CN112979280A - Cr-doped YMnO3Magnetic material and annealing method thereof - Google Patents

Cr-doped YMnO3Magnetic material and annealing method thereof Download PDF

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CN112979280A
CN112979280A CN202110241688.2A CN202110241688A CN112979280A CN 112979280 A CN112979280 A CN 112979280A CN 202110241688 A CN202110241688 A CN 202110241688A CN 112979280 A CN112979280 A CN 112979280A
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magnetic material
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万凤
曹崇德
白晓军
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Northwestern Polytechnical University
Xianyang Normal University
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Xianyang Normal University
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Abstract

The invention discloses Cr-doped YMnO3An annealing method of a magnetic material belongs to the technical field of magnetic materials. The method comprises the following steps: powder-providing Cr-doped YMnO3A magnetic material; doping Cr in the powder with YMnO3And pressing and forming the magnetic material, placing the magnetic material in air, sintering the magnetic material for 4-8 h at 1100-1450 ℃, then placing the magnetic material in an oxygen atmosphere, and annealing the magnetic material for 18-48 h at 1200-1350 ℃ to obtain the annealed magnetic material. The invention provides a method for doping YMnO into Cr in an oxygen atmosphere3The magnetic material is annealed, so that the ferromagnetic content of the magnetic material can be greatly improvedEffectively enhance the magnetic performance of the magnetic material.

Description

Cr-doped YMnO3Magnetic material and annealing method thereof
Technical Field
The invention belongs to the technical field of magnetic materials, and particularly relates to Cr-doped YMnO3Magnetic materialAnd an annealing method thereof.
Background
The multiferroic material integrates ferroelectricity and ferromagnetism, and the magnetoelectric coupling effect between the multiferroic material and the ferromagnetism can realize the mutual regulation and control of the ferroelectricity and the ferromagnetism, so that the multiferroic material becomes one of the research hotspots of material science. Hexagonal yttrium manganate (YMnO)3) Is one of multiferroic materials which are currently in great interest, and has a ferroelectric transition temperature of 900K and an antiferromagnetic transition temperature of 70K. Because the multiferroic property of the material is the coexistence of antiferromagnetic order and ferroelectricity, the material is not very sensitive to external magnetic fields, and the practical application of the material is limited. To enhance its ferromagnetic properties, many researchers have focused on YMnO3Mn site ion doping is performed in an attempt to introduce ferromagnetic double-exchange or tilted antiferromagnetic states into the system. By doping element in YMnO3Introducing Mn therein4+Ion generation of Mn3+-O2--Mn4+Superexchange due to Mn3+-O2--Mn4+And Mn4+-O2--Mn3+The energy between is degenerate. However, the energy between Mn ions and doping element ions is not degenerated because the electrostatic potential of ions of different elements cannot be completely the same; in addition, some researchers say that ferromagnetic double exchange effect exists between Mn-site doped transition metal ions and Mn ions, but it is also considered that the ferromagnetic component is increased only due to antiferromagnetic inclination caused by doping, and no theory is given according to the current research. From the above situation, the Cr ion is selected as the Mn site replacement ion, mainly due to Cr3+Ions and Mn3+Having the same valence state but different effective magnetic moment, but which is different from Mn4+The ions have the same electronic configuration t2g 3eg0 and similar ionic radius, and only one eg0 orbit is introduced into the system, which is convenient for research on YMnO3The mechanism of multiferroic properties. YMnO on the other hand3Oxygen vacancies are easy to form after high-temperature sintering, the concentration of the oxygen vacancies influences the valence state distribution of Mn and Cr ions under the condition of maintaining charge balance, and further YMn is subjected to0.9Cr0.1O3The magnetic properties of the ceramic are affected. In addition, the magnetic exchange between Mn ion and Cr ion is oxygen ionThe change of oxygen vacancy concentration can affect the magnetic exchange coupling effect of the ceramic.
Disclosure of Invention
The present invention is directed to providing a Cr-doped YMnO, which overcomes the disadvantages and shortcomings of the above-mentioned methods3Magnetic materials and annealing methods thereof. The method comprises the steps of doping YMnO into Cr in an oxygen atmosphere3The magnetic material is annealed, so that the ferromagnetic content of the magnetic material can be greatly improved, and the magnetic performance of the magnetic material is effectively enhanced.
The first purpose of the invention is to provide Cr-doped YMnO3The annealing method of the magnetic material comprises the following steps:
powder-providing Cr-doped YMnO3A magnetic material;
doping Cr in the powder with YMnO3And pressing and forming the magnetic material, placing the magnetic material in air, sintering the magnetic material for 4-8 hours at 1100-1450 ℃, and then placing the magnetic material in an oxygen atmosphere to anneal the magnetic material for 18-48 hours at 1200-1400 ℃ to obtain the annealed magnetic material.
Preferably, the sintering temperature is 1300-1400 ℃.
Preferably, the annealing temperature is 1350 ℃.
Preferably, the Cr is doped with YMnO3The magnetic material being YMn0.9Cr0.1O3、YMn0.8Cr0.2O3Or YMn0.7Cr0.3O3A magnetic material.
More preferably, the Cr is doped with YMnO3Magnetic material the magnetic material is made by a solid phase sintering process.
More preferably, the Cr is doped with YMnO3Magnetic material the magnetic material is prepared by the following steps:
with Y2O3，MnO2And Cr2O3Uniformly mixing the powder serving as a raw material, presintering the mixture for 12 hours at 1110 ℃ in the air, ball-milling the sintered compound into powder, and then continuously presintering the powder for 12 hours at 1110 ℃ in the air; thus obtaining Cr-doped YMnO3A magnetic material.
The second object of the present inventionProviding a Cr-doped YMnO3A magnetic material.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides Cr-doped YMnO3Annealing method of magnetic material by doping Cr with YMnO in oxygen atmosphere3The magnetic material is annealed, so that the ferromagnetic content of the magnetic material can be greatly improved, and the magnetic performance of the magnetic material is effectively enhanced; and certain theoretical and technical foundation is laid for further developing novel multiferroic materials.
Drawings
FIG. 1 is the example of Cr-doped YMnO3A preparation flow chart of the magnetic material.
FIG. 2 is a M-T graph and a derivative of magnetization (dM/dT) with temperature T of the magnetic material provided in example 1 and comparative examples 1-2 in Zero Field Cooling (ZFC) and Field Cooling (FC) modes, wherein FIG. 2a is the M-T graph of the magnetic material provided in example 1 in ZFC and FC modes, and the insets are a temperature change curve of the reciprocal of the sample magnetic susceptibility in FC mode and a Curie-Weiss fitting graph in a high temperature region; FIG. 2b is a graph of M-T curves of the magnetic material provided in comparative example 1 in ZFC and FC modes, and a graph of a temperature change curve of reciprocal magnetic susceptibility of the sample in FC mode and a Curie-Weiss fitting curve of a high temperature zone; FIG. 2c is a graph of M-T curves of the magnetic material provided in comparative example 2 in ZFC and FC modes, and a graph of a temperature change curve of the reciprocal of the magnetic susceptibility of the sample in FC mode and a Curie-Weiss fitting curve of the high temperature zone; FIG. 2d is a graph showing the variation of the derivative of magnetization (dM/dT) with temperature T in the temperature range of 50-125K for ZFC as the magnetic material provided in example 1 and comparative examples 1-2.
Fig. 3 is an XPS spectrum of the 2p orbitals of Mn in the magnetic materials provided in example 1 and comparative example 1; fig. 3a is an XPS spectrum of the 2p orbital of Mn in the magnetic material provided in example 1; fig. 3b is an XPS spectrum of the 2p orbital of Mn in the magnetic material provided in example 1.
FIG. 4 shows YMn treated in example 1 and comparative examples 1 and 20.9Cr0.1O3XPS spectra of the 1s orbit of O in magnetic material.
Detailed Description
In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described below with reference to the following specific embodiments and the accompanying drawings, but the embodiments are not meant to limit the present invention.
In the following examples, reagents and materials were used and were commercially available without specific reference.
YMn used in the following examples0.9Cr0.1O3The magnetic material is prepared according to the following steps:
step 1: with high purity Y2O3，MnO2And Cr2O3The raw materials are mixed according to a molar ratio and then put into a ball milling tank, and the mixture is ball milled for 12 hours by taking ethanol as a solvent, discharged and dried. Before weighing, the required raw materials are dried at 75 ℃ to ensure that the powder is dry;
step 2: putting the mixed and dried powder into a high-temperature sintering furnace, and presintering the powder in air at 1110 ℃ for 12 hours;
and step 3: ball-milling the pre-sintered powder for the second time, and pre-sintering the powder in the air at 1110 ℃ for 12 hours to obtain YMn0.9Cr0.1O3A magnetic material.
Example 1
Cr-doped YMnO3The annealing method of the magnetic material, as shown in fig. 1, comprises the following steps:
weighing YMn0.9Cr0.1O3A magnetic material;
mixing YMn of the powder0.9Cr0.1O3Adding 20 Vol% polyvinyl alcohol into the magnetic material, mixing, pressing under 7MPa to obtain disc blank with diameter of about 10mm and thickness of about 2mm, and maintaining the pressure for not less than 5 min; placing in air, sintering at 1350 deg.C for 6h, and keeping at 500 deg.C for 2 hr to discharge organic substances such as polyvinyl alcohol; then placing the mixture in an oxygen atmosphere, and annealing the mixture for 30 hours at 1350 ℃ to obtain annealed YMn0.9Cr0.1O3A magnetic material.
Example 2
Cr-doped YMnO3A method of annealing a magnetic material thereof, comprising the steps of:
preparation of YMn powder0.9Cr0.1O3Magnetic material:
mixing YMn of the powder0.9Cr0.1O3Adding 20 Vol% polyvinyl alcohol into the magnetic material, mixing, pressing under 6Mpa to obtain wafer blank with diameter of about 10mm and thickness of about 2mm, and maintaining the pressure for not less than 5 min; placing in air, sintering at 1300 deg.C for 6h, placing in oxygen atmosphere, and annealing at 1350 deg.C for 18h to obtain annealed YMn0.9Cr0.1O3A magnetic material.
Example 3
Cr-doped YMnO3A method of annealing a magnetic material thereof, comprising the steps of:
preparation of YMn powder0.9Cr0.1O3Magnetic material:
mixing YMn of the powder0.9Cr0.1O3Adding 20 Vol% polyvinyl alcohol into the magnetic material, mixing, pressing under 8Mpa to obtain wafer blank with diameter of about 10mm and thickness of about 2mm, and maintaining the pressure for not less than 5 min; placing in air, sintering at 1150 deg.C for 8h, and annealing at 1200 deg.C for 48h in oxygen atmosphere to obtain annealed YMn0.9Cr0.1O3A magnetic material.
Example 4
Cr-doped YMnO3A method of annealing a magnetic material thereof, comprising the steps of:
preparation of YMn powder0.9Cr0.1O3Magnetic material:
mixing YMn of the powder0.9Cr0.1O3Adding 20 Vol% polyvinyl alcohol into the magnetic material, mixing, pressing under 7MPa to obtain disc blank with diameter of about 10mm and thickness of about 2mm, and maintaining the pressure for not less than 5 min; placing in air, sintering at 1450 deg.C for 4 hr, placing in oxygen atmosphere, and annealing at 1300 deg.C for 36 hr to obtain the final productAnnealed YMn0.9Cr0.1O3A magnetic material.
Comparative example 1
The same as in example 1 except that the oxygen atmosphere was replaced with a nitrogen atmosphere.
Comparative example 2
The same as in example 1, except that the oxygen atmosphere was replaced with Air atmosphere (Air).
To illustrate the invention, the Cr-doped YMnO is provided3The correlation performance of the magnetic material obtained by the annealing method of the magnetic material was only tested on the magnetic materials provided in example 1 and comparative examples 1 to 2, as shown in fig. 2 and 3.
FIG. 2 is a M-T graph and a derivative of magnetization (dM/dT) with temperature T of the magnetic material provided in example 1 and comparative examples 1-2 in Zero Field Cooling (ZFC) and Field Cooling (FC) modes, wherein FIG. 2a is the M-T graph of the magnetic material provided in example 1 in ZFC and FC modes, and the insets are a temperature change curve of the reciprocal of the sample magnetic susceptibility in FC mode and a Curie-Weiss fitting graph in a high temperature region; FIG. 2b is a graph of M-T curves of the magnetic material provided in comparative example 1 in ZFC and FC modes, and a graph of a temperature change curve of reciprocal magnetic susceptibility of the sample in FC mode and a Curie-Weiss fitting curve of a high temperature zone; FIG. 2c is a graph of M-T curves of the magnetic material provided in comparative example 2 in ZFC and FC modes, and a graph of a temperature change curve of the reciprocal of the magnetic susceptibility of the sample in FC mode and a Curie-Weiss fitting curve of the high temperature zone; FIG. 2d is a graph showing the variation of the derivative of magnetization (dM/dT) with temperature T in the temperature range of 50-125K for ZFC as the magnetic material provided in example 1 and comparative examples 1-2.
As can be seen from fig. 2, the interpolated graphs in fig. 2(a) - (c) are the curves of the inverse susceptibility and the temperature under different annealing atmospheres, respectively. Fitting the reciprocal of the magnetic susceptibility and the temperature to obtain a straight line at a temperature of more than 150K, and calculating Air and O2And N2Atmosphere annealing and YMn in air0.9Cr0.1O3The Curie-Weiss temperatures of the ceramic samples were-76.48K, -47.45K and-139.41K, respectively, and the Curie-Weiss temperatures were all negativeIndicating that the antiferromagnetic property inside the sample plays a dominant role. However, different atmosphere annealing has an effect on the ferromagnetic content inside the sample, where O2Atmosphere annealed samples with highest ferromagnetic content, N2The ferromagnetic content of the atmosphere annealed samples was the lowest. In addition, from the results of the temperature derivative (dM/dT) of magnetization in the 50-125K temperature range in the ZFC mode shown in FIG. 2(d), it was found that the antiferromagnetic transition temperature T was observed in three casesNIs expressed as TN(O2)>TN(Air)>TN(N2) Likewise indicates O2The ferromagnetic content of the atmosphere annealed samples was highest.
Fig. 3 is an XPS spectrum of the 2p orbitals of Mn in the magnetic materials provided in example 1 and comparative example 1; fig. 3a is an XPS spectrum of the 2p orbital of Mn in the magnetic material provided in example 1; fig. 3b is an XPS spectrum of the 2p orbital of Mn in the magnetic material provided in example 1.
As can be seen from FIG. 3, FIG. 3 is at O2And N2Atmosphere annealed YMn0.9Cr0.1O3XPS spectra of the Mn2p orbital of the ceramic sample after C1s correction. The results of the peak areas of the fitting sub-peaks are compared to obtain the results of FIG. 3(a) at O2Annealing treated YMn in atmosphere0.9Cr0.1O3Mn in ceramic sample3+63.37% of Mn4+Is 36.63%, and FIG. 3(b) is N2YMn after atmosphere annealing0.9Cr0.1O3XPS spectrum fitting results of Mn2p orbits of ceramic samples, and YMn is obtained by comparing areas of peaks0.9Cr0.1O3Mn in ceramic samples2+，Mn3+And Mn4+The proportions were 24.67%, 54.68% and 20.66%, respectively, and this result indicated Mn in the interior of the sample3+And Mn4+The content is greatly reduced, and a large amount of Mn appears2+Ions. From this it can be deduced that N2The magnetic properties of the atmosphere annealed sample become complicated because not only Mn is present in the system3+-O2--Mn4+And Mn2+-O2--Mn3+And an antiferromagnetic exchange exists between cations of the same species.
As can be seen from the measurement results of fig. 2(a) - (c), the maximum magnetization of the sample does not change very significantly; however, it can be observed from the results of the magnetization derivative versus temperature curves for the three treatment conditions given in FIG. 3(d)2Antiferromagnetic transition temperature in annealing atmosphere is higher than that of O2The antiferromagnetic transition temperature of the atmosphere annealed and non-atmosphere treated samples was reduced to 75K, which is clearly the strongest antiferromagnetic exchange among the three samples, indicating N2Annealing enhances the antiferromagnetic exchange between the same cations.
FIG. 4 shows YMn treated in example 1 and comparative examples 1 and 20.9Cr0.1O3XPS spectra of the 1s orbit of O in magnetic material.
As can be seen from FIG. 4, in the air annealing atmosphere and O2The annealing treatment of O1s spectral line respectively comprises two peaks, the main peak is located at binding energy of 529.0eV, the peak is a normal peak of the formed compound, and in addition, a binding energy of 531.3eV (air) and 531.0eV (O) respectively exist near the main peak2) Sub-peak of (A)u. Main peak and OuDifference of binding energy corresponding to peak Δ E from O2The reduction of 2.3eV in the annealing atmosphere to 2.0eV without atmosphere treatment is demonstrated in O2The annealing treatment contributes to the reduction of the oxygen vacancy concentration. However for N2YMn under annealing atmosphere treatment0.9Cr0.1O3Ceramic sample, main peak located at 530.7eV binding energy, with O2529eV of atmosphere annealing treatment and air atmosphere treatment was reduced by 1.7eV, and OuThe peak disappeared. The decrease in binding energy of the main peak is illustrated in N2YMn under annealing atmosphere treatment0.9Cr0.1O3Oxygen vacancies are more easily formed in the sample. The increase in the concentration of oxygen vacancies in the sample leads to a large reduction in ferromagnetism, and hence in N2YMn under annealing atmosphere treatment0.9Cr0.1O3The corresponding decrease in antiferromagnetic transition temperature, i.e., an increase in the concentration of oxygen vacancies in the manganese oxide, results in reduced ferromagnetism, increased antiferromagnetic and increased magnetic anisotropy.
In summary, the present invention provides a Cr-doped alloyYMnO3Annealing method of magnetic material, in oxygen atmosphere, Cr is doped with YMnO3The magnetic material is annealed, so that the ferromagnetic content of the magnetic material can be greatly improved, and the magnetic performance is effectively enhanced; and certain theoretical and technical foundation is laid for further developing novel multiferroic materials.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the appended claims and their equivalents.

Claims (7)

1. Cr-doped YMnO3The annealing method of the magnetic material is characterized by comprising the following steps of:
powder-providing Cr-doped YMnO3A magnetic material;
doping Cr in the powder with YMnO3And pressing and forming the magnetic material, placing the magnetic material in air, sintering the magnetic material for 4-8 hours at 1100-1450 ℃, and then placing the magnetic material in an oxygen atmosphere to anneal the magnetic material for 18-48 hours at 1200-1400 ℃ to obtain the annealed magnetic material.
2. The Cr-doped YMnO of claim 13The annealing method of the magnetic material is characterized in that the sintering temperature is 1300-1400 ℃.
3. The Cr-doped YMnO of claim 13The annealing method of the magnetic material is characterized in that the annealing temperature is 1350 ℃.
4. The Cr-doped YMnO of claim 13The annealing method of the magnetic material is characterized in that the Cr is doped with YMnO3The magnetic material being YMn0.9Cr0.1O3、YMn0.8Cr0.2O3Or YMn0.7Cr0.3O3A magnetic material.
5. According to the claimsObtaining 4 the Cr-doped YMnO3The annealing method of the magnetic material is characterized in that the Cr is doped with YMnO3The magnetic material is produced by a solid-phase sintering method.
6. The Cr-doped YMnO of claim 53The annealing method of the magnetic material is characterized in that the Cr is doped with YMnO3The magnetic material is prepared by the following steps:
with Y2O3，MnO2And Cr2O3Uniformly mixing the powder serving as a raw material, presintering the mixture for 12 hours at 1110 ℃ in the air, ball-milling the sintered compound into powder, and then continuously presintering the powder for 12 hours at 1110 ℃ in the air; thus obtaining Cr-doped YMnO3A magnetic material.
7. Cr-doped YMnO prepared by the method of any one of claims 1 to 63A magnetic material.
CN202110241688.2A 2021-03-04 2021-03-04 Cr-doped YMnO3Magnetic material and annealing method thereof Pending CN112979280A (en)

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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN102910913A (en) * 2012-09-26 2013-02-06 河南科技大学 Preparation process of YMnO3 dielectric ceramic and YMnO3 dielectric ceramic capacitor
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Publication number Priority date Publication date Assignee Title
CN102910913A (en) * 2012-09-26 2013-02-06 河南科技大学 Preparation process of YMnO3 dielectric ceramic and YMnO3 dielectric ceramic capacitor
US20190348201A1 (en) * 2017-06-20 2019-11-14 Shibaura Electronics Co., Ltd. Thermistor sintered body and thermistor element

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