阅读说明：本技术 类钙钛矿结构固体材料及其制备 (Perovskite-like structure solid material and preparation thereof ) 是由 郭为民 肖亦芳 刘新梅 秦利平 凌新龙 乐志文 于 2020-11-02 设计创作，主要内容包括：本发明实施例公开了类钙钛矿结构固体材料及其制备,具体涉及钙钛矿领域,所使用的主料包括以下按重量份数计包括：锰粉20-30份；氧化镧5-10份；氯化镧5-10份；碳酸钙20-30份；二氧化锰10-20份。通过在对碳酸盐与硝酸盐等物质研磨过程中,先将各种物质进行单独研磨,当单独研磨完毕后,按一定的比例搅拌混合,增加了研磨的效果,然后将物质进行电阻丝煅烧,当到达燃烧温度后,关闭电阻丝电源,物质会进行内部自燃,无需补充能量,减少热能的消耗,然后进行自然降温,在降温的过程中将煅烧容器关闭,减缓物质降温的效率,从而减少亚稳物相的产生,避免在后期的研磨中时材料发生晶格畸变,增加了材料的磁性性能。(The embodiment of the invention discloses a perovskite-like structure solid material and a preparation method thereof, and particularly relates to the field of perovskite, wherein the used main materials comprise the following components in parts by weight: 20-30 parts of manganese powder; 5-10 parts of lanthanum oxide; 5-10 parts of lanthanum chloride; 20-30 parts of calcium carbonate; 10-20 parts of manganese dioxide. Through in the grinding process to substances such as carbonate and nitrate, grind various substances alone earlier, after grinding alone finishes, stir the mixture according to certain proportion, the effect of grinding has been increased, then carry out the resistance wire calcination with the substance, after reaching combustion temperature, close the resistance wire power, the substance can carry out inside spontaneous combustion, need not the supplemental energy, reduce the consumption of heat energy, then carry out natural cooling, the in-process at the cooling will calcine the container and close, slow down the efficiency of substance cooling, thereby reduce the production of metastable phase, material takes place lattice distortion when avoiding in the grinding in later stage, the magnetic properties of material has been increased.)

1. The perovskite-like structure solid material is characterized in that: the used main materials comprise the following components in parts by weight: 20-30 parts of manganese powder; 5-10 parts of lanthanum oxide; 5-10 parts of lanthanum chloride; 20-30 parts of calcium carbonate; 10-20 parts of manganese dioxide; 5-10 parts of sodium perchlorate; 5-10 parts of sodium peroxide; 1-5 parts of sodium superoxide; 15-30 parts of lanthanum nitrate; 15-30 parts of strontium nitrate; 5-10 parts of melamine.

2. The perovskite-like structure solid material according to claim 1, characterized in that: the used main materials comprise the following components in parts by weight: 22-28 parts of manganese powder; 6-8 parts of lanthanum oxide; 6-8 parts of lanthanum chloride; 22-28 parts of calcium carbonate; 12-18 parts of manganese dioxide; 6-8 parts of sodium perchlorate; 6-8 parts of sodium peroxide; 2-4 parts of sodium superoxide; 18-28 parts of lanthanum nitrate; 18-28 parts of strontium nitrate; 6-8 parts of melamine.

3. The perovskite-like structure solid material according to claim 1, characterized in that: the purity of the manganese powder is 96-99%, the purity of lanthanum oxide is 95-98%, the purity of lanthanum chloride is 97-99.5%, the purity of calcium carbonate is 96-99%, the purity of manganese dioxide is 88-92%, the purity of sodium perchlorate is 94-98%, the purity of sodium peroxide is 97-99.2%, the purity of sodium superoxide is 92-96%, the purity of lanthanum nitrate is 89-93.5%, the purity of strontium nitrate is 96-99%, and the purity of melamine is 97-99.5%.

4. A perovskite-like structure solid material according to any one of claims 1 to 3, characterized in that: the preparation method of the perovskite-like structure solid material comprises the following specific steps:

the method comprises the following steps: respectively putting manganese powder, lanthanum oxide, lanthanum chloride, calcium carbonate, manganese dioxide, sodium perchlorate, sodium peroxide, sodium superoxide, lanthanum nitrate, strontium nitrate and melamine into a grinding container, and then grinding by using an agate object;

step two: after the materials are ground into uniform powdery objects, pouring the ground powdery objects into a stirrer according to a certain proportion, and fully mixing the powdery objects through the stirrer;

step three: taking out the mixed powder material, introducing the powder material into a shaping machine, and preparing the powder raw material into a cylindrical blank with a certain volume by applying certain pressure;

step four: then, putting a plurality of cylindrical blanks into a combustion box, starting a power supply in an internal resistance wire, igniting the raw materials of the cylindrical blanks through the high temperature of the resistance wire, and immediately closing the resistance wire after ignition;

step five: the raw materials begin to record the temperature and the speed of the reaction in the process of reaction spontaneous combustion, and after the spontaneous combustion is finished, the vent hole of the combustion box is closed, so that the materials are naturally cooled;

step six: when the temperature is reduced to a proper temperature, taking out the material, then putting the material into a grinder for grinding, keeping the grinding space closed all the time, and after grinding is finished, washing the product by deionized water;

step seven: and after cleaning, taking out the product, performing air drying treatment, and testing various performances of the product.

5. The method for producing a perovskite-like structure solid material according to claim 4, characterized in that: the grinding time of the raw materials in the step one is 30-40 min, and the volume of the grinding container in the step one is 500-1000 ml.

6. The method for producing a perovskite-like structure solid material according to claim 4, characterized in that: the stirring time of the stirrer in the second step is 30-50 min, and the pressure applied to the raw material in the third step for solidifying the raw material is 0.5-0.8 MPA.

7. The method for producing a perovskite-like structure solid material according to claim 4, characterized in that: the size of the cylindrical blank in the third step is 20mm-30mm in diameter and 50mm-60mm in height, and the weight of each cylindrical blank in the third step is 20g-30 g.

8. The method for producing a perovskite-like structure solid material according to claim 4, characterized in that: the ignition temperature of the resistance wire to the material in the fourth step is 350-400 ℃, and the ignition time of the material in the fifth step is 15-20 min.

9. The method for producing a perovskite-like structure solid material according to claim 4, characterized in that: the highest temperature in the ignition process of the material in the fifth step is 450-500 ℃, the time for cooling the material in the fifth step is 2-3 h, and the suitable temperature for cooling the material in the sixth step is 40-50 ℃.

10. The method for producing a perovskite-like structure solid material according to claim 4, characterized in that: the grinding time in the sixth step is 20-40 min, and the air drying time of the material in the seventh step is 3-5 h.

Technical Field

The embodiment of the invention relates to the field of perovskite, in particular to a perovskite-like structure solid material and a preparation method thereof.

Background

The perovskite type composite oxide is a general compound with the same structure as perovskite CaTiO3, the perovskite structure can be represented by ABO3, the A site is alkaline earth element, the cation is in 12 coordination structure and is positioned in a cavity formed by octahedron; the B site is transition metal element, and the transition metal ion and six oxygen ions form octahedral coordination.

The prior art has the following defects: the existing perovskite-like structure solid material is easy to obtain a metastable phase due to high temperature gradient and fast cooling rate in the combustion process in the preparation process, but impurities are easy to introduce in the process, the difference between atoms of the metastable phase and the atomic radius of a substance is large, so that the difference between the diameters of the atoms is large, the adjacent layers are not matched, and lattice defects and lattice distortion are usually generated in the material in the grinding process, thereby the magnetic performance of the material is reduced.

Disclosure of Invention

Therefore, the perovskite-like structure solid material and the preparation method thereof are provided by the embodiment of the invention, various substances are ground separately in the grinding process of carbonate, nitrate and other substances, after the grinding is finished separately, the substances are stirred and mixed according to a certain proportion, the grinding effect is increased, then the substances are subjected to resistance wire calcination, after the combustion temperature is reached, the resistance wire power supply is turned off, the substances can perform internal spontaneous combustion, energy supplement is not needed, the consumption of heat energy is reduced, then natural cooling is performed, the calcination container is turned off in the cooling process, the efficiency of substance cooling is slowed down, the generation of metastable phases is reduced, the lattice distortion of the materials in the later grinding process is avoided, the magnetic property of the materials is increased, and the problem caused by the grinding process in the prior art is solved.

In order to achieve the above object, the embodiments of the present invention provide the following technical solutions: the perovskite-like structure solid material comprises the following main materials in parts by weight: 20-30 parts of manganese powder; 5-10 parts of lanthanum oxide; 5-10 parts of lanthanum chloride; 20-30 parts of calcium carbonate; 10-20 parts of manganese dioxide; 5-10 parts of sodium perchlorate; 5-10 parts of sodium peroxide; 1-5 parts of sodium superoxide; 15-30 parts of lanthanum nitrate; 15-30 parts of strontium nitrate; 5-10 parts of melamine.

Further, the used main materials comprise the following components in parts by weight: 22-28 parts of manganese powder; 6-8 parts of lanthanum oxide; 6-8 parts of lanthanum chloride; 22-28 parts of calcium carbonate; 12-18 parts of manganese dioxide; 6-8 parts of sodium perchlorate; 6-8 parts of sodium peroxide; 2-4 parts of sodium superoxide; 18-28 parts of lanthanum nitrate; 18-28 parts of strontium nitrate; 6-8 parts of melamine.

Furthermore, the purity of the manganese powder is 96-99%, the purity of lanthanum oxide is 95-98%, the purity of lanthanum chloride is 97-99.5%, the purity of calcium carbonate is 96-99%, the purity of manganese dioxide is 88-92%, the purity of sodium perchlorate is 94-98%, the purity of sodium peroxide is 97-99.2%, the purity of sodium superoxide is 92-96%, the purity of lanthanum nitrate is 89-93.5%, the purity of strontium nitrate is 96-99%, and the purity of melamine is 97-99.5%.

A preparation method for a solid material with a perovskite-like structure comprises the following specific steps:

the method comprises the following steps: respectively putting manganese powder, lanthanum oxide, lanthanum chloride, calcium carbonate, manganese dioxide, sodium perchlorate, sodium peroxide, sodium superoxide, lanthanum nitrate, strontium nitrate and melamine into a grinding container, and then grinding by using an agate object;

step two: after the materials are ground into uniform powdery objects, pouring the ground powdery objects into a stirrer according to a certain proportion, and fully mixing the powdery objects through the stirrer;

step three: taking out the mixed powder material, introducing the powder material into a shaping machine, and preparing the powder raw material into a cylindrical blank with a certain volume by applying certain pressure;

step four: then, putting a plurality of cylindrical blanks into a combustion box, starting a power supply in an internal resistance wire, igniting the raw materials of the cylindrical blanks through the high temperature of the resistance wire, and immediately closing the resistance wire after ignition;

step five: the raw materials begin to record the temperature and the speed of the reaction in the process of reaction spontaneous combustion, and after the spontaneous combustion is finished, the vent hole of the combustion box is closed, so that the materials are naturally cooled;

step six: when the temperature is reduced to a proper temperature, taking out the material, then putting the material into a grinder for grinding, keeping the grinding space closed all the time, and after grinding is finished, washing the product by deionized water;

step seven: and after cleaning, taking out the product, performing air drying treatment, and testing various performances of the product.

Further, the grinding time of the raw materials in the step one is 30min to 40min, and the volume of the grinding container in the step one is 500ml to 1000 ml.

Further, the stirring time of the stirrer in the second step is 30-50 min, and the pressure applied to the raw material solid in the third step is 0.5-0.8 MPA.

Further, the size of the cylindrical blank in the third step is 20mm-30mm in diameter and 50mm-60mm in height, and the weight of each cylindrical blank in the third step is 20g-30 g.

Furthermore, the ignition temperature of the resistance wire to the material in the fourth step is 350-400 ℃, and the ignition time of the material in the fifth step is 15-20 min.

Further, the maximum temperature in the ignition process of the material in the fifth step is 450-500 ℃, the temperature reduction time of the material in the fifth step is 2-3 h, and the suitable temperature for reducing the material in the sixth step is 40-50 ℃.

Further, the grinding time in the sixth step is 20-40 min, and the air drying time of the material in the seventh step is 3-5 h.

The embodiment of the invention has the following advantages:

through in the grinding process to substances such as carbonate and nitrate, grind various substances alone earlier, after grinding alone finishes, stir the mixture according to certain proportion, the effect of grinding has been increased, then carry out the resistance wire calcination with the substance, after reaching combustion temperature, close the resistance wire power, the substance can carry out inside spontaneous combustion, need not the supplemental energy, reduce the consumption of heat energy, then carry out natural cooling, the in-process at the cooling will calcine the container and close, slow down the efficiency of substance cooling, thereby reduce the production of metastable phase, material takes place lattice distortion when avoiding in the grinding in later stage, the magnetic properties of material has been increased.

Detailed Description

The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1:

the perovskite-like structure solid material comprises the following main materials in parts by weight: 22 parts of manganese powder; 6 parts of lanthanum oxide; 6 parts of lanthanum chloride; 22 parts of calcium carbonate; 12 parts of manganese dioxide; 6 parts of sodium perchlorate; 6 parts of sodium peroxide; 2 parts of sodium superoxide; 18 parts of lanthanum nitrate; 18 parts of strontium nitrate; 6 parts of melamine.

Further, the purity of the manganese powder is 96%, the purity of lanthanum oxide is 95%, the purity of lanthanum chloride is 97%, the purity of calcium carbonate is 96%, the purity of manganese dioxide is 88%, the purity of sodium perchlorate is 94%, the purity of sodium peroxide is 97%, the purity of sodium superoxide is 92%, the purity of lanthanum nitrate is 89%, the purity of strontium nitrate is 96%, and the purity of melamine is 97%.

A preparation method for a solid material with a perovskite-like structure comprises the following specific steps:

the method comprises the following steps: respectively putting manganese powder, lanthanum oxide, lanthanum chloride, calcium carbonate, manganese dioxide, sodium perchlorate, sodium peroxide, sodium superoxide, lanthanum nitrate, strontium nitrate and melamine into a grinding container, and then grinding by using an agate object;

step two: after the materials are ground into uniform powdery objects, pouring the ground powdery objects into a stirrer according to a certain proportion, and fully mixing the powdery objects through the stirrer;

step three: taking out the mixed powder material, introducing the powder material into a shaping machine, and preparing the powder raw material into a cylindrical blank with a certain volume by applying certain pressure;

step four: then, putting a plurality of cylindrical blanks into a combustion box, starting a power supply in an internal resistance wire, igniting the raw materials of the cylindrical blanks through the high temperature of the resistance wire, and immediately closing the resistance wire after ignition;

step five: the raw materials begin to record the temperature and the speed of the reaction in the process of reaction spontaneous combustion, and after the spontaneous combustion is finished, the vent hole of the combustion box is closed, so that the materials are naturally cooled;

step six: when the temperature is reduced to a proper temperature, taking out the material, then putting the material into a grinder for grinding, keeping the grinding space closed all the time, and after grinding is finished, washing the product by deionized water;

step seven: and after cleaning, taking out the product, performing air drying treatment, and testing various performances of the product.

Further, the time for grinding the raw material in the first step is 30min, and the volume of the grinding container in the first step is 500 ml.

Further, the stirring time of the stirrer in the second step is 30min, and the pressure applied to the raw material solid in the third step is 0.5 MPA.

Further, the size of the cylindrical blank in the third step is 20mm in diameter and 50mm in height, and the weight of each cylindrical blank in the third step is 20 g.

Further, the ignition temperature of the resistance wire to the material in the fourth step is 350 ℃, and the ignition time of the material in the fifth step is 15 min.

Further, the maximum temperature in the ignition process of the material in the fifth step is 450 ℃, the time for cooling the material in the fifth step is 2 hours, and the suitable temperature for cooling the material in the sixth step is 40 ℃.

Further, the grinding time in the sixth step is 20min, and the air drying time of the material in the seventh step is 3 h.

Example 2:

the perovskite-like structure solid material comprises the following main materials in parts by weight: 24 parts of manganese powder; 7 parts of lanthanum oxide; 7 parts of lanthanum chloride; 24 parts of calcium carbonate; 15 parts of manganese dioxide; 7 parts of sodium perchlorate; 7 parts of sodium peroxide; 3 parts of sodium superoxide; 24 parts of lanthanum nitrate; 24 parts of strontium nitrate; 7 parts of melamine.

Further, the purity of the manganese powder is 98%, the purity of lanthanum oxide is 96%, the purity of lanthanum chloride is 98%, the purity of calcium carbonate is 97%, the purity of manganese dioxide is 90%, the purity of sodium perchlorate is 96%, the purity of sodium peroxide is 98%, the purity of sodium superoxide is 94%, the purity of lanthanum nitrate is 92%, the purity of strontium nitrate is 98%, and the purity of melamine is 98%.

A preparation method for a solid material with a perovskite-like structure comprises the following specific steps:

the method comprises the following steps: respectively putting manganese powder, lanthanum oxide, lanthanum chloride, calcium carbonate, manganese dioxide, sodium perchlorate, sodium peroxide, sodium superoxide, lanthanum nitrate, strontium nitrate and melamine into a grinding container, and then grinding by using an agate object;

step two: after the materials are ground into uniform powdery objects, pouring the ground powdery objects into a stirrer according to a certain proportion, and fully mixing the powdery objects through the stirrer;

step three: taking out the mixed powder material, introducing the powder material into a shaping machine, and preparing the powder raw material into a cylindrical blank with a certain volume by applying certain pressure;

step four: then, putting a plurality of cylindrical blanks into a combustion box, starting a power supply in an internal resistance wire, igniting the raw materials of the cylindrical blanks through the high temperature of the resistance wire, and immediately closing the resistance wire after ignition;

step five: the raw materials begin to record the temperature and the speed of the reaction in the process of reaction spontaneous combustion, and after the spontaneous combustion is finished, the vent hole of the combustion box is closed, so that the materials are naturally cooled;

step six: when the temperature is reduced to a proper temperature, taking out the material, then putting the material into a grinder for grinding, keeping the grinding space closed all the time, and after grinding is finished, washing the product by deionized water;

step seven: and after cleaning, taking out the product, performing air drying treatment, and testing various performances of the product.

Further, the time for grinding the raw material in the first step is 35min, and the volume of the grinding container in the first step is 800 ml.

Further, the stirring time of the stirrer in the second step is 40min, and the pressure applied to the raw material solid in the third step is 0.6 MPA.

Further, the size of the cylindrical blank in the third step is 25mm in diameter and 55mm in height, and the weight of each cylindrical blank in the third step is 25 g.

Further, the ignition temperature of the resistance wire to the material in the fourth step is 380 ℃, and the ignition time of the material in the fifth step is 18 min.

Further, the maximum temperature in the ignition process of the material in the fifth step is 480 ℃, the time for cooling the material in the fifth step is 2.5 hours, and the suitable temperature for cooling the material in the sixth step is 45 ℃.

Further, the grinding time in the sixth step is 30min, and the air drying time of the material in the seventh step is 4 h.

Example 3:

the perovskite-like structure solid material comprises the following main materials in parts by weight: 28 parts of manganese powder; 8 parts of lanthanum oxide; 8 parts of lanthanum chloride; 28 parts of calcium carbonate; 18 parts of manganese dioxide; 8 parts of sodium perchlorate; 8 parts of sodium peroxide; 4 parts of sodium superoxide; 28 parts of lanthanum nitrate; 28 parts of strontium nitrate; 8 parts of melamine.

Further, the purity of the manganese powder is 99%, the purity of lanthanum oxide is 98%, the purity of lanthanum chloride is 99.5%, the purity of calcium carbonate is 99%, the purity of manganese dioxide is 92%, the purity of sodium perchlorate is 98%, the purity of sodium peroxide is 99.2%, the purity of sodium superoxide is 96%, the purity of lanthanum nitrate is 93.5%, the purity of strontium nitrate is 99%, and the purity of melamine is 99.5%.

A preparation method for a solid material with a perovskite-like structure comprises the following specific steps:

the method comprises the following steps: respectively putting manganese powder, lanthanum oxide, lanthanum chloride, calcium carbonate, manganese dioxide, sodium perchlorate, sodium peroxide, sodium superoxide, lanthanum nitrate, strontium nitrate and melamine into a grinding container, and then grinding by using an agate object;

step two: after the materials are ground into uniform powdery objects, pouring the ground powdery objects into a stirrer according to a certain proportion, and fully mixing the powdery objects through the stirrer;

step three: taking out the mixed powder material, introducing the powder material into a shaping machine, and preparing the powder raw material into a cylindrical blank with a certain volume by applying certain pressure;

step four: then, putting a plurality of cylindrical blanks into a combustion box, starting a power supply in an internal resistance wire, igniting the raw materials of the cylindrical blanks through the high temperature of the resistance wire, and immediately closing the resistance wire after ignition;

step five: the raw materials begin to record the temperature and the speed of the reaction in the process of reaction spontaneous combustion, and after the spontaneous combustion is finished, the vent hole of the combustion box is closed, so that the materials are naturally cooled;

step six: when the temperature is reduced to a proper temperature, taking out the material, then putting the material into a grinder for grinding, keeping the grinding space closed all the time, and after grinding is finished, washing the product by deionized water;

step seven: and after cleaning, taking out the product, performing air drying treatment, and testing various performances of the product.

Further, the time for grinding the raw material in the first step is 40min, and the volume of the grinding container in the first step is 1000 ml.

Further, the stirring time of the stirrer in the second step is 50min, and the pressure applied to the raw material solid in the third step is 0.8 MPA.

Further, the size of the cylindrical blank in the third step is 30mm in diameter and 60mm in height, and the weight of each cylindrical blank in the third step is 30 g.

Further, the ignition temperature of the resistance wire to the material in the fourth step is 400 ℃, and the ignition time of the material in the fifth step is 20 min.

Further, the maximum temperature in the ignition process of the material in the fifth step is 500 ℃, the time for cooling the material in the fifth step is 3 hours, and the suitable temperature for cooling the material in the sixth step is 50 ℃.

Further, the grinding time in the sixth step is 40min, and the air drying time of the material in the seventh step is 5 h.

Example 4:

the rubber cables prepared in the above examples 1 to 3 were respectively grouped, and then the prepared rubber cables were tested for various properties, to obtain the following data:

as can be seen from the above table, the perovskite-like structure solid material prepared in example 1 takes a short time, has high purity, and has low loss.

Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.