CN111205091B - Zirconium-doped gadolinium manganate multiferroic ceramic and preparation method thereof - Google Patents
Zirconium-doped gadolinium manganate multiferroic ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses zirconium-doped gadolinium manganate multiferroic ceramic and a preparation method thereof, belonging to the technical field of electronic ceramics. The chemical formula of the ceramic material is GdMn x1‑Zr x O3Wherein the doping amountxThe range of (A) is as follows: 0 < (R) >x≤0.10。GdMn x1‑Zr x O3The powder is prepared by a sol-gel method. The ceramic material has single-phase structure, giant dielectric property at room temperature and low-temperature magnetism, and Zr is changed4+The doping amount of the material can adjust the dielectric property and magnetism of the material. The invention has the advantages of simple preparation process, low sintering phase forming temperature, short sintering time, low cost, environmental protection, harmlessness and good application prospect in the fields of high dielectric capacitors, information storage, sensitive magnetoelectric sensors, energy converters, filters and the like.
Description
Technical Field
The invention belongs to the technical field of multiferroic ceramic materials, and particularly relates to a non-magnetic high-valence transition metal ion Zr4+Gadolinium manganate-doped multiferroic ceramic and a preparation method thereof.
Background
The multiferroic material has two or more than two ferroic sequences such as ferroelectricity, (anti-) ferromagnetism, ferroelasticity and the like, and generates new physical effects such as magnetoelectric coupling, magnetodielectric effect, magnetoresistive effect and the like due to mutual coupling among multiple sequence parameters, thereby having huge application prospects in the high-tech fields of novel magnetoelectric devices, spintronics, transducers, sensors, memories and the like, and becoming the international research of thermoelectricity.
Gadolinium manganate (GdMnO) of strongly-associated system with orthogonal perovskite structure3) Is a core member and a representative of single-phase multiferroic materials, and has unique and complex physical characteristics.GdMnO3The ground state belongs to an A-type antiferromagnetic ordered phase, and the ground state is at 40K, 20K and 7K due to Gd3+、Mn3+Change of spin structure, GdMnO3Respectively consists of a paramagnetic structure → an antiferromagnetic structure → a ferromagnetic structure → a ferrimagnetic structure, and each magnetic phase change is accompanied with lattice evolution, so that the magnetic material has good spin-lattice coupling effect; more remarkably, recent studies have found that GdMnO is3The ceramics show ferroelectricity at room temperature without external magnetic field. GdMnO with simple structure3The material has remarkable physical connotation and obvious magnetic control electric effect, so that the material becomes a candidate material with great application potential in a multifunctional magnetoelectronic device.
Research shows that the microstructure of the material can be regulated and controlled by ion substitution so as to influence the physical properties of the material. The invention adopts a sol-gel method to prepare GdMnO3Multiferroic ceramics, by Zr4+Mn site substitution is carried out on ions to prepare GdMn x1-Zr x O3Has obvious low-temperature magnetism and simultaneously shows room-temperature giant dielectricity. At present, the sol-gel method for preparing Zr is not seen4+Doped GdMnO3Multiferroic ceramic materials have been reported.
The invention content is as follows:
the invention aims to solve the technical problem of providing zirconium-doped gadolinium manganate multiferroic ceramic and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
zirconium-doped gadolinium manganate multiferroic ceramic with chemical formula of GdMn x1-Zr x O3Wherein, the doping amount of zirconiumxThe range of (A) is as follows: 0 < (R) >x≤0.10。
The preparation method of the zirconium-doped gadolinium manganate multiferroic ceramic comprises the following steps:
(1) gadolinium nitrate hexahydrate (Gd (NO)3)3·6H2O), manganese acetate tetrahydrate (C)4H6MnO4·4H2O), zirconium nitrate pentahydrate (Zr (NO)3)4·5H2O), citric acid monohydrate (C)6H8O7·H2O) according to GdMn x1-Zr x O3In a stoichiometric ratio of (a), wherein the cation: the citric acid is in a molar ratio of 1: 1-1: 2;
(2) pouring deionized water into a beaker, sequentially adding citric acid monohydrate, gadolinium nitrate hexahydrate, manganese acetate tetrahydrate and zirconium nitrate pentahydrate at room temperature, and stirring until all the materials are dissolved;
(3) under the condition of continuous stirring, adding ammonia water to adjust the pH value to 7-9;
(4) adding ethylene glycol, and continuously stirring to uniformly mix the solution;
(5) placing the uniformly mixed solution in a water bath kettle to remove water to obtain a jelly;
(6) drying in an oven;
(7) fully grinding the dried sample into powder, filling the powder into a crucible, and performing heat treatment to obtain precursor powder;
(8) grinding the obtained precursor powder again, tabletting and sintering in air or oxygen to obtain GdMn1- x Zr x O3Ceramic samples.
Further, the ethylene glycol is added in the step (4), and the solution is uniformly mixed by continuously stirring for 6 hours at 80 ℃ with a magnetic stirrer under nitrogen or argon atmosphere.
Further, the molar ratio of the ethylene glycol added in the step (4) to the metal cation in the step (1) is 2:1-2.5:1, preferably 2.2: 1.
Further, the set temperature of the water bath kettle in the step (5) is 85-100 ℃.
Further, the drying temperature in the step (6) is 155-190 ℃, and the drying time is 8-11 hours.
Further, the heat treatment in the step (7) is divided into a first heat treatment and a second heat treatment, wherein the first heat treatment is carried out for 10-15 hours at 200-300 ℃ in a nitrogen or argon atmosphere to remove nitrate; the second heat treatment is heat treatment at 460-650 ℃ for 5-7 hours in nitrogen or argon atmosphere to remove organic matters.
Further, the sintering temperature in the step (8) is 880-920 ℃, and preferably 900 ℃; the sintering time is 1.5 to 3 hours, preferably 2 hours.
Further, the time for re-grinding in the step (8) is 10-30 minutes.
The invention has the following beneficial effects:
GdMn prepared by the invention x1-Zr x O3The multiferroic ceramic material has a single-phase structure, low-temperature magnetism and room-temperature giant dielectricity, and Mn ions in the sol and the gel are kept Mn by carrying out heat treatment on the sol and the gel in a nitrogen or argon atmosphere3+State of being conducive to improvement of dielectric and magnetic properties of the material, and by changing Zr4+The amount of doping of (A) influences Mn3+-Mn3+、Gd3 +-Gd3+、Gd3+-Mn3+Interaction between them, introduction of cation vacancies, influence of Mn3+Spin arrangement, causing lattice structure distortion, thereby regulating and controlling the magnetism and the dielectricity of the material, and being a multifunctional ceramic material with wide application prospect. Compared with the traditional solid phase reaction method, the preparation method of the invention has the advantages of low sintering phase forming temperature, short sintering time, simple preparation process, low cost and environmental protection, and is a good low-temperature ceramic sintering process.
Drawings
FIG. 1 GdMn at different sintering temperatures0.95Zr0.05O3XRD pattern of ceramic sample.
FIG. 2 different Zr4+Substitution amount GdMnO3XRD pattern of ceramic sample.
FIG. 3 different Zr4+Substitution amount GdMnO3Hysteresis loop of ceramic sample.
FIG. 4 different Zr4+Substitution amount GdMnO3Dielectric frequency curve of ceramic sample.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
Preparing undoped Gd at different temperatures by using a citric acid-nitrate sol-gel method0.95Mn0.05O3The multiferroic ceramic comprises the following steps:
(1) gadolinium nitrate hexahydrate (Gd (NO)3)3·6H2O), manganese acetate tetrahydrate (C)4H6MnO4·4H2O), zirconium nitrate pentahydrate (Zr (NO)3)4·5H2O), citric acid monohydrate (C)6H8O7·H2O) according to GdMn0.95Zr0.05O3In a stoichiometric ratio of (a), wherein the cation: the citric acid molar ratio is 1: 1.5;
(2) measuring deionized water by using a measuring cylinder, pouring the deionized water into a beaker, sequentially adding citric acid, gadolinium nitrate hexahydrate, manganese acetate tetrahydrate and zirconium nitrate pentahydrate at room temperature, and immediately stirring by using a glass rod until all the reagents are dissolved;
(3) under the condition of continuous stirring, adding ammonia water to adjust the pH value to 8;
(4) adding ethylene glycol, and continuously stirring for 6 hours at 80 ℃ in an argon atmosphere by using a magnetic stirrer to uniformly mix the solution, wherein the molar ratio of the ethylene glycol to the metal cations is 2.2: 1;
(5) removing water from the uniformly mixed solution in a water bath kettle at 97 ℃ until the solution is in a jelly shape;
(6) drying in an oven at 180 ℃ for 10 hours;
(7) fully grinding the dried sample into powder, loading the powder into a crucible, carrying out heat treatment for 10 hours at 180 ℃ in argon gas to remove nitrate, then carrying out heat treatment for 6 hours at 500 ℃ in argon gas to remove organic matters, and obtaining precursor powder;
(8) grinding the obtained precursor powder for 20 min again, tabletting, sintering in air, and performing sintering at 850 deg.C, 900 deg.C and 950 deg.C respectivelySintering for 2 hours to obtain GdMn at different sintering temperatures0.95Zr0.05O3Ceramic samples.
GdMn obtained at different sintering temperatures was prepared using example 10.95Zr0.05O3XRD of multiferroic ceramic sample is shown in FIG. 1, and main diffraction peak and orthogonal perovskite structure GdMnO of all samples are observed from FIG. 13Coincidentally, the 900 ℃ sample exhibited a single phase structure, but the 850 ℃ sample had insufficiently reacted Gd2O3And Mn2O3Hetero-phase, sample preparation at 950 ℃ Presence of GdMnO3Decomposed GdMn2O5And (3) impurity phase. Thus, GdMn x1-Zr x O3The sintering temperature range of the selected ceramic is 880-920 ℃, and 900 ℃ is preferred.
Example 2
Preparation of undoped GdMnO by citric acid-nitrate sol-gel method3The multiferroic ceramic comprises the following steps:
(1) gadolinium nitrate hexahydrate (Gd (NO)3)3·6H2O), manganese acetate tetrahydrate (C)4H6MnO4·4H2O), citric acid monohydrate (C)6H8O7·H2O) according to GdMnO respectively3In a stoichiometric ratio of (a), wherein the cation: the citric acid molar ratio is 1: 1.5;
(2) measuring deionized water by using a measuring cylinder, pouring the deionized water into a beaker, sequentially adding citric acid, gadolinium nitrate hexahydrate, manganese acetate tetrahydrate and zirconium nitrate pentahydrate at room temperature, and immediately stirring by using a glass rod until all the reagents are dissolved;
(3) under the condition of continuous stirring, adding ammonia water to adjust the pH value to 8;
(4) adding ethylene glycol, and continuously stirring for 6 hours at 80 ℃ in an argon atmosphere by using a magnetic stirrer to uniformly mix the solution, wherein the molar ratio of the ethylene glycol to the metal cations is 2.2: 1;
(5) removing water from the uniformly mixed solution in a water bath kettle at 97 ℃ until the solution is in a jelly shape;
(6) drying in an oven at 180 ℃ for 10 hours;
(7) fully grinding the dried sample into powder, loading the powder into a crucible, carrying out heat treatment at 180 ℃ for 10 hours in argon gas to remove nitrate, then carrying out heat treatment at 500 ℃ for 6 hours in argon gas to remove organic matters, and obtaining precursor powder;
(8) grinding the obtained precursor powder for 20 minutes again, and then tabletting and sintering in air at 900 ℃ for 2 hours to obtain GdMnO3Ceramic samples.
GdMnO prepared in example 2 was used3XRD of multiferroic ceramic sample is shown in FIG. 2, and all diffraction peaks and orthogonal perovskite structure GdMnO are observed from FIG. 23And the phase is coincided and shows a single-phase structure, and no diffraction peak of a second phase appears. GdMnO is shown in FIG. 3 and FIG. 43Hysteresis loop and medium frequency curve. Wherein, the curves of the embodiment 2 shown in fig. 2, 3 and 4 arex=0.00。
Example 3
GdMn is prepared by using citric acid-nitrate sol-gel method0.95Zr0.05O3The multiferroic ceramic comprises the following steps:
(1) gadolinium nitrate hexahydrate (Gd (NO)3)3·6H2O), manganese acetate tetrahydrate (C)4H6MnO4·4H2O), zirconium nitrate pentahydrate (Zr (NO)3)4·5H2O), citric acid monohydrate (C)6H8O7·H2O) according to GdMn0.95Zr0.05O3In a stoichiometric ratio of (a), wherein the cation: the citric acid molar ratio is 1: 1.5;
(2) measuring deionized water by using a measuring cylinder, pouring the deionized water into a beaker, sequentially adding citric acid, gadolinium nitrate hexahydrate, manganese acetate tetrahydrate and zirconium nitrate pentahydrate at room temperature, and immediately stirring by using a glass rod until all the reagents are dissolved;
(3) under the condition of continuous stirring, adding ammonia water to adjust the pH value to 8;
(4) adding ethylene glycol, and continuously stirring for 6 hours by using a magnetic stirrer at 80 ℃ in an argon atmosphere to uniformly mix the solution, wherein the molar ratio of the ethylene glycol to the metal cations is 2.2: 1;
(5) removing water from the uniformly mixed solution in a water bath kettle at 97 ℃ until the solution is in a jelly shape;
(6) drying in an oven at 180 ℃ for 10 hours;
(7) fully grinding the dried sample into powder, loading the powder into a crucible, carrying out heat treatment at 180 ℃ for 10 hours in argon gas to remove nitrate, then carrying out heat treatment at 500 ℃ for 6 hours in argon gas to remove organic matters, and obtaining precursor powder;
(8) grinding the obtained precursor powder for 20 minutes again, and then tabletting and sintering in air at 900 ℃ for 2 hours to obtain GdMn0.95Zr0.05O3Ceramic samples.
GdMn prepared in example 3 was used0.95Zr0.05O3XRD of multiferroic ceramic sample is shown in FIG. 2, and all diffraction peaks and orthogonal perovskite structure GdMnO are observed from FIG. 23The obtained product is consistent and shows a single-phase structure, no diffraction peak of a second phase appears, and the Zr is shown4+Can completely replace Mn3+Enter GdMnO3To the crystal lattice of (1). GdMn is shown in FIG. 3 and FIG. 4, respectively0.95Zr0.05O3Hysteresis loop and medium frequency curve. Wherein, the curves of the embodiment 3 shown in FIG. 2, FIG. 3 and FIG. 4 arex=0.05。
Example 4
GdMn is prepared by using citric acid-nitrate sol-gel method0.90Zr0.10O3The multiferroic ceramic comprises the following steps:
(1) gadolinium nitrate hexahydrate (Gd (NO)3)3·6H2O), manganese acetate tetrahydrate (C)4H6MnO4·4H2O), zirconium nitrate pentahydrate (Zr (NO)3)4·5H2O), citric acid monohydrate (C)6H8O7·H2O) according to GdMn0.90Zr0.10O3In a stoichiometric ratio of (a), wherein the cation: lemonThe acid molar ratio is 1: 1.5;
(2) measuring deionized water by using a measuring cylinder, pouring the deionized water into a beaker, sequentially adding citric acid, gadolinium nitrate hexahydrate, manganese acetate tetrahydrate and zirconium nitrate pentahydrate at room temperature, and immediately stirring by using a glass rod until all the reagents are dissolved;
(3) under the condition of continuous stirring, adding ammonia water to adjust the pH value to 8;
(4) adding ethylene glycol, and continuously stirring for 6 hours at 80 ℃ in an argon atmosphere by using a magnetic stirrer to uniformly mix the solution, wherein the molar ratio of the ethylene glycol to the metal cations is 2.2: 1;
(5) removing water from the uniformly mixed solution in a water bath kettle at 97 ℃ until the solution is in a jelly shape;
(6) drying in an oven at 180 ℃ for 10 hours;
(7) fully grinding the dried sample into powder, loading the powder into a crucible, carrying out heat treatment at 180 ℃ for 10 hours in argon gas to remove nitrate, then carrying out heat treatment at 500 ℃ for 6 hours in argon gas to remove organic matters, and obtaining precursor powder;
(8) grinding the obtained precursor powder for 20 minutes again, and then tabletting and sintering in air at 900 ℃ for 2 hours to obtain GdMn0.90Zr0.10O3Ceramic samples.
GdMn prepared in example 4 was used0.90Zr0.10O3XRD of multiferroic ceramic sample is shown in FIG. 2, and all diffraction peaks and orthogonal perovskite structure GdMnO are observed from FIG. 23The obtained product is consistent and shows a single-phase structure, no diffraction peak of a second phase appears, and the Zr is shown4+Can completely replace Mn3+Enter GdMnO3To the crystal lattice of (1). GdMn is shown in FIG. 3 and FIG. 4, respectively0.90Zr0.10O3Hysteresis loop and medium frequency curve. Wherein, the curves of the embodiment 4 shown in fig. 2, 3 and 4 arex=0.10。
Comparative example 1
GdMn is prepared by using citric acid-nitrate sol-gel method0.85Zr0.15O3The multiferroic ceramic comprises the following steps:
(1) gadolinium nitrate hexahydrate (Gd (NO)3)3·6H2O), manganese acetate tetrahydrate (C)4H6MnO4·4H2O), zirconium nitrate pentahydrate (Zr (NO)3)4·5H2O), citric acid monohydrate (C)6H8O7·H2O) according to GdMn0.85Zr0.15O3In a stoichiometric ratio of (a), wherein the cation: the citric acid molar ratio is 1: 1.5;
(2) measuring deionized water by using a measuring cylinder, pouring the deionized water into a beaker, sequentially adding citric acid, gadolinium nitrate hexahydrate, manganese acetate tetrahydrate and zirconium nitrate pentahydrate at room temperature, and immediately stirring by using a glass rod until all the reagents are dissolved;
(3) under the condition of continuous stirring, adding ammonia water to adjust the pH value to 8;
(4) adding ethylene glycol, and continuously stirring for 6 hours at 80 ℃ in an argon atmosphere by using a magnetic stirrer to uniformly mix the solution, wherein the molar ratio of the ethylene glycol to the metal cations is 2.2: 1;
(5) removing water from the uniformly mixed solution in a water bath kettle at 97 ℃ until the solution is in a jelly shape;
(6) drying in an oven at 180 ℃ for 10 hours;
(7) fully grinding the dried sample into powder, loading the powder into a crucible, carrying out heat treatment at 180 ℃ for 10 hours in argon gas to remove nitrate, then carrying out heat treatment at 500 ℃ for 6 hours in argon gas to remove organic matters, and obtaining precursor powder;
(8) grinding the obtained precursor powder for 20 minutes again, and then tabletting and sintering in air at 900 ℃ for 2 hours to obtain GdMn0.85Zr0.15O3Ceramic samples.
GdMn prepared by comparative example 10.85Zr0.15O3XRD of multiferroic ceramic sample is shown in FIG. 2, and from FIG. 2, the main diffraction peak and the orthogonal perovskite structure GdMnO of the sample are observed3The coincidence indicates that the main phase of the sample is GdMnO3But the sample appeared ZrO2Second phase, indicating Zr4+In GdMnO3The medium doping limit is 0.15, therefore, GdMn in the invention x1-Zr x O3Zr of ceramic choice4+In the doping amount range of 0 < (R) >xLess than or equal to 0.10. GdMn is shown in FIG. 3 and FIG. 4, respectively0.85Zr0.15O3Hysteresis loop and medium frequency curve. Wherein the curves of comparative example 1 shown in FIGS. 2, 3 and 4 arex=0.15。
In order to investigate the phase structure of the zirconium-doped gadolinium manganate multiferroic ceramic prepared by the method of the present invention, phase analysis was performed on the samples obtained in examples 1 to 4 and comparative example 1 using an X-ray diffractometer (XRD), and the results are shown in fig. 1 and 2. As can be seen from FIG. 1, the main diffraction peaks and the orthogonal perovskite structure GdMnO of all samples3Coincidentally, the samples prepared at 850 ℃ had insufficient reacted Gd2O3And Mn2O3Hetero-phase, the sample prepared at 900 ℃ exhibiting a monophasic structure, the sample prepared at 950 ℃ presenting a structure formed by GdMnO3Decomposed GdMn2O5And (3) impurity phase. Thus, GdMn x1-Zr x O3The sintering temperature range of the selected ceramic is 880-920 ℃. As can be seen from the view in figure 2,xsamples of which the density is 0.00-0.10 are all in an orthogonal perovskite structure, no second phase is generated, and the doping amount of zirconium is changedxThe major diffraction peak is shifted to a small angle, indicating Zr4+Can completely replace Mn3+Enter GdMnO3And cause structural distortion. But do notx=0.15 sample occurrence of ZrO2Second phase, description shows Zr4+In GdMnO3The medium doping limit is 0.15. Therefore, GdMn in the present invention x1-Zr x O3Zr of ceramic choice4+In the range of 0 < doping amountx≤0.10。
In order to study the magnetic properties of the zirconium-doped gadolinium manganate multiferroic ceramic prepared by the method of the present invention, the samples of examples 2-4 and comparative example 1 were subjected to magnetic measurement using a PPMS comprehensive physical property testing system of Quantum Design, and the results are shown in fig. 3. As can be seen from FIG. 3, the undoped GdMnO3Exhibits a counter iron at both 40 and 30KMagnetic, ferromagnetic at 5K, when doped with Zr4+Thereafter, samples 40K, 30K and 5K all showed ferromagnetism, in particular Zr4+The doping amount isxFor the sample of =0.10, the hysteresis loops at the temperatures of 40K and 30K are significant. This is due to non-magnetic high valence Zr4+Doping affects Mn3+-Mn3+、Gd3+-Gd3+、Gd3+-Mn3+Interaction between, Mn3+The spins align and cation vacancies are introduced, causing distortion of the lattice structure and thus a change in the magnetic properties of the sample. When Zr4+The doping amount isxMagnetic property of sample and =0.15xA significant decrease in the sample of =0.10, indicating excess Zr4+Doping is detrimental to the magnetic properties of the material, which may be associated with ZrO2The second phase is related. The experimental result shows that the proper amount of Zr4+Doping can increase the magnetic transition temperature and ferromagnetism of the sample.
In order to study the dielectric properties of the zirconium-doped gadolinium manganate multiferroic ceramic prepared by the method of the present invention, the samples of examples 2-4 and comparative example 1 were subjected to dielectric property measurement using an Agilent 4294A type precision impedance analyzer, and the results are shown in fig. 4. As can be seen from FIG. 4, the undoped GdMnO3The dielectric constant of (2) has stronger frequency dependence, the dielectric constant is larger at low frequency and lower at high frequency; zr4+After doping, the frequency dependence of the dielectric constant of the sample is improved, and the frequency stability is good; while Zr4+The doped sample has giant dielectric property at high frequency, and GdMn at 1MHz test frequency0.95Zr0.05O3、GdMn0.90Zr0.10O3The dielectric constants of the samples were 3034.3, 7180.0, respectively. This is in conjunction with the high valence of Zr4+Doped GdMnO3In which mixed valency states of Mn (Mn) are present2+And Mn3+) And lattice distortion. However, Zr4+The doping amount isxDielectric constant of =0.15 sample is relativelyxSample clearly decreased by =0.10, indicating excess Zr4+Doping does not contribute to the increase of the dielectric constant of the material, which may be related to ZrO2The second phase is related. In addition, Zr4+Small dielectric loss of doped samplesIn undoped GdMnO3And Zr4+Dielectric loss with Zr when the doping amount is increased from 0.00 to 0.104+The doping amount is increased and decreased; but Zr4+Dielectric loss ratio of 0.15 doping amountxAn increase of =0.10, indicating excess Zr4+Doping is not conducive to reducing the dielectric loss of the material, which may be associated with ZrO2The second phase is related. The experimental result shows that Zr4+The high-frequency region of the doped sample room has giant dielectric property at the temperature and contains a proper amount of Zr4+The doping can improve the dielectric constant of the sample and reduce the dielectric loss.
In conclusion, the zirconium-doped gadolinium manganate multiferroic ceramic GdMn provided by the invention x1-Zr x O3The magnetic property and the dielectric property of gadolinium manganate can be well regulated and controlled by doping Zr, and meanwhile, Zr4+Doped GdMnO3Has giant dielectric property, and is a novel multiferroic material which is expected to be further researched and explored.
Finally, it should be noted that the examples described herein are only intended to illustrate technical embodiments of the present invention and not to limit the same, and although the present invention has been described in detail with reference to preferred examples, it will be understood by those skilled in the art that modifications and equivalent substitutions can be made to the technical embodiments of the present invention without departing from the spirit and scope of the technical embodiments of the present invention, which should be covered by the claims of the present invention.
Claims (7)
1. The zirconium-doped gadolinium manganate multiferroic ceramic is characterized by having a chemical formula of GdMn x1-Zr x O3Wherein, the doping amount of zirconiumxThe range of (A) is as follows: 0 < (R) >x≤0.10。
2. The method for preparing the zirconium-doped gadolinium manganate multiferroic ceramic as claimed in claim 1, characterized by comprising the following steps:
(1) gd (NO) nitrate hexahydrate3)3·6H2O, manganese acetate tetrahydrate C4H6MnO4·4H2O and Zr nitrate pentahydrate (NO)3)4·5H2O is according to GdMn respectively x1-Zr x O3The stoichiometric ratio of the citric acid C is weighed, and then the citric acid C monohydrate is weighed6H8O7·H2O, wherein the molar ratio of the cation to the citric acid is 1: 1-1: 2;
(2) pouring deionized water into a beaker, sequentially adding citric acid monohydrate, gadolinium nitrate hexahydrate, manganese acetate tetrahydrate and zirconium nitrate pentahydrate at room temperature, and stirring until all the materials are dissolved;
(3) under the condition of continuous stirring, adding ammonia water to adjust the pH value to 7-9;
(4) adding ethylene glycol, and continuously stirring to uniformly mix the solution;
(5) placing the uniformly mixed solution in a water bath kettle to remove water to obtain a jelly;
(6) drying in an oven;
(7) fully grinding the dried sample into powder, filling the powder into a crucible, and performing heat treatment to obtain precursor powder;
(8) grinding the obtained precursor powder again, tabletting and sintering in air or oxygen to obtain GdMn x1-Zr x O3A ceramic sample;
the heat treatment in the step (7) is divided into a first heat treatment and a second heat treatment, wherein the first heat treatment is heat treatment for 10-15 hours at 200-300 ℃ in a nitrogen or argon atmosphere to remove nitrate; the second heat treatment is heat treatment for 5 to 7 hours at 460 to 650 ℃ in nitrogen or argon atmosphere to remove organic matters;
the sintering temperature in the step (8) is 880-920 ℃, and the time is 1.5-3 hours.
3. The method of preparing the zirconium-doped gadolinium manganate multiferroic ceramic of claim 2, wherein: and (4) adding ethylene glycol, and continuously stirring for 6 hours at 80 ℃ in a nitrogen or argon atmosphere by using a magnetic stirrer to uniformly mix the solution.
4. The method of preparing the zirconium-doped gadolinium manganate multiferroic ceramic of claim 2, wherein: the molar ratio of the ethylene glycol added in the step (4) to the metal cations in the step (1) is 2:1-2.5: 1.
5. The method of preparing the zirconium-doped gadolinium manganate multiferroic ceramic of claim 2, wherein: and (5) setting the temperature of the water bath kettle in the step (5) to be 85-100 ℃.
6. The method of preparing the zirconium-doped gadolinium manganate multiferroic ceramic of claim 2, wherein: the drying temperature in the step (6) is 155-190 ℃, and the drying time is 8-11 hours.
7. The method of preparing the zirconium-doped gadolinium manganate multiferroic ceramic of claim 2, wherein: and (4) the time for re-grinding in the step (8) is 10-30 minutes.
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