CN116675518A - Single-layer and double-layer perovskite multiferroic multiphase material, and preparation method and application thereof - Google Patents
Single-layer and double-layer perovskite multiferroic multiphase material, and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 86
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- 238000005245 sintering Methods 0.000 claims abstract description 34
- 238000000227 grinding Methods 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 24
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- 239000011572 manganese Substances 0.000 description 43
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 12
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Abstract
The invention discloses a single-layer and double-layer perovskite multiferroic multiphase material, and a preparation method and application thereof, and belongs to the technical field of single-layer and double-layer perovskite multiferroic multiphase materials. The single-layer and double-layer perovskite multiferroic multiphase material is prepared by the following steps: according to formula Ca 3 Mn 2 O 7 Respectively weighing Ca source, mn source and O source according to the stoichiometric ratio, grinding to uniformly mix the Ca source, the Mn source and the O source, and obtaining mixed powder; presintering the mixed powder at 900-1100 ℃, and grinding again after presintering to obtain a precursor; tabletting the precursor material, and sintering at 1200-1300 ℃ for 12-24h to obtain Ca 3 Mn 2 O 7 As the main phase, ca 2 MnO 4 Single and double layer perovskite as secondary phaseMultiferroic multiphase materials. The invention controls the sintering temperature to control Ca 2 MnO 4 The content and the magnetic properties can be adjusted.
Description
Technical Field
The invention relates to the technical field of single-layer and double-layer perovskite multiferroic multiphase materials, in particular to a single-layer and double-layer perovskite multiferroic multiphase material, and a preparation method and application thereof.
Background
The main focus of multiferroics research is coexistence and coupling between the ferroelectric sequence and the spin sequence, and the control of the electric polarization by using an external electric field to control the magnetic sequence or an external magnetic field is realized, so that the cross regulation and control between the magnetism and the electricity are achieved. The intrinsic mechanisms of magnetism and ferroelectricity are traditionally mutually exclusive, e.g. the generation of polarization often requires empty d-orbitals, whereas magnetism results from unpaired electrons of d-orbitals or f-orbitals. The discovery of multiferroics and magnetoelectric coupling combines two major materials of ferroelectricity and magnetism which lack intrinsic relation traditionally, realizes the coupling of ferroelectric sequences and ferromagnetic sequences, integrates the physical advantages of two ordered phases in sequence, and provides a material basis for realizing applications such as polymorphic storage, electrographic magnetic reading and the like.
An R-P (Ruddlesden-Popper) layered manganese-based perovskite oxide is a hybrid extrinsic ferroelectric (Hybirdimproper ferroelectricity) whose spontaneous polarization is induced by other nonpolar distortions, so the occurrence of spontaneous polarization cannot fully describe all symmetry changes during phase transitions. Meanwhile, the phase change is caused by nonpolar distortion, so that the electronic configuration avoids the repulsion with the magnetic electronic configuration.
Ca 2 MnO 4 The oxide is a single-layer layered perovskite structure, and Ca is prepared in the prior art 3 Mn 2 O 7 In the double-layer perovskite multiferroic material technology, researchers only consider Ca 2 MnO 4 Is a heterogeneous phase and is unfavorable to double-layer Ca 3 Mn 2 O 7 Improvement of the properties of double perovskite multiferroic materials, but no way to quantitatively determine Ca 2 MnO 4 The amount of monolayer phase, and how much the amount of monolayer phase has an effect on the overall properties of the material. Therefore, how to provide a simple, efficient and easily controlled single-layer layered perovskite Ca 2 MnO 4 The preparation method of ceramic materials is a problem to be solved by the person skilled in the art.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a single-layer perovskite multiferroic multiphase material and a double-layer perovskite multiferroic multiphase material, and Ca is prepared by regulating and controlling the sintering temperature 2 MnO 4 The content and the magnetic properties can be adjusted.
The first object of the invention is to provide a preparation method of single-layer and double-layer perovskite multiferroic multiphase material, which is prepared according to the following steps:
step 1, according to formula Ca 3 Mn 2 O 7 Respectively weighing Ca source, mn source and O source according to the stoichiometric ratio, grinding to uniformly mix the Ca source, the Mn source and the O source, and obtaining mixed powder;
step 2, presintering the mixed powder at 900-1100 ℃, and grinding again after presintering to obtain a precursor;
step 3, after tabletting the precursor material, sintering the precursor material for 12-24 hours at 1200-1300 ℃ to obtain Ca 3 Mn 2 O 7 As the main phase, ca 2 MnO 4 Single-layer and double-layer perovskite multiferroic multiphase materials which are minor phases.
Preferably, in step 3, sintering is carried out at 1200 ℃ for 24 hours to obtain 28.9% Ca by mole mass 2 MnO 4 And 71.1% by mole of Ca 3 Mn 2 O 7 Multiphase materials.
Preferably, in step 3, sintering is carried out at 1250 ℃ for 24 hours to obtain 11.4% Ca by mole percent 2 MnO 4 And 88.6% Ca by mole 3 Mn 2 O 7 Multiphase materials.
Preferably, in the step 2, the pre-sintering treatment time is 12-24 hours, and the heating rate is 3-10 ℃/min.
Preferably, in the step 3, the compression pressure of the tablet is 15-25 Mpa, and the dwell time is 8-20 min.
Preferably, in step 3, the sintering temperature rising rate is 3-10 ℃/min.
The second object of the invention is to provide the single-layer and double-layer perovskite multiferroic multiphase material prepared by the preparation method.
A third object of the present invention is to provide the application of the single-layer and double-layer perovskite multiferroic multiphase material in preparing magneto-electric sensing devices, high-density memory devices and microwave dielectric ceramics.
Compared with the prior art, the invention has the following beneficial effects:
the single-layer and double-layer perovskite multiferroic (hybrid extrinsic multiferroic) multiphase material Ca of the invention 2 MnO 4 And Ca 3 Mn 2 O 7 The multiphase material finds additional magnetic transition temperatures around 125K; and the single-layer and double-layer perovskite multiferroic (hybrid extrinsic multiferroic) multiphase material Ca of the invention 2 MnO 4 And Ca 3 Mn 2 O 7 The mixture exhibits hysteresis at the magnetic transition temperature; and the residual magnetization measured near the magnetic transition temperature is compared with that of pure Ca 3 Mn 2 O 7 The material is obviously improved, which indicates Ca 2 MnO 4 And Ca 3 Mn 2 O 7 The multiphase material can be used as a multiphase multiferroic functional material, and can even be used as a functional material for magneto-electric coupling, high-density storage and the like after exploration.
The invention is characterized in that in a manganese-based perovskite oxide system, R-P type (Ruddlesden-Popper) layered manganese-based perovskite oxide Ca is adopted 3 Mn 2 O 7 Based on this, ca with different contents is prepared by different sintering processes, i.e. by controlling the sintering temperature 2 MnO 4 A multiphase material; and the residual magnetization also changes with the sintering process.
The preparation method is simple and convenient, has low preparation cost, is low in equipment and equipment, and is suitable for industrial production.
Drawings
FIG. 1 is an XRD pattern of single-layer and double-layer perovskite multiferroic multiphase materials prepared according to example 1 of the present invention;
FIG. 2 is an XRD pattern of single and double layer perovskite multiferroic multiphase materials prepared according to example 2 of the present invention;
FIG. 3 is an XRD pattern of single-layer and double-layer perovskite multiferroic multiphase materials prepared according to comparative example 1 of the present invention;
FIG. 4 is a graph (M-T) showing the magnetization of single-layer and double-layer perovskite multiferroic multiphase materials prepared in example 1 according to the present invention as a function of temperature, and the interpolated graph is the dM/dT curve of FC and ZFC;
FIG. 5 is a graph (M-T) showing the magnetization of single and double perovskite multiferroic multiphase materials prepared according to example 2 of the present invention as a function of temperature, and interpolated graphs are dM/dT curves for FC and ZFC;
FIG. 6 is a graph (M-T) showing the magnetization of single-layer and double-layer perovskite multiferroic multiphase materials prepared according to comparative example 1 of the present invention as a function of temperature, and interpolated graph is the dM/dT curve of FC and ZFC;
FIG. 7 is a graph (M-H) showing the magnetization of single-layer and double-layer perovskite multiferroic multiphase materials prepared in example 1 according to the present invention as a function of external field, and the inset is an enlarged graph of coercivity and remanence;
FIG. 8 is a graph (M-H) showing the magnetization of single-layer and double-layer perovskite multiferroic multiphase materials prepared in example 2 according to the present invention as a function of external field, and the inset is an enlarged graph of coercivity and remanence;
FIG. 9 is a graph (M-H) showing the magnetization of single-layer and double-layer perovskite multiferroic multiphase materials prepared in comparative example 1 according to the present invention as a function of external field, and the inset is an enlarged graph of coercive force and remanence.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The Ca source and the Mn source used in the invention are oxides containing corresponding elements, and the O source is provided by oxygen in each oxide containing corresponding elements.
The percentages in the present invention refer to Ca 2 MnO 4 And Ca 3 Mn 2 O 7 Ca in heterogeneous materials 2 MnO 4 The mole percent of the material is calculated.
Example 1
This example provides a single and double layer perovskite multiferroic (hybrid extrinsic multiferroic) multiphase material with R-P (Ruddlesden-Popper) layered manganese-based perovskite oxide Ca 3 Mn 2 O 7 Based on, 28.9% Ca was prepared 2 MnO 4 And Ca 3 Mn 2 O 7 Multiphase materials.
Step 1, according to the molecular formula Ca 3 Mn 2 O 7 The stoichiometric ratio of Ca source, mn source and O source are respectively weighed and are uniformly mixed by grinding in a mortar to obtain fine mixed powder, and the Ca source and the Mn source are respectively CaCO 3 ，MnO 2 The O source is CaCO 3 ，MnO 2 Oxygen supply in (a);
in this example, caCO 3 ，MnO 2 The purity of the oxide powder is above 99.99%.
Step 2, pre-sintering the mixed powder at the temperature of 1000 ℃ for 24 hours, wherein the heating rate is 5 ℃/min, and then grinding the pre-sintered powder again to obtain a precursor;
and 3, grinding the precursor material, maintaining the pressure at 20MPa for 8min, tabletting, and sintering at 1200 ℃ for 24h, wherein the heating rate is 5 ℃/min, so as to obtain the single-layer and double-layer perovskite multiferroic (hybrid extrinsic multiferroic) multiphase material.
Example 2
The present embodiment provides aSingle-layer and double-layer perovskite multiferroic (hybrid extrinsic multiferroic) multiphase materials with R-P (Ruddlesden-Popper) layered manganese-based perovskite oxide Ca 3 Mn 2 O 7 Based on, 11.4% Ca was prepared 2 MnO 4 And Ca 3 Mn 2 O 7 Multiphase materials.
Step 1, according to formula Ca 3 Mn 2 O 7 Respectively weighing Ca source, mn source and O source according to the stoichiometric ratio in the raw materials, and uniformly mixing the Ca source, the Mn source and the O source by grinding in a mortar to obtain fine mixed powder; the Ca source and Mn source used in this example are CaCO 3 ，MnO 2 The O source is CaCO 3 ，MnO 2 Oxygen supply in (a);
in this example, caCO 3 ，MnO 2 The purity of the oxide powder is above 99.99%.
Step 2, pre-sintering the mixed powder at the temperature of 1000 ℃ for 24 hours, wherein the heating rate is 5 ℃/min, and then grinding the pre-sintered powder again to obtain a precursor;
and 3, grinding the precursor material, maintaining the pressure of 20MPa for 8min, tabletting, and then sintering at 1250 ℃ for 24h respectively, wherein the heating rate is 5 ℃/min, so as to obtain the single-layer and double-layer perovskite multiferroic (hybrid extrinsic multiferroic) multiphase material.
Example 3
This example provides a single and double layer perovskite multiferroic (hybrid extrinsic multiferroic) multiphase material prepared as follows:
step 1, according to the molecular formula Ca 3 Mn 2 O 7 The stoichiometric ratio of Ca source, mn source and O source are respectively weighed and are uniformly mixed by grinding in a mortar to obtain fine mixed powder, and the Ca source and the Mn source are respectively CaCO 3 ，MnO 2 The O source is CaCO 3 ，MnO 2 Oxygen supply in (a);
in this example, caCO 3 ，MnO 2 The purity of the oxide powder is above 99.99%.
Step 2, pre-sintering the mixed powder at 900 ℃ for 20 hours, wherein the heating rate is 10 ℃/min, and then grinding the pre-sintered powder again to obtain a precursor;
and 3, grinding the precursor material, maintaining the pressure at 15MPa for 20min, tabletting, and sintering at 1300 ℃ for 12h, wherein the heating rate is 10 ℃/min, so that the single-layer and double-layer perovskite multiferroic (hybrid extrinsic multiferroic) multiphase material is obtained.
Example 4
This example provides a single and double layer perovskite multiferroic (hybrid extrinsic multiferroic) multiphase material prepared as follows:
step 1, according to the molecular formula Ca 3 Mn 2 O 7 The stoichiometric ratio of Ca source, mn source and O source are respectively weighed and are uniformly mixed by grinding in a mortar to obtain fine mixed powder, and the Ca source and the Mn source are respectively CaCO 3 ，MnO 2 The O source is CaCO 3 ，MnO 2 Oxygen supply in (a);
in this example, caCO 3 ，MnO 2 The purity of the oxide powder is above 99.99%.
Step 2, pre-sintering the mixed powder for 12 hours at 1100 ℃, wherein the heating rate is 3 ℃/min, and then grinding the pre-sintered powder again to obtain a precursor;
and 3, grinding the precursor material, maintaining the pressure at 25MPa for 3min, tabletting, and sintering at 1200 ℃ for 20h, wherein the heating rate is 3 ℃/min, so as to obtain the single-layer and double-layer perovskite multiferroic (hybrid extrinsic multiferroic) multiphase material.
Comparative example 1
This comparative example provides a double layer perovskite multiferroic (hybrid extrinsic multiferroic) multiphase material with R-P (Ruddlesden-Popper) layered manganese-based perovskite oxide Ca 3 Mn 2 O 7 Based on, 0% Ca was prepared 2 MnO 4 And Ca 3 Mn 2 O 7 Multiphase materials.
Step 1, according to formula Ca 3 Mn 2 O 7 Respectively weighing Ca source, mn source and O source according to the stoichiometric ratio in the raw materials, and uniformly mixing the Ca source, the Mn source and the O source by grinding in a mortar to obtain fine mixed powder;
in this comparative example, caCO 3 ，MnO 2 The purity of the oxide powder is above 99.99%.
Step 2, pre-sintering the mixed powder for 24 hours at the temperature of 1000 ℃, and then grinding the pre-sintered powder again to obtain a precursor;
and 3, grinding the precursor material, maintaining the pressure of 20MPa for 8min, tabletting, and then sintering at 1300 ℃ for 24h respectively to obtain the double-layer perovskite multiferroic (hybrid extrinsic multiferroic) multiphase material.
In the preparation process of the present invention, the specific mode of grinding is not limited in step 1, as long as the preparation raw materials can be uniformly mixed. Optionally, mechanical grinding is adopted, such as mechanical ball milling, until the particle size of the mixed powder is 1-5 μm.
In the step 2, the specific heating rate of the pre-sintering treatment is not limited, and the temperature is stably raised. The temperature rising rate of the optional pre-sintering treatment is 3-10 ℃/min. In step 2, the product after the pre-sintering treatment is ground and then subjected to the secondary pre-sintering treatment, and the specific mode of the grinding treatment after the pre-sintering treatment is not limited in this embodiment, so long as the obtained product can be ground into uniform powder. According to the invention, a mechanical grinding mode is optionally adopted for grinding until the particle size of the presintered product is 1-5 mu m, so that the presintered product can be prevented from being heated uniformly in the sintering process, and the condition that the final performance of the material is not thoroughly affected by sintering is avoided.
The specific manner of the precursor material grinding treatment in step 3 is not limited as long as the obtained product can be ground into a uniform powder. Optionally, the precursor material is ground by a mechanical grinding mode until the particle size of the precursor material is 1-5 mu m, so that the precursor material can be conveniently pressed into a sheet and then can be uniformly heated in the sintering treatment process, and single-layer and double-layer perovskite multiferroic (hybrid extrinsic multiferroic) multiphase materials with uniform components are obtained.
According to the present invention, about 2g of the precursor materials obtained in examples 1 to 2 and comparative example 1 (i.e., the precursor obtained in step 2) were obtained in the same manner as in examples 1 to 2 and comparative example 1, respectively, and pressed into tablets in the same manner as in examples 1, 2 and comparative example 1, respectively, and then sintered to obtain samples 1, 2 and 3, which were designated as 1, 2 and 3, respectively.
XRD test
In the invention, XRD tests at room temperature are respectively carried out on a sample 1, a sample 2 and a sample 3, and the test results are respectively shown in figures 1-3.
As can be seen from fig. 1-3: XRD diffraction peaks of the sample 1, the sample 2 and the sample 3 are completely matched with XRD data of the double-layer manganese-based perovskite oxide, and the XRD diffraction peaks are both in an R-P structure, and the space group is I 4 Mmm and A2 1 am.
(II) magnetic Property test
The XRD test at room temperature was performed on each of sample 1, sample 2 and sample 3, and the test results are shown in fig. 4 to 9.
Fig. 4 to 6 are graphs showing the magnetization of the double-layer manganese-based perovskite oxide multiphase material according to the present invention as a function of temperature, wherein fig. 4 is a graph showing the magnetization of sample 1 as a function of temperature, fig. 5 is a graph showing the magnetization of sample 2 as a function of temperature, and fig. 6 is a graph showing the magnetization of sample 3 as a function of temperature.
As can be seen from fig. 4-6: all samples showed complex magnetic phase transitions, as known from the reported double layer manganese-based perovskite oxide multiphase materials, magnetic transitions were shown around 115K and spin-clustering at low temperatures. In addition, all samples had another magnetic phase transition around 125K.
Fig. 7 to 9 are graphs showing the magnetization of the double-layered manganese-based perovskite oxide multiphase material according to the present invention as a function of external field, wherein fig. 7 is a graph showing the magnetization of sample 1 as a function of external field, fig. 8 is a graph showing the magnetization of sample 2 as a function of external field, and fig. 9 is a graph showing the magnetization of sample 3 as a function of external field.
As can be seen from fig. 7-9: as the Ca in the sample 2 MnO 4 The percentage is increased, the residual magnetization of the double-layer manganese-based perovskite oxide multiphase material is improved, and the development of the double-layer manganese-based perovskite oxide multiphase material is promoted.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (8)
1. The preparation method of the single-layer and double-layer perovskite multiferroic multiphase material is characterized by comprising the following steps of:
step 1, according to formula Ca 3 Mn 2 O 7 Respectively weighing Ca source, mn source and O source according to the stoichiometric ratio, grinding to uniformly mix the Ca source, the Mn source and the O source, and obtaining mixed powder;
step 2, presintering the mixed powder at 900-1100 ℃, and grinding again after presintering to obtain a precursor;
step 3, after tabletting the precursor material, sintering the precursor material for 12-24 hours at 1200-1300 ℃ to obtain Ca 3 Mn 2 O 7 As the main phase, ca 2 MnO 4 Single-layer and double-layer perovskite multiferroic multiphase materials which are minor phases.
2. A method for preparing single-layer and double-layer perovskite multiferroic multiphase material according to claim 1Characterized in that in the step 3, ca with the mol percent of 28.9% is obtained by sintering for 24 hours at 1200 DEG C 2 MnO 4 And 71.1% by mole of Ca 3 Mn 2 O 7 Multiphase materials.
3. The method for producing a single-layer and double-layer perovskite multiferroic multiphase material according to claim 1, wherein in step 3, ca having a molar mass percentage of 11.4% is obtained by sintering at 1250 ℃ for 24 hours 2 MnO 4 And 88.6% Ca by mole 3 Mn 2 O 7 Multiphase materials.
4. The method for preparing a single-layer and double-layer perovskite multiferroic multiphase material according to claim 1, wherein in the step 2, the pre-sintering treatment time is 12-24 hours, and the heating rate is 3-10 ℃/min.
5. The method for producing a single-layer and double-layer perovskite multiferroic multiphase material according to claim 1, wherein in step 3, the compression pressure of the tablet is 15 to 25Mpa and the dwell time is 8 to 20min.
6. The method for producing a single-layer and double-layer perovskite multiferroic multiphase material according to claim 1, wherein in step 3, the sintering temperature rise rate is 3 to 10 ℃/min.
7. A single-layer and double-layer perovskite multiferroic multiphase material prepared by the preparation method according to any one of claims 1 to 6.
8. Use of the single-layer and double-layer perovskite multiferroic multiphase material according to claim 7 in the preparation of magneto-electric sensing devices, high density memory devices and in microwave dielectric ceramics.
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| KR20160065415A (en) * | 2014-11-28 | 2016-06-09 | 주식회사 대양신소재 | A semiconductor ceramics composition of perovskite structure |
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| CN114656243A (en) * | 2022-02-25 | 2022-06-24 | 纯钧新材料(深圳)有限公司 | Calcium-manganese-oxygen thermoelectric material and preparation method thereof |
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