CN108726877B - High-temperature spinning glass Ca3CoMnO6Preparation method of (1) - Google Patents

High-temperature spinning glass Ca3CoMnO6Preparation method of (1) Download PDF

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CN108726877B
CN108726877B CN201810616451.6A CN201810616451A CN108726877B CN 108726877 B CN108726877 B CN 108726877B CN 201810616451 A CN201810616451 A CN 201810616451A CN 108726877 B CN108726877 B CN 108726877B
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CN108726877A (en
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龚高尚
王永强
谢罗刚
郭锦锦
苏玉玲
龚庆华
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Zhengzhou University of Light Industry
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/60—Silica-free oxide glasses

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Abstract

The invention discloses high-temperature spin glass Ca3CoMnO6The preparation method comprises dissolving citric acid in distilled water, adding CaCO3、C4H6CoO4·4H2O and C4H6MnO4·4H2Stirring and mixing the mixture O evenly to obtain a mixed solution; adding nitric acid to adjust the pH value of the mixed solution to 3-4; adding glycol to enhance the viscosity of the solution, and stirring for 2 hours at room temperature by magnetic force to fully mix; heating the solution in a water bath at 95-100 deg.C to form a jelly-like wet gel; drying the wet gel in a constant-temperature drying box at the temperature of 150-; fully grinding, pre-sintering, secondary grinding and sintering the xerogel to prepare the high-temperature spinning glass Ca3CoMnO6The crystal has a single-phase rhombic structure, the sample particles are uniform in size, the obvious spin glass characteristic is shown at a high temperature, the preparation process is simple, the cost is low, and mass preparation and production can be realized.

Description

High-temperature spinning glass Ca3CoMnO6Preparation method of (1)
Technical Field
The invention belongs to the technical field of multiferroic ceramic materials and magnetic materials, and particularly relates to high-temperature spin glass Ca3CoMnO6The preparation method of (1).
Background
Multiferroic materials refer to materials that have two or more ferroic orders at the same time. The development of multiferroic materials has enabled the simultaneous manipulation of multiple properties in one material. Particularly, the magnetoelectric multiferroic material has ferromagnetism and ferroelectricity simultaneously, so that the coupling between the ferromagnetic and the ferroelectric ordering has important application in the aspect of miniaturization of devices, and the multi-state storage of data is possible. For example, most of current data storage is magnetic storage, and the storage state of the data storage is only + M and-M states, so that the current computers and the like are 2-system storage. When the multiferroic material is applied to data storage, the four-state storage of data can be realized, namely (+ M, + P), (+ M, -P), (-M, + P), (-M, -P); the density of magnetic storage can be greatly improved. In addition, based on the magnetoelectric coupling effect of the multiferroic material, ferroelectric writing can be adopted during data writing, and magnetic reading is adopted during reading, so that the defect of slow magnetic storage writing can be overcome, the generation of heat in the magnetic writing process can be effectively reduced, and the energy loss in the magnetic writing process is reduced. Ca3CoMnO6As a novel magnetoelectric multiferroic material, the ferroelectric polarization of the material comes from the exchange shrinkage of internal magnetic moments, and the material is theoretically predicted to have high polarization strength and strong magnetoelectric coupling and has wide application prospect.
However, from the results reported in the present experiments, Ca3CoMnO6The spontaneous polarization intensity is still lower than the theoretical value, and the application development is seriously hindered, which is the phenomenon and Ca3CoMnO6Closely related to the microscopic magnetic structure of (a). Therefore, if Ca can be treated3CoMnO6Effective regulation of magnetic order can increase Ca3CoMnO6The multiferroic material has multiferroic properties, and great help is provided for promoting the development and application of the multiferroic material.
Different from Ca in the previous report3CoMnO6The low-temperature antiferromagnetic structure is shown, and the Ca prepared by the invention3CoMnO6The material shows spin glass characteristics at higher temperature, and experiments prove that the preparation mode is used for Ca3CoMnO6Effectiveness of magnetic structure regulation.
Disclosure of Invention
The technical problem to be solved by the invention is to provide high-temperature spin glass Ca3CoMnO6The preparation method of (1) finds a Ca for regulating and controlling3CoMnO6New way of magnetic structure of material. Ca obtained by the production method of the present invention3CoMnO6The material crystallizes into a single-phase orthorhombic structure, the sample particles are uniform in size, and the spinning glass characteristic is shown at a higher temperature.
In order to solve the technical problems, the invention adopts the following technical scheme:
high-temperature spinning glass Ca3CoMnO6The preparation method comprises the following steps:
(1) dissolving citric acid in distilled water, and adding CaCO3、C4H6CoO4•4H2O and C4H6MnO4•4H2Stirring and mixing the mixture O evenly to obtain a mixed solution;
(2) adding nitric acid to adjust the pH value of the mixed solution to 3-4;
(3) adding glycol into the mixed solution after the pH value is adjusted to enhance the viscosity of the solution, and then, carrying out magnetic stirring for 2 hours at room temperature to fully mix;
(4) heating the solution in a water bath at 95-100 deg.C to obtain a jelly-like wet gel;
(5) drying the wet gel in a constant-temperature drying box at the temperature of 150-;
(6) fully grinding, pre-sintering, secondary grinding and sintering the xerogel to prepare the high-temperature spinning glass Ca3CoMnO6。
CaCO in the step (1)3、C4H6CoO4•4H2O and C4H6MnO4•4H2The amount of O is 3:1:1, and the amount of citric acid is CaCO3、C4H6CoO4•4H2O and C4H6MnO4•4H2The total amount of O substance is 1.2-1.5 times.
The concentration of the citric acid in the mixed solution in the step (1) is 1 g/mL.
The volume ratio of the glycol in the step (3) to the distilled water in the step (1) is (1-2) to 3.
The pre-sintering temperature in the step (6) is 800 ℃, and the pre-sintering time is 24 hours.
The sintering temperature in the step (6) is 970-1030 ℃, and the sintering time is 24 hours.
The high-temperature spin glass Ca3CoMnO6The high-temperature spin glass Ca prepared by the preparation method3CoMnO6The crystal is a single-phase rhombic structure, the sample particles are uniform in size, and the spin glass characteristic is shown at a high temperature of 172K.
The invention has the beneficial effects that: the high-temperature spin glass material Ca prepared by the invention3CoMnO6The crystal is a single-phase orthorhombic structure, the sample particles are uniform in size, and the obvious spin glass characteristic is shown at a higher temperature. In addition, the preparation process is simple, the cost is low, and mass production can be realized.
Drawings
FIG. 1 shows a high temperature spin glass Ca in example 1 of the present invention3CoMnO6XRD pattern of (a).
FIG. 2 shows a high temperature spin glass Ca in example 1 of the present invention3CoMnO6SEM spectrum of (d).
FIG. 3 shows Ca under different magnetic fields in example 1 of the present invention3CoMnO6Zero field cooling curve.
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
High-temperature spin glass Ca of the present example3CoMnO6The preparation method comprises the following steps:
(1) dissolving citric acid in distilled water, and adding CaCO with the amount ratio of 3:1:13、C4H6CoO4•4H2O and C4H6MnO4•4H2Stirring and mixing the mixture O uniformly to obtain a mixed solution, wherein the content of the citric acid is CaCO3、C4H6CoO4•4H2O and C4H6MnO4•4H21.3 times of the total amount of the O substances, and the concentration of the citric acid in the mixed solution is 1 g/mL;
(2) adding nitric acid to adjust the pH of the mixed solution to 3-4, wherein the volume ratio of the glycol to the distilled water in the step (1) is 1: 3;
(3) adding glycol into the mixed solution after the pH value is adjusted to enhance the viscosity of the solution, and then, carrying out magnetic stirring for 2 hours at room temperature to fully mix;
(4) heating the solution in a water bath at 100 deg.C to form a jelly-like gel;
(5) drying the wet gel in a constant-temperature drying box at 160 ℃ to obtain dry gel;
(6) fully grinding the xerogel, presintering for 24 hours at 800 ℃, secondarily grinding and sintering for 24 hours at 1000 ℃ to prepare the high-temperature spinning glass Ca3CoMnO6。
For the high temperature spin glass Ca prepared in the above example3CoMnO6The microstructure of the material sample is characterized by adopting an X-ray diffractometer (XRD) to analyze the phase of the material sample, and as can be seen from figure 1, the sample has sharp diffraction peak, good crystallization and no generation of other impurities.
FIG. 2 shows a high-temperature spin glass Ca3CoMnO6The SEM atlas of the material shows that the sample has uniform particle size and better crystallization.
FIG. 3 shows Ca under different magnetic fields3CoMnO6The chart of the zero field cooling curve shows that the freezing peak shifts to the low temperature direction along with the increase of the magnetic field of the sample. When the magnetic field is further increased, the frozen-in peak disappears, indicating its spin glass character.
Example 2
High-temperature spin glass Ca of the present example3CoMnO6The preparation method comprises the following steps:
(1) dissolving citric acid in distilled water, and adding CaCO with the amount ratio of 3:1:13、C4H6CoO4•4H2O and C4H6MnO4•4H2Stirring and mixing the mixture O uniformly to obtain a mixed solution, wherein the content of the citric acid is CaCO3、C4H6CoO4•4H2O and C4H6MnO4•4H21.2 times of the total amount of the O substances, and the concentration of the citric acid in the mixed solution is 1 g/mL;
(2) adding nitric acid to adjust the pH of the mixed solution to 3-4, wherein the volume ratio of the glycol to the distilled water in the step (1) is 2: 3;
(3) adding glycol into the mixed solution after the pH value is adjusted to enhance the viscosity of the solution, and then, carrying out magnetic stirring for 2 hours at room temperature to fully mix;
(4) heating the solution in a water bath at 95 deg.C to form a jelly-like gel;
(5) drying the wet gel in a constant-temperature drying box at 150 ℃ to obtain dry gel;
(6) fully grinding the xerogel, presintering for 24 hours at 800 ℃, secondarily grinding, and sintering for 24 hours at 970 ℃ to prepare the high-temperature spinning glass Ca3CoMnO6。
Example 3
High-temperature spin glass Ca of the present example3CoMnO6The preparation method comprises the following steps:
(1) dissolving citric acid in distilled water, and adding CaCO with the amount ratio of 3:1:13、C4H6CoO4•4H2O and C4H6MnO4•4H2Stirring and mixing the mixture O uniformly to obtain a mixed solution, wherein the content of the citric acid is CaCO3、C4H6CoO4•4H2O and C4H6MnO4•4H21.4 times of the total amount of the O substances, and the concentration of the citric acid in the mixed solution is 1 g/mL;
(2) adding nitric acid to adjust the pH of the mixed solution to 3-4, wherein the volume ratio of the glycol to the distilled water in the step (1) is 1.5: 3;
(3) adding glycol into the mixed solution after the pH value is adjusted to enhance the viscosity of the solution, and then, carrying out magnetic stirring for 2 hours at room temperature to fully mix;
(4) heating the solution in a water bath at 100 deg.C to form a jelly-like gel;
(5) drying the wet gel in a constant-temperature drying oven at 170 ℃ to obtain dry gel;
(6) fully grinding the xerogel, presintering for 24 hours at 800 ℃, secondarily grinding and sintering for 24 hours at 980 ℃ to prepare the high-temperature spinning glass Ca3CoMnO6。
Example 4
High-temperature spin glass Ca of the present example3CoMnO6The preparation method comprises the following steps:
(1) dissolving citric acid in distilled water, and adding CaCO with the amount ratio of 3:1:13、C4H6CoO4•4H2O and C4H6MnO4•4H2Stirring and mixing the mixture O uniformly to obtain a mixed solution, wherein the content of the citric acid is CaCO3、C4H6CoO4•4H2O and C4H6MnO4•4H21.5 times of the total amount of the O substances, and the concentration of the citric acid in the mixed solution is 1 g/mL;
(2) adding nitric acid to adjust the pH of the mixed solution to 3-4, wherein the volume ratio of the glycol to the distilled water in the step (1) is 1: 3;
(3) adding glycol into the mixed solution after the pH value is adjusted to enhance the viscosity of the solution, and then, carrying out magnetic stirring for 2 hours at room temperature to fully mix;
(4) heating the solution in a water bath at 98 deg.C to form a jelly-like gel;
(5) drying the wet gel in a constant-temperature drying oven at 165 ℃ to obtain dry gel;
(6) fully grinding the xerogel, presintering for 24 hours at 800 ℃, secondarily grinding and sintering for 24 hours at 1020 ℃ to prepare the high-temperature spinning glass Ca3CoMnO6。
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (3)

1. High-temperature spinning glass Ca3CoMnO6The preparation method is characterized by comprising the following steps:
(1) dissolving citric acid in distilled water, and adding CaCO3、C4H6CoO4•4H2O and C4H6MnO4•4H2Stirring and mixing the mixture O evenly to obtain a mixed solution;
(2) adding nitric acid to adjust the pH value of the mixed solution to 3-4;
(3) adding glycol into the mixed solution after the pH value is adjusted to enhance the viscosity of the solution, and then, carrying out magnetic stirring for 2 hours at room temperature to fully mix;
(4) heating the solution in a water bath at 95-100 deg.C to obtain a jelly-like wet gel;
(5) drying the wet gel in a constant-temperature drying box at the temperature of 150-;
(6) fully grinding, pre-sintering, secondary grinding and sintering the xerogel to prepare the high-temperature spinning glass Ca3CoMnO6；
CaCO in the step (1)3、C4H6CoO4•4H2O and C4H6MnO4•4H2The amount of O is 3:1:1, and the amount of citric acid is CaCO3、C4H6CoO4•4H2O and C4H6MnO4•4H21.2-1.5 times of the total amount of O substances;
the pre-sintering temperature in the step (6) is 800 ℃, and the pre-sintering time is 24 hours;
the sintering temperature in the step (6) is 970-1030 ℃, and the sintering time is 24 hours;
the concentration of the citric acid in the mixed solution in the step (1) is 1 g/mL.
2. High temperature spin glass Ca according to claim 13CoMnO6The preparation method is characterized by comprising the following steps: the volume ratio of the glycol in the step (3) to the distilled water in the step (1) is (1-2) to 3.
3. High temperature spin glass Ca according to claim 1 or 23CoMnO6The high-temperature spin glass Ca prepared by the preparation method3CoMnO6The crystal is a single-phase rhombic structure, the sample particles are uniform in size, and the spin glass characteristic is shown at a high temperature of 172K.
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Citations (1)

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Publication number Priority date Publication date Assignee Title
CN105887199A (en) * 2016-04-20 2016-08-24 中国科学院物理研究所 Novel compound Ca2CrO4 crystal and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN105887199A (en) * 2016-04-20 2016-08-24 中国科学院物理研究所 Novel compound Ca2CrO4 crystal and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Co位掺杂自旋链化合物Ca3CoMnO6的磁性及ESR研究;阮明岳;《中国博士学位论文全文数据库 工程科技I辑》;20170815(第8期);第45页 *
Effects of disorder and low dimensionality on frozen dynamics in Ca3Co2-xMnxO6;Casas, Brian Wesley;《Graduate Theses and Dissertations》;20151231;第12-13、25页 *
Short-range ferromagnetic correlations in the spin-chain compound Ca3CoMnO6;Z. W. Ouyang等;《PHYSICAL REVIEW B》;20111231;II试验部分，IV结论部分，图1-2 *

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