CN114031122B - Ti doped Gd 2 CoMn 1-x Ti x O 6 Double perovskite type ceramic material and preparation method thereof - Google Patents
Ti doped Gd 2 CoMn 1-x Ti x O 6 Double perovskite type ceramic material and preparation method thereof Download PDFInfo
- Publication number
- CN114031122B CN114031122B CN202111435291.3A CN202111435291A CN114031122B CN 114031122 B CN114031122 B CN 114031122B CN 202111435291 A CN202111435291 A CN 202111435291A CN 114031122 B CN114031122 B CN 114031122B
- Authority
- CN
- China
- Prior art keywords
- temperature
- comn
- ceramic material
- doped
- double perovskite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a Ti doped Gd 2 CoMn 1‑x Ti x O 6 The preparation method of the double perovskite type ceramic material has the characteristics of easily controlled proportion of each component of a sample, low cost, no need of adding a solvent, environmental protection, no pollution, easy operation of equipment, no need of introducing a reaction atmosphere in the reaction process, easy collection of products and capability of preparing a large amount. The standard solid phase reaction of the invention effectively inhibits the phenomena of solid phase sintering and recrystallization in the sintering process through multiple times of grinding. The invention also provides the double perovskite ceramic material prepared by the method, and the product has a single-phase double perovskite structure. Due to Ti 4+ And Mn of 4+ Is different in ionic radius and is non-magnetic Ti 4+ The doping of the Gd-doped material not only can adjust the lattice structure, but also can adjust and control the ferromagnetic interaction in the lattice structure, thereby adjusting and controlling the macroscopic magnetic property of the material so as to obtain the Gd 2 CoMn 1‑x Ti x O 6 Becomes a multifunctional ceramic material with great application prospect.
Description
Technical Field
The invention belongs to the technical field of double perovskite type ceramic materials, and relates to a Ti-doped Gd 2 CoMn 1-x Ti x O 6 Double perovskite ceramic material and a preparation method thereof.
Background
Calcium titanate (CaTiO) 3 ) Was first discovered in the 30 s of the 19 th century in Ural mountain, and was later named perovskite by the name of the mineralogist "Preovshji" with the general formula ABO 3 (A is alkaline earth or rare earth, B is transition metal). With the continuous progress and development of material science, ABO was developed until the forty of the last century 3 Materials and derivatives thereof have gained extensive research attention for their various interesting phenomena and abundant magnetic properties. For example, based on ABO 3 And the derived double perovskite A 2 B′B″O 6 (A is alkaline earth or rare earth, B 'and B' are transition metals), in which multiple interactions between ions are involvedThe coexistence and competition of the materials can be used to show rich physical properties such as spin-phonon coupling, giant magneto resistance, giant dielectric, spin glass, etc., and the rich physical properties lead to A 2 B′B″O 6 The material has important application prospect in the high and new technical fields of electronics, information, sensing, automation and the like. Thus, A 2 B′B″O 6 The system becomes a research hot spot in the fields of condensed state physics and material science.
At a plurality of A 2 B′B″O 6 Gd in the system 2 CoMnO 6 There is a great interest in research because of its coexistence of ferromagnetism, antiferromagnetic, and giant magnetocaloric effect. For Gd 2 CoMnO 6 ，Gd 3+ There are 7 unpaired electrons on the 4f orbital with very large spin angular momentum, single Gd 3+ The theoretical effective magnetic moment of (a) can reach 7.94 mu B While its orbital angular momentum is almost zero. Gd (Gd) 2 CoMnO 6 Exhibits paramagnetic-ferromagnetic transition at-112K, where the ferromagnetism is primarily derived from Co 2+ -O 2- -Mn 4+ Super-exchange between. At lower temperatures (-47K), a distinct antiferromagnetic transition is observed. Gd (Gd) 3+ Magnetically ordered, co at low temperature 2+ -O 2- -Mn 4+ Co due to ferromagnetic interactions, flip-bit disorder 2+ -O 2- -Co 2+ Mn and 4+ -O 2- -Mn 4+ antiferromagnetically interact with Gd 2 CoMnO 6 Provides a good research platform for deeply explaining various properties and phenomena in a strongly-correlated multi-electron system, and has important theoretical and experimental research values. In a rare earth double perovskite system, the doping of B-site ions brings new thought and knowledge for researching the internal physical mechanism of the rare earth double perovskite system. However, synthesizing single-phase Gd 2 CoMnO 6 Relatively difficult, often accompanied by rare earth oxide Gd in the product 2 O 3 Is a mixed peak of (2).
The existing technology for preparing the double perovskite material comprises a sol-gel method, a precipitation method, a hydrothermal method, a gas phase method and the like. For the sol-gel method, the raw materials required for preparing the material are expensive, and the polymerization reaction speed is too high to conduct easilyThe components are unevenly distributed, and some organic solvents are toxic, not friendly to the environment and harmful to the health of human bodies; for the precipitation method, the ion sedimentation period is long, ion impurities are not completely introduced during washing, and the loss of the precipitate during washing can cause tiny change of components; for the hydrothermal method, high-temperature high-pressure reaction conditions are required, and strict requirements are imposed on the temperature, time and precursor concentration during the reaction; for the gas phase process, special equipment is required and the reaction conditions are stringent. Therefore, a method for preparing single-phase Gd without adding solvent and pollution and with low cost is explored 2 CoMn 1-x Ti x O 6 The method for preparing the double perovskite ceramic material has important significance.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the invention is to provide a Ti-doped Gd 2 CoMn 1- x Ti x O 6 The preparation method of the double perovskite type ceramic material has the characteristics of easy control of the proportion of each component in the prepared sample, low cost, no need of adding solvents, environmental protection and no pollution.
The second purpose of the invention is to provide the Ti-doped Gd obtained by the preparation method 2 CoMn 1-x Ti x O 6 The double perovskite ceramic material has a single-phase double perovskite structure.
One of the purposes of the invention is realized by adopting the following technical scheme:
ti doped Gd 2 CoMn 1-x Ti x O 6 The preparation method of the double perovskite type ceramic material comprises the following steps:
(1) Putting nano titanium dioxide, manganese carbonate, cobalt oxide and gadolinium oxide into a mortar, and grinding to uniformly mix the powder.
(2) Carrying out heat treatment on the powder material which is ground and uniformly mixed in the step (1), and heating to a temperature T 1 Then entering a first stage for heat preservation, naturally cooling to room temperature along with a furnace after heat preservation is finished, and grinding the obtained powder; the purpose of this step of burn-in is to exclude organics from the sample.
(3) Grinding the step (2)Is heated up again to the temperature T 2 Performing heat preservation in the second stage, naturally cooling to room temperature along with a furnace after heat preservation is finished, and grinding the obtained powder; the purpose of this step of pre-firing is to allow the sample to undergo a sufficient oxidation decarbonization reaction.
(4) Sintering the powder with the ground thickness in the step (3) at a high temperature, and heating to a sintering temperature T 3 Then enter the third stage to keep warm; and cooling after the heat preservation is finished, and grinding the obtained powder to obtain a final product. The purpose of controlling the cooling rate is to ensure that the oxide can fully absorb oxygen in the cooling process and improve the crystallization and phase formation uniformity of the sample.
Further, in the step (1), the molar ratio of the nano titanium dioxide to the manganese carbonate to the cobalt oxide to the gadolinium oxide is (0.1-0.4): (0.6-0.9): 1:1.
Further, the temperature rising rate in the step (2) is 5-10 ℃/min, and the temperature T is 1 The temperature is 950-1050 ℃, and the heat preservation time is 24 hours.
Further, the temperature rising rate in the step (3) is 5-10 ℃/min, and the temperature T is 2 The temperature is 1150-1250 ℃ and the heat preservation time is 24 hours.
Further, the temperature rising rate in the step (4) is 5-10 ℃/min, and the temperature T is 3 The temperature is 1350 ℃ and the heat preservation time is 24 hours.
Further, the cooling stage in the step (4) firstly reduces the temperature to 50 ℃ at the speed of 1-3 ℃/min, and then naturally cools the temperature to room temperature along with the furnace.
Further, the grinding time of the step (1) is 1.5-2h, the grinding time of the step (2) and the grinding time of the step (3) is 1-1.5h, and the grinding time of the step (4) is 10-30min.
The second purpose of the invention is realized by adopting the following technical scheme:
ti doped Gd 2 CoMn 1-x Ti x O 6 The double perovskite ceramic material is prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a Ti doped Gd 2 CoMn 1-x Ti x O 6 A preparation method of a double perovskite type ceramic material,the method has the characteristics of easily controlled proportion of each component of the sample, low cost, no need of adding solvent, environmental protection, no pollution, easy operation of equipment, no need of introducing reaction atmosphere in the reaction process, easy collection of products and capability of mass preparation. The preparation method is standard solid phase reaction, and the particle size of the powder particles is reduced by grinding, so that the reaction rate is accelerated. Through multiple grinding in the preparation process, the solid-phase sintering and recrystallization phenomena which often occur in the sintering process are effectively inhibited, and the forward progress of the reaction is facilitated.
The invention also provides the double perovskite ceramic material prepared by the method, and the product obtained by the method has a single-phase double perovskite structure. Due to Ti 4+ And Mn of 4+ Is different in ionic radius and Ti 4+ Belongs to non-magnetic ion, ti 4+ The doping of the Gd-doped material not only can influence the atomic distance in the material and adjust the lattice structure, but also can adjust and control the ferromagnetic interaction in the material so as to adjust and control the macroscopic magnetic property of the material, so that the obtained Gd-doped material is prepared 2 CoMn 1-x Ti x O 6 Becomes a multifunctional ceramic material with great application prospect.
Drawings
FIG. 1 shows the Ti-doped Gd obtained in examples 1 to 4 and comparative example 1 of the present invention 2 CoMn 1-x Ti x O 6 XRD pattern of the double perovskite ceramic material;
FIG. 2 shows the Ti-doped Gd obtained in examples 1 to 4 and comparative example 1 of the present invention 2 CoMn 1-x Ti x O 6 Scanning electron microscopy images of the double perovskite type ceramic material;
FIG. 3 shows the Ti-doped Gd obtained in examples 1 to 4 and comparative example 1 of the present invention 2 CoMn 1-x Ti x O 6 Magnetization-temperature curve of double perovskite type ceramic material;
FIG. 4 shows the Ti-doped Gd obtained in examples 1 to 4 and comparative example 1 of the present invention 2 CoMn 1-x Ti x O 6 Hysteresis loop of double perovskite type ceramic material.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and detailed description, wherein it is to be understood that, on the premise of no conflict, the following embodiments or technical features may be arbitrarily combined to form new embodiments.
Example 1
Ti doped Gd 2 CoMn 1-x Ti x O 6 Double perovskite type ceramic material Gd 2 CoMn 1-x Ti x O 6 (x=0.1), the preparation process comprises the following steps:
(1) Sequentially weighing 0.00025mol of nano titanium dioxide, 0.00225mol of manganese carbonate, 0.0025mol of cobalt oxide and 0.0025mol of gadolinium oxide by using a high-precision electronic balance, putting the materials into an agate mortar, and grinding for 1.6h to uniformly mix the materials.
(2) And (3) carrying out heat treatment on the powder material which is ground and uniformly mixed in the step (1) in the air, heating to 975 ℃ at a speed of 6 ℃ per minute, carrying out first-stage heat preservation for 24 hours, naturally cooling to room temperature along with a furnace to obtain black powder, and carrying out intermediate grinding on the obtained powder for 1.2 hours.
(3) Heating the powder subjected to intermediate grinding in the step (2) to 1175 ℃ in air at a speed of 6 ℃/min, performing heat preservation in the second stage for heat treatment for 24 hours, naturally cooling to room temperature along with a furnace to obtain black powder, and fully grinding the powder for 1.2 hours.
(4) And (3) sintering the fully ground powder in the step (3) at a high temperature, heating to 1350 ℃ at a speed of 6 ℃/min, and performing heat preservation in a third stage for 24 hours. Cooling from 1350 ℃ to 50 ℃ at a speed of 2.5 ℃/min after the heat preservation is finished, and naturally cooling to room temperature along with a furnace. Taking out the powder and grinding for 15min to obtain Gd 2 CoMn 0.9 Ti 0.1 O 6 And (3) a ceramic sample.
Example 2
Ti doped Gd 2 CoMn 1-x Ti x O 6 Double perovskite type ceramic material Gd 2 CoMn 1-x Ti x O 6 (x=0.2), the preparation process comprises the following steps:
(1) Sequentially weighing 0.0005mol of nano titanium dioxide, 0.002mol of manganese carbonate, 0.0025mol of cobalt oxide and 0.0025mol of gadolinium oxide by using a high-precision electronic balance, placing the materials in an agate mortar, and grinding for 1.7h to uniformly mix the materials.
(2) And (3) carrying out heat treatment on the powder material which is ground and uniformly mixed in the step (1) in the air, heating to 1000 ℃ at 7 ℃/min, carrying out first-stage heat preservation, keeping for 24 hours, naturally cooling to room temperature along with a furnace to obtain black powder, and carrying out intermediate grinding on the obtained powder for 1.3 hours.
(3) Heating the powder subjected to intermediate grinding in the step (2) to 1200 ℃ in air at a speed of 7 ℃/min, performing heat preservation in the second stage for heat treatment for 24 hours, naturally cooling to room temperature along with a furnace to obtain black powder, and fully grinding the powder for 1.3 hours.
(4) And (3) sintering the fully ground powder in the step (3) at a high temperature, heating to 1350 ℃ at a speed of 7 ℃/min, and performing heat preservation in a third stage for 24 hours. Cooling from 1350 ℃ to 50 ℃ at a speed of 2 ℃/min after the heat preservation is finished, and naturally cooling to room temperature along with a furnace. Taking out the powder and grinding for 20min to obtain Gd 2 CoMn 0.8 Ti 0.2 O 6 And (3) a ceramic sample.
Example 3
Ti doped Gd 2 CoMn 1-x Ti x O 6 Double perovskite type ceramic material Gd 2 CoMn 1-x Ti x O 6 (x=0.3), the preparation process comprises the following steps:
(1) Sequentially weighing 0.00075mol of nano titanium dioxide, 0.00175mol of manganese carbonate, 0.0025mol of cobalt oxide and 0.0025mol of gadolinium oxide by using a high-precision electronic balance, putting the materials into an agate mortar, and grinding for 1.8h to uniformly mix the materials.
(2) And (3) carrying out heat treatment on the powder material which is ground and uniformly mixed in the step (1) in the air, heating to 1025 ℃ at 8 ℃/min, carrying out first-stage heat preservation for 24 hours, naturally cooling to room temperature along with a furnace to obtain black powder, and carrying out intermediate grinding on the obtained powder for 1.4 hours.
(3) Heating the powder subjected to intermediate grinding in the step (2) to 1225 ℃ in air at a speed of 8 ℃/min, performing heat treatment in a second-stage heat preservation for 24 hours, naturally cooling to room temperature along with a furnace to obtain black powder, and fully grinding the powder for 1.4 hours.
(4) And (3) sintering the fully ground powder in the step (3) at a high temperature, heating to 1350 ℃ at a speed of 8 ℃/min, and performing heat preservation in a third stage for 24 hours. Cooling from 1350 ℃ to 50 ℃ at a speed of 1.5 ℃/min after the heat preservation is finished, and naturally cooling to room temperature along with a furnace. Taking out the powder and grinding for 25min to obtain Gd 2 CoMn 0.7 Ti 0.3 O 6 And (3) a ceramic sample.
Example 4
Ti doped Gd 2 CoMn 1-x Ti x O 6 Double perovskite type ceramic material Gd 2 CoMn 1-x Ti x O 6 (x=0.4), the preparation process comprises the following steps:
(1) Sequentially weighing 0.001mol of nano titanium dioxide, 0.0015mol of manganese carbonate, 0.0025mol of cobalt oxide and 0.0025mol of gadolinium oxide by using a high-precision electronic balance, placing the materials in an agate mortar, and grinding for 2 hours to uniformly mix the materials.
(2) And (3) carrying out heat treatment on the powder material which is ground and uniformly mixed in the step (1) in the air, heating to 1050 ℃ at 10 ℃/min, carrying out first-stage heat preservation for 24 hours, naturally cooling to room temperature along with a furnace to obtain black powder, and carrying out intermediate grinding on the obtained powder for 1.5 hours.
(3) Heating the powder subjected to intermediate grinding in the step (2) to 1250 ℃ in air at a speed of 10 ℃/min, performing heat preservation in the second stage for 24 hours, naturally cooling to room temperature along with a furnace to obtain black powder, and fully grinding the powder for 1.5 hours.
(4) And (3) sintering the fully ground powder in the step (3) at a high temperature, heating to 1350 ℃ at a speed of 10 ℃/min, and performing heat preservation in a third stage for 24 hours. After the heat preservation is finished, the temperature is reduced from 1350 ℃ to 50 ℃ at a speed of 1 ℃/min, and then the temperature is naturally cooled to room temperature along with a furnace. Taking out the powder and grinding for 30min to obtain Gd 2 CoMn 0.6 Ti 0.4 O 6 And (3) a ceramic sample.
Comparative example 1
Gd 2 CoMnO 6 Double perovskite type ceramic material Gd 2 CoMn 1-x Ti x O 6 (x=0), the preparation process comprises the following steps:
(1) 0.0025mol of manganese carbonate, 0.0025mol of cobalt oxide and 0.0025mol of gadolinium oxide are weighed in sequence by a high-precision electronic balance and put into an agate mortar to be ground for 1.5 hours so as to uniformly mix the powder.
(2) And (3) carrying out heat treatment on the powder material which is ground and uniformly mixed in the step (1) in air, heating to 1000 ℃ at 5 ℃/min, keeping for 24 hours, naturally cooling to room temperature along with a furnace to obtain black powder, and carrying out intermediate grinding on the obtained powder for 1 hour.
(3) And (3) carrying out heat treatment on the powder subjected to intermediate grinding in the step (2) in air at a heating rate of 5 ℃/min for 24 hours at 1200 ℃, naturally cooling to room temperature along with a furnace to obtain black powder, and fully grinding the powder for 1 hour.
(4) And (3) sintering the fully ground powder in the step (3) at a high temperature, wherein the heating rate is 5 ℃/min, the sintering temperature is 1350 ℃, and the sintering time is 24 hours. After the heat preservation is finished, the temperature is reduced from 1350 ℃ to 50 ℃ at a speed of 1 ℃/min, and then the temperature is naturally cooled to room temperature along with a furnace. Taking out the powder and grinding for 10min to obtain Gd 2 CoMnO 6 And (3) a ceramic sample.
Experimental example
The double perovskite ceramic materials obtained in examples 1 to 4 and comparative example 1 were subjected to physical and chemical property characterization, and the results were as follows:
XRD patterns of the double perovskite-type ceramic materials obtained in examples 1 to 4 and comparative example 1 of the present invention were shown in fig. 1, and a Smartlab 9X-ray machine was used to obtain a ceramic material having a high-purity double perovskite-type ceramic material using a Cu-ka (45 kv,100ma,) The phase analysis is carried out on the sample, and the sample is crystallized into an orthorhombic crystal structure of the Pnma space group. The graph shows XRD pattern diffraction peaks of double perovskite ceramic materials corresponding to Ti doping amounts x of 0, 0.1, 0.2, 0.3 and 0.4 and Gd of an orthogonal structure 2 CoMnO 6 (PDF: 98-002-3562) diffraction peak kissThe mixture shows a single phase, and no impurity peak appears, indicating Ti 4+ Can completely replace Mn 4+ Into Gd 2 CoMnO 6 Is eliminated from the crystal lattice of the crystal.
Fig. 2 is a scanning electron microscope image of the double perovskite ceramic material obtained in examples 1 to 4 and comparative example 1, and the surface morphology of the double perovskite ceramic material is observed by using a field emission scanning electron microscope (FESEM, hitachi S-4800), wherein the double perovskite ceramic material has uniformly distributed particles, no obvious agglomeration phenomenon and random change of particle size, and the Ti doping amount x is 0, 0.1, 0.2, 0.3 and 0.4. Statistically, the average particle size of sample x=0 was 2.74 μm, the average particle size of sample x=0.1 was 2.05 μm, the average particle size of sample x=0.2 was 1.93 μm, the average particle size of sample x=0.3 was 1.82 μm, and the average particle size of sample x=0.4 was 1.68 μm. It can be seen that the average particle size decreases with increasing Ti doping content.
FIG. 3 shows the results of magnetization-temperature measurements of the double perovskite ceramic materials according to examples 1 to 4 and comparative example 1 of the present invention, wherein the magnetization of the samples was measured by using a PPMS-DynaCool-9T integrated property measuring system from Quantum Design, and the temperature-dependent DC magnetization-temperature curve (M-T) of the samples was measured in two modes of Zero Field Cooling (ZFC) and Field Cooling (FC) by using the integrated property measuring system (PPMS): in a ZFC measurement mode, the sample is cooled to 5K from room temperature under zero externally applied magnetic field, then a direct current magnetic field of 100Oe is applied, and data are acquired when the temperature is increased to 300K from 5K; in the FC mode, the sample is cooled from 300K to 5K under an applied magnetic field of 100 Oe. For Gd 2 CoMnO 6 (x=0), as shown in fig. 3 (a), as the temperature decreases to the curie temperature T c About 112K, the magnetization increases significantly with decreasing temperature, indicating that a transition from the high temperature paramagnetic state to the low temperature ferromagnetic state occurs around this temperature. This magnetic transition is mainly derived from Co 2+ -O 2- -Mn 4+ The hyperexchange interactions between ions follow the rule of Goodenough-Kanamori. With further decrease in temperature, the magnetization increases further and then starts to decrease, showing a broad peak centered at 47K, which indicates the systemCo is also present in 2 + -O 2- -Gd 3+ 、Mn 4+ -O 2- -Gd 3+ Antiferromagnetic effect caused by interactions between ions.
Furthermore, in the high temperature region, the FC curve and ZFC curve are substantially coincident, but separation begins to occur near-112K, below which the ZFC curve lies below the FC curve, i.e., in the low temperature region, and the difference between the two increases as the temperature decreases, further indicating the presence of antiferromagnetic interactions in the system. Magnetization of sample with Ti 4+ Is gradually decreased due to the increase of the doping amount of the nonmagnetic ion Ti 4+ Doping Co 2+ -O 2- -Mn 4+ The interaction between them is reduced. As shown in fig. 3 (f), the curie temperatures of the x=0, 0.1, 0.2, 0.3, and 0.4 samples were 112, 104, 97, 88, and 80K, respectively, and the curie temperature T c With Ti 4+ The increase in doping amount gradually decreases. Experiments show that the magnetic phase transition temperature of the material can be effectively regulated and controlled through Mn-site Ti doping.
Fig. 4 is a graph showing the hysteresis loop measurement results of the double perovskite ceramic materials according to examples 1 to 4 and comparative example 1, wherein the hysteresis loop of the x=0 sample is significantly hysteresis at 50K, and the magnetization is still not saturated when the applied magnetic field is as high as 5T, as can be seen from fig. 4 (a). With Ti 4+ The area enclosed by the hysteresis loop of the sample is smaller and smaller due to the Ti 4+ Doping to cause Co 2+ -O 2- -Mn 4+ Interaction is suppressed, resulting in weakening of ferromagnetism. As in fig. 4 (f), where x=0, 0.1, 0.2, 0.3, 0.4 coercive field (H c ) 7900, 4021, 2395, 2100 and 1762Oe, respectively, coercive field (H c ) With Ti 4+ The doping amount increases and gradually decreases. Experimental results show that the coercive field and the residual magnetization of the material can be effectively regulated and controlled by doping Mn site Ti.
In summary, the invention provides a Ti-doped Gd 2 CoMn 1-x Ti x O 6 The preparation method of the double perovskite type ceramic material adopts a standard solid phase reaction method to prepare the non-magnetic metal ion Ti dopedHetero Gd 2 CoMn 1-x Ti x O 6 The single-phase double perovskite ceramic material has the advantages of simple preparation method, easy control of the proportion of each component of a sample, no need of adding a solvent, easy operation of equipment, no need of introducing a reaction atmosphere, easy collection of products and capability of mass preparation. The Ti doped Gd prepared by the invention 2 CoMn 1-x Ti x O 6 3d-3d interaction, 3d-4f interaction, inversion disorder degree and octahedral distortion in crystal lattice on the B '/B' position can be regulated, and the magnetic phase transition temperature, coercive force and residual magnetization of the material can be obviously regulated. Gd (Gd) 2 CoMn 1-x Ti x O 6 Ti doping with different Mn contents can effectively regulate and control the macroscopic magnetic property of the material, and has great significance in the aspects of spintronics and the like.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (8)
1. Ti doped Gd 2 CoMn 1-x Ti x O 6 The preparation method of the double perovskite ceramic material is characterized by comprising the following steps of:
(1) Putting nano titanium dioxide, manganese carbonate, cobalt oxide and gadolinium oxide into a mortar, and grinding to uniformly mix the powder;
(2) Carrying out heat treatment on the powder material which is ground and uniformly mixed in the step (1), and heating to a temperature T 1 Then entering a first stage for heat preservation, naturally cooling to room temperature along with a furnace after heat preservation is finished, and grinding the obtained powder;
(3) Raising the temperature of the powder ground in the step (2) to a temperature T again 2 Performing heat preservation in the second stage, naturally cooling to room temperature along with a furnace after heat preservation is finished, and grinding the obtained powder;
(4) Sintering the powder with the ground thickness in the step (3) at a high temperature, and heating to a sintering temperature T 3 Then enter the third stage to keep warm; protection deviceCooling after finishing the temperature, and grinding the obtained powder to obtain a final product;
wherein in step (2), the temperature T 1 The temperature is 950-1050 ℃ and the heat preservation time is 24 hours; in step (3), the temperature T 2 The temperature is 1150-1250 ℃ and the heat preservation time is 24 hours; in step (4), the temperature T 3 The temperature is 1350 ℃ and the heat preservation time is 24 hours.
2. Ti-doped Gd according to claim 1 2 CoMn 1-x Ti x O 6 The preparation method of the double perovskite ceramic material is characterized in that the molar ratio of nano titanium dioxide, manganese carbonate, cobalt oxide and gadolinium oxide in the step (1) is (0.1-0.4) to (0.6-0.9) to 1:1.
3. Ti-doped Gd according to claim 1 2 CoMn 1-x Ti x O 6 The preparation method of the double perovskite ceramic material is characterized in that the heating rate of the step (2) is 5-10 ℃/min.
4. Ti-doped Gd according to claim 1 2 CoMn 1-x Ti x O 6 The preparation method of the double perovskite ceramic material is characterized in that the heating rate of the step (3) is 5-10 ℃/min.
5. Ti-doped Gd according to claim 1 2 CoMn 1-x Ti x O 6 The preparation method of the double perovskite ceramic material is characterized in that the heating rate of the step (4) is 5-10 ℃/min.
6. Ti-doped Gd according to claim 1 2 CoMn 1-x Ti x O 6 The preparation method of the double perovskite ceramic material is characterized in that the cooling stage in the step (4) firstly reduces the temperature to 50 ℃ at the speed of 1-3 ℃/min, and then naturally cools the ceramic material to room temperature along with a furnace.
7. Ti-doped Gd according to claim 1 2 CoMn 1-x Ti x O 6 The preparation method of the double perovskite ceramic material is characterized in that the grinding time of the step (1) is 1.5-2h, the grinding time of the step (2) and the grinding time of the step (3) are 1-1.5h, and the grinding time of the step (4) is 10-30min.
8. Ti doped Gd 2 CoMn 1-x Ti x O 6 A double perovskite ceramic material, characterized in that it is prepared by the method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111435291.3A CN114031122B (en) | 2021-11-29 | 2021-11-29 | Ti doped Gd 2 CoMn 1-x Ti x O 6 Double perovskite type ceramic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111435291.3A CN114031122B (en) | 2021-11-29 | 2021-11-29 | Ti doped Gd 2 CoMn 1-x Ti x O 6 Double perovskite type ceramic material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114031122A CN114031122A (en) | 2022-02-11 |
| CN114031122B true CN114031122B (en) | 2023-08-22 |
Family
ID=80145889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111435291.3A Active CN114031122B (en) | 2021-11-29 | 2021-11-29 | Ti doped Gd 2 CoMn 1-x Ti x O 6 Double perovskite type ceramic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114031122B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3401018A1 (en) * | 2017-05-12 | 2018-11-14 | Leibnitz-Institut für Festkörper- und Werkstoffforschung Dresden e.V. | Method, device and arrangement for filtration of magnetic particles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106653264B (en) * | 2016-11-28 | 2019-05-10 | 宁波科星材料科技有限公司 | A kind of SmCo based composite magnetic material preparation method and SmCo based composite magnetic material |
-
2021
- 2021-11-29 CN CN202111435291.3A patent/CN114031122B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3401018A1 (en) * | 2017-05-12 | 2018-11-14 | Leibnitz-Institut für Festkörper- und Werkstoffforschung Dresden e.V. | Method, device and arrangement for filtration of magnetic particles |
Non-Patent Citations (1)
| Title |
|---|
| Giant magnetocaloric effect in Gd2NiMnO6 and Gd2CoMnO6 ferromagnetic insulators;J. Krishna Murthy et al.;J. Phys. D: Appl. Phys.;第48卷(第35期);1-14 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114031122A (en) | 2022-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Park et al. | Composition-dependent magnetic properties of BiFeO 3-BaTiO 3 solid solution nanostructures | |
| Kumar et al. | Effect of lattice strain on structural and magnetic properties of Ca substituted barium hexaferrite | |
| Zhong et al. | Preparation and magnetic properties of barium hexaferrite nanoparticles produced by the citrate process | |
| Yu et al. | Effects of pH and citric acid contents on characteristics of ester-derived BaFe12O19 powder | |
| Kang | High saturation magnetization in La–Ce–Zn–doped M-type Sr-hexaferrites | |
| Rehman et al. | Magnetic properties of Ce doped M-type strontium hexaferrites synthesized by ceramic route | |
| Thomas et al. | Comparative study of the structural and magnetic properties of alpha and beta phases of lithium ferrite nanoparticles synthesized by solution combustion method | |
| Troyanchuk et al. | Magnetic phase diagrams of the Ln (Mn 1− x Co x) O 3 (Ln= Eu, Nd, Y) systems | |
| Li et al. | Effect of Fe substitution on structure and exchange interactions within and between the sublattices of frustrated CoCr 2 O 4 | |
| Jia et al. | Effect of sintering temperature on microstructure and magnetic properties of double perovskite Y2CoMnO6 | |
| Yuping et al. | Effect of K2CO3 addition on the microstructure and magnetic properties of Sr-Ferrites | |
| Tian et al. | Synthesis and magnetic properties of vanadium doped anatase TiO2 nanoparticles | |
| Troyanchuk et al. | Magnetic ordering in perovskites containing manganese and cobalt | |
| CN114031122B (en) | Ti doped Gd 2 CoMn 1-x Ti x O 6 Double perovskite type ceramic material and preparation method thereof | |
| Liu et al. | Synthesis of nanocrystalline Zn0. 5Mn0. 5Fe2O4 via in situ polymerization technique | |
| Shukla et al. | Structural and magnetic characterization of spin canted mixed ferrite-cobaltites: LnFe0. 5Co0. 5O3 (Ln= Eu and Dy) | |
| Jian-Ping et al. | Structural and magnetic properties of Fe-doped anatase TiO2 films annealed in vacuum | |
| Panda et al. | Insights on the role of defects on the magnetic and magneto electric coupling effects in nano BiFeO3 | |
| Pourroy et al. | Low temperature syntheses of NbFeO4 and TaFeO4: influence of recrystallization on the magnetic properties | |
| Zhang et al. | Extrinsic negative magnetization and exchange bias: Impact of the SmCrO3 particle size | |
| Ferreira et al. | Effects of laser floating zone processing on electrical and magnetic properties of (Ca, Pr) MnO3 system | |
| Yamaguchi et al. | Magnetic properties of iron-boron-oxide and iron-phosphor-oxide glasses prepared by sol-gel method | |
| Shi et al. | The evolution of structure and magnetic properties of GdCr1-xFexO3 (0≤ x≤ 0.5) polycrystalline samples | |
| Hessien et al. | Low-Temperature Synthesis of Nanocrystalline Mn 0.2 Ni 0.8 Fe2O 4 by Oxalate Precursor Route | |
| Vedmid’ et al. | Structural and Magnetic Characteristics of Gadolinium Manganite Modified with Barium Gd0. 9Ba0. 1MnO3 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |