by using a sol-gel spontaneous combustion method, and adding a proper amount of citric acid serving as a complexing agent to obtain a clear sol; stirring the sol in an oil bath and drying at constant temperature to prepare dry gel; heating the xerogel and preserving heat to prepare powder, and pre-synthesizing, tabletting and sintering the powder to obtain Sr which is a chemical formula x Bi x6‑Fe x1‑/2Co x1‑/2Ti x3+O18The prepared product has good ferroelectricity and ferromagnetism at room temperature. The process is reasonable and efficient, the sample preparation temperature is far lower than that of the existing solid phase sintering process, the energy consumption is reduced, and the industrial production is very convenient.
Description
Technical Field
The invention belongs to the field of multiferroic oxide ceramic materials, and particularly relates to a ferrotitanium strontium bismuth cobaltate ceramic material with a multiferroic five-layer layered structure and a preparation method thereof.
Background
A single-phase multiferroic material refers to a single-phase compound containing two or more basic ferroelectrics, including ferroelectrics (antiferroelectricity), ferromagnetics (antiferromagnetism), and ferroelasticity, and there is a coupling effect between them, such as magnetoelectric effect, magnetodielectric effect, etc. The effects can provide an additional degree of freedom for the design and application of equipment, can be widely applied to converters, sensors, storage equipment and the like, and show extremely attractive application prospects in the aspects of miniaturization and multi-functionalization of devices. However, most of the currently discovered and studied multiferroic materials show the coexistence of ferroelectricity and magnetism only at low temperature, and such materials generally have the problems of large leakage current, insignificant magnetoelectric effect, and the like.
In recent years, Bi has been satisfied n+1Fe n-3Ti3O n3+3The bismuth-based layered perovskite oxide material of the Aurivillius (Aurivillius) phase of the general formula (n is the number of layers of the perovskite-like) attracts people's attention, the special layered structure and the larger tolerance of the bismuth-based layered perovskite oxide material provide space for ion doping, and the bismuth-based layered perovskite oxide material is a single-phase multiferroic material with potential application value. Structurally, the material consists of a bismuth-oxygen layer (Bi)2O2)2+And perovskite-like layer (Bi) n-1Fe n-3Ti3O n3+1)2-Alternately arranged and grown along the c-axis. The bismuth-oxygen layer has the functions of an insulating layer and a space charge reservoir, and can effectively reduce the leakage current of the multiferroic material. When n is five, Bi with a typical five-layer structure is obtained6Fe2Ti3O18The ferroelectric Curie temperature of the material is 973K, and the antiferromagnetic Neille temperature is 160K. In the research, the problems of insufficient polarization strength, larger electric leakage and the like always exist in the ferroelectric property of the sample; the magnetic property of the material usually shows a paramagnetic state at room temperature, which greatly limits the practical application of the material, and therefore, the improvement of the ferroelectricity and the ferromagnetism of the material becomes a research focus.
Disclosure of Invention
The invention aims to provide a ferrotitanium strontium bismuth cobaltate ceramic material with a five-layer layered structure and multiferroic performance and a preparation method thereof, so as to optimize the ferroelectric performance and ferromagnetic performance of Aurivillius-type layered ceramics.
The technical solution for realizing the purpose of the invention is as follows:
the invention provides a construction of a ferrotitanium strontium bismuth cobaltate ceramic material with multiferroic performance and a five-layer layered structure, and the chemical formula of the ferrotitanium strontium bismuth cobaltate ceramic material is Sr x Bi x6-Fe x1-/2Co x1-/2Ti x3+O18(SBFCT), whereinxThe range of (A) is 0 to lessx Less than or equal to 1, and has a structure of 2 bismuth-oxygen layers ((Bi)2O2)2+) Are clamped with 3+xTitanium oxide (Ti-O) octahedron, 1-x2 ferrite (Fe-O) octahedron, 1-x2 cobalt-oxygen (Co-O) octahedra.
The invention also provides a method for preparing the ferrotitanium strontium bismuth cobaltate multiferroic ceramic material with the multiferroic performance and a five-layer layered structure, which comprises the following steps:
(1) mixing a titanium source, a strontium source, a bismuth source, an iron source, a cobalt source and citric acid in a 4M nitric acid solution, and simultaneously dropwise adding ammonia water (the mass fraction is 28%) to adjust the pH value to be neutral to obtain transparent sol; the molar ratio of titanium, strontium, bismuth, iron and cobalt in the titanium source, strontium source, bismuth source, iron source and cobalt source is (3 +)x):x:(6-x):(1-x/2):(1-x/2)，0 ≤ x ≤ 1；
(2) Stirring the sol in the step (1) in an oil bath at the temperature of 80-100 ℃ until gel is formed;
(3) drying the gel in the step (2) at a constant temperature of 80-120 ℃ until xerogel is obtained;
(4) heating the xerogel in the step (3) at the temperature of 300-500 ℃ and preserving heat to enable the xerogel to self-combust to generate powder a;
(5) pre-sintering the powder a in the step (4) at the temperature of 700-800 ℃ for 1-6 hours to obtain powder b;
(6) and (4) tabletting and molding the powder b in the step (5), and sintering at the temperature of 800-1100 ℃ for 4-6 hours to obtain the target product.
Further, the titanium source in the step (1) is tetrabutyl titanate; the strontium source is one or more of strontium nitrate, strontium oxide and strontium acetate, and is preferably strontium nitrate; the bismuth source is one or more of bismuth nitrate pentahydrate, bismuth oxide and bismuth acetate, and bismuth nitrate pentahydrate is preferred; the iron source is one or more of ferric nitrate nonahydrate, ferric oxide and ferric acetate, and preferably ferric nitrate nonahydrate; the cobalt source is one or more of bismuth acetate tetrahydrate, bismuth oxide and cobalt nitrate hexahydrate, and cobalt nitrate hexahydrate is preferred.
Further, the concentration of the metal ions in the sol in the step (1) is 0.01-1mol/L, preferably 0.05 mol/L.
Further, the molar ratio of citric acid to metal ions in the sol in the step (1) is (1-2): 1, preferably 1.5: 1.
further, in the present invention, in order to compensate for the loss of bismuth during combustion, the bismuth source needs to be in excess (by mass) of 3 to 10%, preferably 5%.
Further, the method of the present invention for forming the tablet in step (6) is not particularly limited, and the tablet is preferably formed into a cylinder or other tablet structure under a pressure of 10Mpa or less.
The invention has simple process, adopts the sol-gel self-combustion method to prepare Sr x Bi x6-Fe x1-/2Co x1-/2Ti x3+O18The five-layer layered multiferroic oxide ceramic material has good ferroelectricity and ferromagnetism at room temperature. Wherein, the + 2-valent strontium ions are used for partially replacing the + 3-valent bismuth ions at the A site, and the equivalent + 4-valent titanium ions are used for partially replacing the + 3-valent iron ion cobalt ions at the B site, so that the valence compensation is carried out, the leakage current can be effectively reduced, and the ferroelectric property of the sample is improved; on the other hand, because the iron-cobalt atomic structures are similar, after partial cobalt ions replace the positions of partial iron ions, Fe-O octahedrons and Co-O octahedrons are arranged relatively orderly, and Fe-O-Co coupling can be generated locally, so that the ferromagnetic performance of a sample is improved. The experimental result shows that at normal temperature, the ferrotitanium bismuth strontium cobaltate multiferroic ceramic material provided by the invention has good ferroelectricity and ferromagnetism, and when a sample SBFCT-0.25 is used for measuring 250kV/cm, the remanent polarization intensity is (2)P r) About 17.9μC/cm2(ii) a Its remanent magnetization (2)M r) About 0.38 emu/g.
Mixing a titanium source, a strontium source, a bismuth source, an iron source and a cobalt source in a nitric acid solution according to a molar ratio by using a sol-gel self-combustion method, and adding a proper amount of citric acid serving as a complexing agent to obtain a clear sol; stirring the sol in an oil bath and drying at constant temperature to prepare dry gel; heating the xerogel and preserving heat to prepare powder, and pre-synthesizing, tabletting and sintering the powder to obtain Sr which is a chemical formula x Bi x6-Fe x1-/ 2Co x1-/2Ti x3+O18The prepared product has good ferroelectricity and ferromagnetism at room temperature. The process is reasonable and efficient, and the sample isThe preparation temperature is far lower than that of the existing solid phase sintering process, the energy consumption is reduced, and the industrial production is very convenient.
Drawings
FIG. 1 is an X-ray diffraction pattern of SBFCT of a sample according to an embodiment of the present invention;
FIG. 2 shows sample SBFCT-0.25(0.25 isxValue of (d) scanning electron microscope photographs;
FIG. 3 shows sample SBFCT-0.25(0.25 isxValue of) is calculated;
FIG. 4 is a graph showing ferromagnetic property measurements of a sample SBFCT according to an example of the present invention.
Detailed Description
For the convenience of understanding the present invention, the following examples are listed. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
(1) According to the molar ratio of titanium to bismuth to iron to cobalt of 3:6:1:1, 5.6437g of tetra-n-butyl titanate, 15.4341g of bismuth nitrate pentahydrate, 2.0508g of ferric nitrate nonahydrate and 1.2517g of cobalt acetate tetrahydrate are selected, accurately weighed and dissolved in a 4M nitric acid solution (19 g of nitric acid and 36g of deionized water), and according to the molar ratio of citric acid to metal ions of 1.5: 17.4237g of citric acid is added according to the molar ratio of 1, and ammonia water is added dropwise to adjust the pH value to be neutral, so that transparent sol is obtained.
(2) Stirring the sol in the step (1) in an oil bath at 80 ℃ for 6 hours to form gel;
(3) drying the gel obtained in the step (2) at a constant temperature of 100 ℃ until a dry gel is obtained;
(4) heating the dried gel obtained in the step (3) in a muffle furnace to 400 ℃, and keeping the temperature for 30min to enable the dried gel to self-combust to generate powder a;
(5) presintering the powder a in the step (4) at 750 ℃ for 6 hours to obtain powder b;
(6) pressing the powder b in the step (5) into a cylinder sample with phi 12mm multiplied by 2mm under the condition of 6Mpa pressure, and sintering the cylinder sample in a muffle furnace at 820 ℃ for 4 hours to obtain the powder bTarget product Bi6FeCoTi3O18。
The product sample was subjected to structural analysis using an X-ray diffractometer of XRD-7000 type, SHK company, Japan, and as a result, referring to FIG. 1, the sample was a ceramic sample having a single layered perovskite structure, and no significant second phase was found.
The morphology of the sample is observed by a VEGA3 scanning electron microscope of the Czech TESCAN company, the grain shape of the sample is basically consistent, the density of the sample is better, and no obvious cavity appears.
The ferroelectric property of the sample at normal temperature was measured by a Precision LC type ferroelectric property measuring instrument of radial Technology corporation, USA, and the sample showed ferroelectric property at normal temperature and residual polarization intensity (2) at measuring electric field of 160kV/cmP r) Is 1.9μC/cm2。
The magnetic properties of the sample at room temperature were measured using a vibrating sample magnetometer model EV7 from ADE, USA, and the results are shown in FIG. 4. at room temperature, the sample shows ferromagnetism and residual magnetization (2)M r) It was 0.29 emu/g.
Example 2
(1) According to the molar ratio of titanium to strontium to bismuth to iron to cobalt of 3.25:0.25:5.75:0.875:0.875, 5.6437g of tetra-n-butyl titanate, 14.7910g of bismuth nitrate pentahydrate, 0.2659g of strontium nitrate, 1.7944g of iron nitrate nonahydrate and 1.0952g of cobalt acetate tetrahydrate are selected, accurately weighed and dissolved in 4M nitric acid solution (19 g of nitric acid and 36g of deionized water), and the weight ratio of citric acid to metal ions is 1.5: 17.4237g of citric acid is added according to the molar ratio of 1, and ammonia water is added dropwise to adjust the pH value to be neutral, so that transparent sol is obtained.
(2) Stirring the sol in the step (1) in an oil bath at 90 ℃ for 6 hours to form gel;
(3) drying the gel obtained in the step (2) at a constant temperature of 110 ℃ until a dry gel is obtained;
(4) heating the dried gel obtained in the step (3) in a muffle furnace to 400 ℃, and keeping the temperature for 30min to enable the dried gel to self-combust to generate powder a;
(5) presintering the powder a in the step (4) at 750 ℃ for 6 hours to obtain powder b;
(6) pressing the powder b in the step (5) into a cylinder sample with phi 12mm multiplied by 2mm under the condition of 6Mpa pressure, and sintering the cylinder sample in a muffle furnace at 830 ℃ for 4 hours to obtain a target product Sr0.25Bi5.75Fe0.875Co0.875Ti3.2 5O18。
The product sample was subjected to structural analysis using an X-ray diffractometer of XRD-7000 type, SHK company, Japan, and as a result, referring to FIG. 1, the sample was a ceramic sample having a single layered perovskite structure, and no significant second phase was found.
The morphology of the sample is observed by a VEGA3 scanning electron microscope of Czech TESCAN, and the result is shown in figure 2, the crystal grain shape of the sample is basically consistent, the density of the sample is better, and no obvious cavity appears.
The ferroelectric properties of the samples at room temperature were measured by a Precision LC type ferroelectric measuring instrument of radial Technology, USA, and the results are shown in FIG. 3. at room temperature, the samples showed ferroelectricity, and the remanent polarization was measured at an electric field of 250kV/cm (2)P r) Is 17.9μC/cm2。
The magnetic properties of the sample at room temperature were measured using a vibrating sample magnetometer model EV7 from ADE, USA, and the results are shown in FIG. 4. at room temperature, the sample shows ferromagnetism and residual magnetization (2)M r) It was 0.38 emu/g.
Example 3
(1) According to the molar ratio of titanium to strontium to bismuth to iron to cobalt of 3.5:0.5:5.5:0.75:0.75, 6.0779g of tetra-n-butyl titanate, 14.1479g of bismuth nitrate pentahydrate, 0.5317g of strontium nitrate, 1.5381g of iron nitrate nonahydrate and 0.9387g of cobalt acetate tetrahydrate are selected, accurately weighed and dissolved in 4M nitric acid solution (19 g of nitric acid and 36g of deionized water), and the weight ratio of citric acid to metal ions is 1.5: 17.4237g of citric acid is added according to the molar ratio of 1, and ammonia water is added dropwise to adjust the pH value to be neutral, so that transparent sol is obtained.
(2) Stirring the sol in the step (1) in an oil bath at 100 ℃ for 4 hours to form gel;
(3) drying the gel obtained in the step (2) at a constant temperature of 120 ℃ until a dry gel is obtained;
(4) heating the dried gel obtained in the step (3) in a muffle furnace to 450 ℃, and keeping the temperature for 30min to enable the dried gel to self-combust to generate powder a;
(5) presintering the powder a in the step (4) at 800 ℃ for 6 hours to obtain powder b;
(6) pressing the powder b in the step (5) into a cylinder sample with phi 12mm multiplied by 2mm under the condition of 8Mpa pressure, and sintering the cylinder sample in a muffle furnace at 960 ℃ for 4 hours to obtain a target product Sr0.5Bi5.5Fe0.75Co0.75Ti3.5O18。
The product sample was subjected to structural analysis using an X-ray diffractometer of XRD-7000 type, SHK company, Japan, and as a result, referring to FIG. 1, the sample was a ceramic sample having a single layered perovskite structure, and no significant second phase was found.
The morphology of the sample is observed by a VEGA3 scanning electron microscope of the Czech TESCAN company, the grain shape of the sample is basically consistent, the density of the sample is better, and no obvious cavity appears.
The ferroelectric property of the sample at normal temperature was measured by a Precision LC type ferroelectric property measuring instrument of radial Technology corporation, USA, and the sample showed ferroelectric property at normal temperature and residual polarization intensity (2) at measuring electric field of 160kV/cmP r) Is 9.8μC/cm2。
The magnetic properties of the sample at room temperature were measured using a vibrating sample magnetometer model EV7 from ADE, USA, and the results are shown in FIG. 4. at room temperature, the sample shows ferromagnetism and residual magnetization (2)M r) It was 0.74 emu/g.
Example 4
(1) According to the molar ratio of titanium to strontium to bismuth to iron to cobalt of 3.75:0.75:5.25:0.625:0.625, 6.5120g of tetra-n-butyl titanate, 13.5048g of bismuth nitrate pentahydrate, 0.7976g of strontium nitrate, 1.2817g of iron nitrate nonahydrate and 0.7823g of cobalt acetate tetrahydrate are selected, accurately weighed and dissolved in 4M nitric acid solution (19 g of nitric acid and 36g of deionized water), and the weight ratio of citric acid to metal ions is 1.5: 17.4237g of citric acid is added according to the molar ratio of 1, and ammonia water is added dropwise to adjust the pH value to be neutral, so that transparent sol is obtained.
(2) Stirring the sol in the step (1) in an oil bath at 100 ℃ for 4 hours to form gel;
(3) drying the gel obtained in the step (2) at a constant temperature of 120 ℃ until a dry gel is obtained;
(4) heating the dried gel obtained in the step (3) in a muffle furnace to 500 ℃, and preserving heat for 30min to enable the dried gel to self-combust to generate powder a;
(5) presintering the powder a in the step (4) at 800 ℃ for 6 hours to obtain powder b;
(6) pressing the powder b in the step (5) into a cylinder sample with phi 12mm multiplied by 2mm under the condition of 10Mpa pressure, and sintering the cylinder sample in a muffle furnace at 1040 ℃ for 4 hours to obtain a target product Sr0.75Bi5.25Fe0.625Co0.625Ti3.75O18。
The product sample was subjected to structural analysis using an X-ray diffractometer of XRD-7000 type, SHK company, Japan, and as a result, referring to FIG. 1, the sample was a ceramic sample having a single layered perovskite structure, and no significant second phase was found.
The morphology of the sample is observed by a VEGA3 scanning electron microscope of the Czech TESCAN company, the grain shape of the sample is basically consistent, the density of the sample is better, and no obvious cavity appears.
The ferroelectric property of the sample at normal temperature was measured by a Precision LC type ferroelectric property measuring instrument of radial Technology corporation, USA, and the sample showed ferroelectric property at normal temperature and residual polarization intensity (2) at measuring electric field of 160kV/cmP r) Is 13.1μC/cm2。
The magnetic properties of the sample at room temperature were measured using a vibrating sample magnetometer model EV7 from ADE, USA, and the results are shown in FIG. 4. at room temperature, the sample shows ferromagnetism and residual magnetization (2)M r) It was 0.21 emu/g.
Example 5
(1) According to the molar ratio of titanium to strontium to bismuth to iron to cobalt of 4:1:5:1:1, 6.9461g of tetra-n-butyl titanate, 12.8617g of bismuth nitrate pentahydrate, 1.0635g of strontium nitrate, 1.0254g of ferric nitrate nonahydrate and 0.6258 g of cobalt acetate tetrahydrate are selected, accurately weighed and dissolved in 4M nitric acid solution (19 g of nitric acid and 36g of deionized water), and the weight ratio of citric acid to metal ions is 1.5: 17.4237g of citric acid is added according to the molar ratio of 1, and ammonia water is added dropwise to adjust the pH value to be neutral, so that transparent sol is obtained.
(2) Stirring the sol in the step (1) in an oil bath at 100 ℃ for 4 hours to form gel;
(3) drying the gel obtained in the step (2) at a constant temperature of 120 ℃ until a dry gel is obtained;
(4) heating the dried gel obtained in the step (3) in a muffle furnace to 500 ℃, and preserving heat for 30min to enable the dried gel to self-combust to generate powder a;
(5) presintering the powder a in the step (4) at 800 ℃ for 6 hours to obtain powder b;
(6) pressing the powder b in the step (5) into a cylinder sample with phi 12mm multiplied by 2mm under the condition of 10Mpa pressure, and sintering the cylinder sample in a muffle furnace at 1060 ℃ for 4 hours to obtain a target product SrBi5Fe0.5Co0.5Ti4O18。
The product sample was subjected to structural analysis using an X-ray diffractometer of XRD-7000 type, SHK company, Japan, and as a result, referring to FIG. 1, the sample was a ceramic sample having a single layered perovskite structure, and no significant second phase was found.
The morphology of the sample is observed by a VEGA3 scanning electron microscope of the Czech TESCAN company, the grain shape of the sample is basically consistent, the density of the sample is better, and no obvious cavity appears.
The ferroelectric property of the sample at normal temperature was measured by a Precision LC type ferroelectric property measuring instrument of radial Technology corporation, USA, and the sample showed ferroelectric property at normal temperature and residual polarization intensity (2) when the measured electric field was 120kV/cmP r) Is 17.4μC/cm2。
The magnetic properties of the sample at room temperature were measured using a vibrating sample magnetometer model EV7 from ADE, USA, and the results are shown in FIG. 4. at room temperature, the sample shows ferromagnetism and residual magnetization (2)M r) It was 0.09 emu/g.
Claims (6)
1. A ferrotitanium strontium bismuth cobaltate ceramic material with a five-layer layered structure and multiferroic performance is characterized in that the chemical formula of the material is SrxBi6-xFe1-x/2Co1-x/2Ti3+xO18Wherein x is in the range of 0.25-0.75.
2. The preparation method of the five-layer layered ferrotitanium strontium bismuth cobaltate ceramic material with multiferroic properties as claimed in claim 1, which is characterized by comprising the following steps:
(1) mixing a titanium source, a strontium source, a bismuth source, an iron source, a cobalt source and citric acid in a nitric acid solution, and simultaneously dropwise adding ammonia water to adjust the pH value to be neutral to obtain transparent sol; the molar ratio of titanium, strontium, bismuth, iron and cobalt in the titanium source, the strontium source, the bismuth source, the iron source and the cobalt source is (3+ x) x (6-x) to (1-x/2), wherein x is within the range of 0.25-0.75; the titanium source, the strontium source, the bismuth source, the iron source and the cobalt source are respectively tetrabutyl titanate, strontium nitrate, bismuth nitrate pentahydrate, ferric nitrate nonahydrate and cobalt acetate tetrahydrate;
(2) stirring the sol in the step (1) in an oil bath at the temperature of 80-100 ℃ until gel is formed;
(3) drying the gel in the step (2) at a constant temperature of 80-120 ℃ until xerogel is obtained;
(4) heating the xerogel in the step (3) at the temperature of 300-500 ℃ and preserving heat to enable the xerogel to self-combust to generate powder a;
(5) pre-sintering the powder a in the step (4) at the temperature of 700-800 ℃ for 1-6 hours to obtain powder b;
(6) and (4) tabletting and molding the powder b in the step (5), and sintering at the temperature of 800-1100 ℃ for 4-6 hours to obtain the target product.
3. The preparation method of the five-layer layered ferrotitanium strontium bismuth cobaltate ceramic material with multiferroic properties as claimed in claim 2, wherein the concentration of metal ions in the sol in step (1) is 0.01-1 mol/L.
4. The preparation method of the five-layer layered ferrotitanium bismuth strontium cobaltate ceramic material with multiferroic properties as claimed in claim 2, wherein the molar ratio of citric acid to metal ions in the sol of step (1) is (1-2): 1.
5. the process for preparing a five-layer layered ferrotitanium strontium bismuth cobaltate ceramic material with multiferroic properties as claimed in claim 2, wherein the bismuth source is required to be in excess of 3-10% in order to compensate for the loss of bismuth during combustion.
6. The preparation method of the five-layer layered ferrotitanium strontium bismuth cobaltate ceramic material with multiferroic properties as claimed in claim 2, wherein the nitric acid concentration in step (1) is 4 mol/L.
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| CN102875145A (en) * | 2012-09-29 | 2013-01-16 | 中国科学技术大学 | Layered perovskite structural ceramic and preparation method thereof |
| CN102942361A (en) * | 2012-10-10 | 2013-02-27 | 中国科学技术大学 | Ferrotitanium bismuth cobaltate ceramic material having layered structure and preparation method thereof |
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| CN102875145A (en) * | 2012-09-29 | 2013-01-16 | 中国科学技术大学 | Layered perovskite structural ceramic and preparation method thereof |
| CN102942361A (en) * | 2012-10-10 | 2013-02-27 | 中国科学技术大学 | Ferrotitanium bismuth cobaltate ceramic material having layered structure and preparation method thereof |
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