CN111646798A - Preparation method of lanthanum calcium manganese oxygen low-doped samarium nitrate - Google Patents
Preparation method of lanthanum calcium manganese oxygen low-doped samarium nitrate Download PDFInfo
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- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- HEOGEEMADXKTBU-UHFFFAOYSA-N [O].[Mn].[Ca].[La] Chemical compound [O].[Mn].[Ca].[La] HEOGEEMADXKTBU-UHFFFAOYSA-N 0.000 title claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 42
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 40
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000919 ceramic Substances 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000011575 calcium Substances 0.000 claims abstract description 29
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 25
- 238000000227 grinding Methods 0.000 claims abstract description 21
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000005303 weighing Methods 0.000 claims abstract description 13
- 229910021117 Sm(NO3)3 Inorganic materials 0.000 claims abstract description 3
- 239000002270 dispersing agent Substances 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 23
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000004570 mortar (masonry) Substances 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 239000013077 target material Substances 0.000 claims description 3
- 239000002738 chelating agent Substances 0.000 claims description 2
- 230000009920 chelation Effects 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011858 nanopowder Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 239000000499 gel Substances 0.000 abstract description 9
- 239000011240 wet gel Substances 0.000 abstract description 6
- 238000003980 solgel method Methods 0.000 abstract description 3
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910003410 La0.7Ca0.3MnO3 Inorganic materials 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/624—Sol-gel processing
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
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Abstract
The invention discloses a preparation method of lanthanum calcium manganese oxygen low-doped samarium nitrate, which is used for preparing high-purity La (NO)3)3·6H2O，Sm(NO3)3,Ca(NO3)2·4H2O，Mn(NO3)2·4H2O and C6H8O7·H2Calculating O according to the molar ratio of (0.7-x) x:0.3:1:4(x is 0.01-0.05), weighing the components, using methanol as solvent and ethylene glycol as dispersant, and chelating La0.7‑ xSmxCa0.3MnO3Wet gel, drying in a drying oven, fully grinding the obtained dry gel, performing primary sintering at 500 ℃ for 8h, fully grinding the obtained primary sintering powder, tabletting, performing final sintering at 1400 ℃ for 12h, and preparingDischarge La0.7‑ xSmxCa0.3MnO3A polycrystalline ceramic target sample; in the method, when the low-doped samarium nitrate is 0.03mol by a sol-gel method, La is added0.67Sm0.03Ca0.3MnO3The Temperature Coefficient of Resistance (TCR) and the Magnetoresistance (MR) of the polycrystalline ceramic material reach 20.23%. K‑1And 72.31 percent of the total weight of the material, so that the application of the material can better meet the use requirement, and the method has the advantages of convenient preparation, short period and low preparation cost, and can be used for large-scale industrial production.
Description
Technical Field
The invention relates to a preparation method of lanthanum calcium manganese oxygen low-doped samarium nitrate, belonging to the technical field of electronic functional ceramics.
Background
La0.7Ca0.3MnO3Is a typical strongly associated electron system, the metal-insulator transition around the Curie temperature can cause a large resistance jump in a very small temperature range, LaCaMnO3The oxide has various special physical properties as a strongly-associated oxide, has giant magnetoresistance effect and metal-insulator transition behavior, and has great research and application values in photoelectric fast devices, bolometers, high-density magnetic storage heads, refrigerators and infrared detectors. For LaCaMnO3In material systems, the Temperature Coefficient of Resistance (TCR) represents the degree of sensitivity of the material to temperature, which determines the possibility of application of the detection device. Meanwhile, the higher Low Field Magnetoresistance (LFMR) provides a foundation for preparing equipment such as a magnetic sensing device and the like depending on the magnetoresistance performance, and the existing pure LaCaMnO3The MR is low, and the application of the material is limited to a great extent.
Disclosure of Invention
The invention provides a preparation method of lanthanum calcium manganese oxygen low-doped samarium nitrate to solve the problems in the prior art, so that LaCaMnO is utilized3The MR of the system material is greatly improved when the system material is low-doped with samarium nitrate and is used for preparing pure La0.7Ca0.3MnO3On the basis, samarium nitrate is directly mixed with La by a sol-gel method0.7Ca0.3MnO3Decocting into a whole to ensure that samarium nitrate is uniformly doped to form La0.7-xSmxCa0.3MnO3Gelling, then drying, pre-firing and final firing to obtain La0.7-xSmxCa0.3MnO3The preparation method of the polycrystalline ceramic target material is that when the doping amount is 0.03mol, La is added0.67Sm0.03Ca0.3MnO3The MR of the ceramic is up to 72.31 percent, and the preparation method can enable the MR of the material to be up to 72.31 percent, thereby better meeting the use requirement of the material.
The invention aims to provide a preparation method of lanthanum calcium manganese oxygen low-doped samarium nitrate, which specifically comprises the following steps:
(1) preparation of sample 2.5g of La0.7-xSmxCa0.3MnO3Polycrystalline ceramic target material prepared by mixing lanthanum nitrate (La (NO)3)3·nH2O), samarium nitrate (Sm (NO)3)3) Calcium nitrate (Ca (NO)3)2·4H2O), manganese nitrate (Mn (NO)3)2·4H2O) and citric acid (C)6H8O7·H2O) calculating the stoichiometric ratio, weighing and placing into a beaker, and adding methanol into the beaker as a solvent;
(2) putting the beaker after the step (1) is finished on a magnetic stirrer, uniformly stirring, simultaneously dropwise adding a small amount of glycol into the beaker, and continuously stirring until the medicine is completely dissolved;
(3) heating the mixed solution obtained in the step (2) in a water bath, and simultaneously stirring by magnetic force until the sol becomes dark yellow, viscous and transparent gel;
(4) quickly putting the gel obtained in the step (3) into a drying box, and drying for 8-12h to obtain dry gel;
(5) pouring the xerogel obtained in the step (4) into a mortar, fully grinding, filling into a ceramic crucible, and placing in a box-type furnace for pre-sintering to obtain nano powder;
fully grinding the powder obtained in the step (5) in a mortar, pressing the powder into blocks by using a tablet press, filling the blocks into a corundum crucible, and placing the corundum crucible in a box furnace for final burning to obtain La0.67Sm0.03Ca0.3MnO3Polycrystalline ceramic targets.
La (NO) in step (1) of the present invention3)3·6H2O，Sm(NO3)3,Ca(NO3)2·4H2O，Mn(NO3)2·4H2O and C6H8O7·H2The molar ratio of O is (0.7-x) x:0.3:1:4, the amount of methanol is n(methanol)：n(CA)3: methanol as a solvent for colloidal chelation.
Step (2) of the present inventionThe amount of ethylene glycol in (1) is n(EG)：n(CA)1: 2, ethylene glycol is used as a dispersant, and citric acid is used as a chelating agent.
The heating temperature of the water bath heating in the step (3) of the invention is 85-88 ℃, and the stirring speed is slowly reduced in the process of thickening the sol.
The temperature of the drying box in the step (4) of the invention is 140-.
The initial firing process in the step (5) of the invention is heat preservation for 8h at 500 ℃, wherein in order to ensure that the sample is fully reacted, the heat preservation is carried out for 1h when the temperature is respectively raised to 200 ℃ and 400 ℃.
The final firing process in step (6) of the invention is heat preservation at 1400 ℃ for 12 h.
The invention has the beneficial effects that: the invention relates to a preparation method of lanthanum calcium manganese oxygen low-doped samarium nitrate, which is characterized in that when the lanthanum calcium manganese oxygen low-doped samarium nitrate is doped by 0.03mol by a sol-gel method, La is added0.67Sm0.03Ca0.3MnO3The Temperature Coefficient of Resistance (TCR) of the polycrystalline ceramic material and the resistance (MR) under a 1T magnetic field reach 20.23%. K-1And 72.31 percent of the total weight of the material, so that the application of the material can better meet the use requirement, and the method has the advantages of convenient preparation, short period and low preparation cost, and can be used for large-scale industrial production.
Drawings
FIG. 1 is an XRD pattern of a series of polycrystalline ceramic targets obtained in examples 1-5;
FIGS. 2-6 are SEM images corresponding to examples 1-5;
FIG. 7 is a TCR curve of a series of polycrystalline ceramic targets obtained in examples 1-5;
FIG. 8 is an MR plot of a series of polycrystalline ceramic targets obtained in examples 1-5;
Detailed Description
The invention will be described in more detail hereinafter with reference to the drawings and the detailed description, without limiting the scope of the invention to the same.
Example 1
(1) Weighing and dissolving raw materials: firstly, calculating the dosage of each raw material according to a stoichiometric ratio, then sequentially weighing lanthanum nitrate, samarium nitrate, calcium nitrate, manganese nitrate and citric acid according to the molar ratio of 0.69:0.01:0.3:1:4, dissolving the lanthanum nitrate, the samarium nitrate, the calcium nitrate, the manganese nitrate and the citric acid in a methanol solvent, and adding a proper amount of ethylene glycol after the lanthanum nitrate, the samarium nitrate, the calcium nitrate, the manganese nitrate and the citric acid are completely dissolved.
(2) Heating and stirring to form glue: and (2) placing the mixed solution obtained in the step (1) on a constant-temperature water bath kettle, stirring at a constant temperature of 88 ℃, heating while stirring, slowly evaporating the solvent, and gradually generating a foaming phenomenon to form wet sol when the solution is evaporated to a certain amount.
(3) Drying: and (3) immediately putting the wet gel obtained in the step (2) into a drying oven, wherein the temperature of the drying oven is 180 ℃, and the heat preservation time is 12 hours, so that dry gel is formed.
(4) Grinding and pre-sintering: and (4) pouring all the xerogel obtained in the step (3) into an agate mortar, fully grinding for 30min to obtain powder, putting the powder into a ceramic crucible, putting the ceramic crucible into a box-type furnace for primary burning, and preserving heat at 500 ℃ for 8h for primary burning to obtain black powder.
(5) Tabletting and sintering: fully grinding the black powder obtained in the step (4) by using an agate mortar, pressing the black powder into a block with the diameter of 20mm by using a tablet press, then putting the block into a box type furnace, preserving the heat at 1400 ℃ for 12h for final burning to finally obtain La0.69Sm0.01Ca0.3MnO3Polycrystalline ceramic targets.
Example 1 La with low-doped samarium nitrate content of 0.01mol was obtained0.69Sm0.01Ca0.3MnO3As can be seen from FIGS. 1, 2, 7 and 8, when the amount of low-doped samarium nitrate was 0.01mol, La was added to the polycrystalline ceramic target0.69Sm0.01Ca0.3MnO3The sample has a typical perovskite structure, no second phase, good crystallization quality, low TCR and MR, respectively 18.06%. K-1And 52.50%.
Example 2
(1) Weighing and dissolving raw materials: firstly, calculating the dosage of each raw material according to a stoichiometric ratio, then sequentially weighing lanthanum nitrate, samarium nitrate, calcium nitrate, manganese nitrate and citric acid according to the molar ratio of 0.68:0.02:0.3:1:4, dissolving the lanthanum nitrate, the samarium nitrate, the calcium nitrate, the manganese nitrate and the citric acid in a methanol solvent, and adding a proper amount of ethylene glycol after the lanthanum nitrate, the samarium nitrate, the calcium nitrate, the manganese nitrate and the citric acid are completely dissolved.
(2) Heating and stirring to form glue: and (2) placing the mixed solution obtained in the step (1) on a constant-temperature water bath kettle, stirring at a constant temperature of 88 ℃, heating while stirring, slowly evaporating the solvent, and gradually generating a foaming phenomenon to form wet sol when the solution is evaporated to a certain amount.
(3) Drying: and (3) immediately putting the wet gel obtained in the step (2) into a drying oven, wherein the temperature of the drying oven is 180 ℃, and the heat preservation time is 12 hours, so that dry gel is formed.
(4) Grinding and pre-sintering: and (4) pouring all the xerogel obtained in the step (3) into an agate mortar, fully grinding for 30min to obtain powder, putting the powder into a ceramic crucible, putting the ceramic crucible into a box-type furnace for primary burning, and preserving heat at 500 ℃ for 8h for primary burning to obtain black powder.
(5) Tabletting and sintering: fully grinding the black powder obtained in the step (4) by using an agate mortar, pressing the black powder into a block with the diameter of 20mm by using a tablet press, then putting the block into a box type furnace, preserving the heat at 1400 ℃ for 12h for final burning to finally obtain La0.68Sm0.02Ca0.3MnO3Polycrystalline ceramic targets.
Example 2 La with low-doped samarium nitrate content of 0.02mol was obtained0.68Sm0.02Ca0.3MnO3As can be seen from FIGS. 1, 3, 7 and 8, when the amount of low-doped samarium nitrate was 0.02mol, La was added to the polycrystalline ceramic target0.68Sm0.02Ca0.3MnO3The sample has a typical perovskite structure, no second phase, good crystallization quality, low TCR and MR, respectively, 19.03%. K-1And 69.63%.
Example 3
(1) Weighing and dissolving raw materials: firstly, calculating the dosage of each raw material according to a stoichiometric ratio, then sequentially weighing lanthanum nitrate, samarium nitrate, calcium nitrate, manganese nitrate and citric acid according to the molar ratio of 0.67:0.03:0.3:1:4, dissolving the lanthanum nitrate, the samarium nitrate, the calcium nitrate, the manganese nitrate and the citric acid in a methanol solvent, and adding a proper amount of ethylene glycol after the lanthanum nitrate, the samarium nitrate, the calcium nitrate, the manganese nitrate and the citric acid are completely dissolved.
(2) Heating and stirring to form glue: and (2) placing the mixed solution obtained in the step (1) on a constant-temperature water bath kettle, stirring at a constant temperature of 88 ℃, heating while stirring, slowly evaporating the solvent, and gradually generating a foaming phenomenon to form wet sol when the solution is evaporated to a certain amount.
(3) Drying: and (3) immediately putting the wet gel obtained in the step (2) into a drying oven, wherein the temperature of the drying oven is 180 ℃, and the heat preservation time is 12 hours, so that dry gel is formed.
(4) Grinding and pre-sintering: and (4) pouring all the xerogel obtained in the step (3) into an agate mortar, fully grinding for 30min to obtain powder, putting the powder into a ceramic crucible, putting the ceramic crucible into a box-type furnace for primary burning, and preserving heat at 500 ℃ for 8h for primary burning to obtain black powder.
(5) Tabletting and sintering: fully grinding the black powder obtained in the step (4) by using an agate mortar, pressing the black powder into a block with the diameter of 20mm by using a tablet press, then putting the block into a box type furnace, preserving the heat at 1400 ℃ for 12h for final burning to finally obtain La0.67Sm0.03Ca0.3MnO3Polycrystalline ceramic targets.
Example 3 La with low-doped samarium nitrate content of 0.03 mol/l0.67Sm0.03Ca0.3MnO3As can be seen from FIGS. 1, 4, 7 and 8, when the amount of low-doped samarium nitrate was 0.03mol, La was added to the polycrystalline ceramic target0.67Sm0.03Ca0.3MnO3The sample has a typical perovskite structure, no second phase, good crystallization quality, and the highest TCR and MR of 20.23% K-1And 72.31%.
Example 4
(1) Weighing and dissolving raw materials: firstly, calculating the dosage of each raw material according to a stoichiometric ratio, then sequentially weighing lanthanum nitrate, samarium nitrate, calcium nitrate, manganese nitrate and citric acid according to the molar ratio of 0.66:0.04:0.3:1:4, dissolving the lanthanum nitrate, the samarium nitrate, the calcium nitrate, the manganese nitrate and the citric acid in a methanol solvent, and adding a proper amount of ethylene glycol after the lanthanum nitrate, the samarium nitrate, the calcium nitrate, the manganese nitrate and the citric acid are completely dissolved.
(2) Heating and stirring to form glue: and (2) placing the mixed solution obtained in the step (1) on a constant-temperature water bath kettle, stirring at a constant temperature of 88 ℃, heating while stirring, slowly evaporating the solvent, and gradually generating a foaming phenomenon to form wet sol when the solution is evaporated to a certain amount.
(3) Drying: and (3) immediately putting the wet gel obtained in the step (2) into a drying oven, wherein the temperature of the drying oven is 180 ℃, and the heat preservation time is 12 hours, so that dry gel is formed.
(4) Grinding and pre-sintering: and (4) pouring all the xerogel obtained in the step (3) into an agate mortar, fully grinding for 30min to obtain powder, putting the powder into a ceramic crucible, putting the ceramic crucible into a box-type furnace for primary burning, and preserving heat at 500 ℃ for 8h for primary burning to obtain black powder.
(5) Tabletting and sintering: fully grinding the black powder obtained in the step (4) by using an agate mortar, pressing the black powder into a block with the diameter of 20mm by using a tablet press, then putting the block into a box type furnace, preserving the heat at 1400 ℃ for 12h for final burning to finally obtain La0.66Sm0.04Ca0.3MnO3Polycrystalline ceramic targets.
Example 4 La with low-doped samarium nitrate content of 0.04 mol/l was obtained0.66Sm0.04Ca0.3MnO3As can be seen from FIGS. 1, 5, 7 and 8, when the amount of low-doped samarium nitrate was 0.04mol, La was added to the polycrystalline ceramic target0.66Sm0.04Ca0.3MnO3The sample has a typical perovskite structure, no second phase, good crystallization quality, low TCR and MR, respectively 15.48%. K-1And 61.40%.
Example 5
(1) Weighing and dissolving raw materials: firstly, calculating the dosage of each raw material according to a stoichiometric ratio, then sequentially weighing lanthanum nitrate, samarium nitrate, calcium nitrate, manganese nitrate and citric acid according to the molar ratio of 0.65:0.05:0.3:1:4, dissolving the lanthanum nitrate, the samarium nitrate, the calcium nitrate, the manganese nitrate and the citric acid in a methanol solvent, and adding a proper amount of ethylene glycol after the lanthanum nitrate, the samarium nitrate, the calcium nitrate, the manganese nitrate and the citric acid are completely dissolved.
(2) Heating and stirring to form glue: and (2) placing the mixed solution obtained in the step (1) on a constant-temperature water bath kettle, stirring at a constant temperature of 88 ℃, heating while stirring, slowly evaporating the solvent, and gradually generating a foaming phenomenon to form wet sol when the solution is evaporated to a certain amount.
(3) Drying: and (3) immediately putting the wet gel obtained in the step (2) into a drying oven, wherein the temperature of the drying oven is 180 ℃, and the heat preservation time is 12 hours, so that dry gel is formed.
(4) Grinding and pre-sintering: and (4) pouring all the xerogel obtained in the step (3) into an agate mortar, fully grinding for 30min to obtain powder, putting the powder into a ceramic crucible, putting the ceramic crucible into a box-type furnace for primary burning, and preserving heat at 500 ℃ for 8h for primary burning to obtain black powder.
(5) Tabletting and sintering: fully grinding the black powder obtained in the step (4) by using an agate mortar, pressing the black powder into a block with the diameter of 20mm by using a tablet press, then putting the block into a box type furnace, preserving the heat at 1400 ℃ for 12h for final burning to finally obtain La0.65Sm0.05Ca0.3MnO3Polycrystalline ceramic targets.
Example 5 La with low-doped samarium nitrate content of 0.05 mol/l0.65Sm0.05Ca0.3MnO3As can be seen from FIGS. 1, 6, 7 and 8, when the amount of low-doped samarium nitrate was 0.05mol, La was added to the polycrystalline ceramic target0.65Sm0.05Ca0.3MnO3The sample has a typical perovskite structure, no second phase, good crystallization quality, low TCR and MR, respectively 14.51% K-1And 56.10%.
Claims (7)
1. A preparation method of lanthanum calcium manganese oxygen low-doped samarium nitrate is characterized by comprising the following steps:
(1) preparation of sample 2.5g of La0.7-xSmxCa0.3MnO3Polycrystalline ceramic target material prepared by mixing lanthanum nitrate (La (NO)3)3·nH2O), samarium nitrate (Sm (NO)3)3) Calcium nitrate (Ca (NO)3)2·4H2O), manganese nitrate (Mn (NO)3)2·4H2O) and citric acid (C)6H8O7·H2O) calculating the stoichiometric ratio, weighing and placing into a beaker, and adding methanol into the beaker as a solvent;
(2) putting the beaker after the step (1) is finished on a magnetic stirrer, uniformly stirring, simultaneously dropwise adding a small amount of glycol into the beaker, and continuously stirring until the medicine is completely dissolved;
(3) heating the mixed solution obtained in the step (2) in a water bath, and simultaneously stirring by magnetic force until the sol becomes dark yellow, viscous and transparent gel;
(4) quickly putting the gel obtained in the step (3) into a drying box, and drying for 8-12h to obtain dry gel;
(5) pouring the xerogel obtained in the step (4) into a mortar, fully grinding, filling into a ceramic crucible, and placing in a box-type furnace for pre-sintering to obtain nano powder;
(6) fully grinding the powder obtained in the step (5) in a mortar, pressing the powder into blocks by using a tablet press, filling the blocks into a corundum crucible, and placing the corundum crucible in a box furnace for final burning to obtain La0.7-xSmxCa0.3MnO3Polycrystalline ceramic targets.
2. The method for preparing lanthanum calcium manganese oxygen low-doped samarium nitrate according to claim 1, which is characterized in that: la (NO) in step (1)3)3·6H2O，Sm(NO3)3,Ca(NO3)2·4H2O，Mn(NO3)2·4H2O and C6H8O7·H2The molar ratio of O is (0.7-x) x:0.3:1:4, the amount of methanol is n(methanol)：n(CA)3: methanol as a solvent for colloidal chelation.
3. The method for preparing lanthanum calcium manganese oxygen low-doped samarium nitrate according to claim 1, which is characterized in that: the amount of ethylene glycol in the step (2) is n(EG)：n(CA)1: 2, ethylene glycol is used as a dispersant, and citric acid is used as a chelating agent.
4. The method for preparing lanthanum calcium manganese oxygen low-doped samarium nitrate according to claim 1, which is characterized in that: the heating temperature of the water bath heating in the step (3) is 85-88 ℃, and the stirring speed is slowly reduced in the process that the sol becomes viscous.
5. The method for preparing lanthanum calcium manganese oxygen low-doped samarium nitrate according to claim 1, which is characterized in that: the temperature of the drying box in the step (4) is 140-180 ℃, and the drying time is 8-12 h.
6. The method for preparing lanthanum calcium manganese oxygen low-doped samarium nitrate according to claim 1, which is characterized in that: the initial firing process in the step (5) is carried out for 8 hours at 500 ℃, wherein in order to ensure that the sample is fully reacted, the temperature is respectively kept for 1 hour when the temperature is raised to 200 ℃ and 400 ℃.
7. The method for preparing lanthanum calcium manganese oxygen low-doped samarium nitrate according to claim 1, which is characterized in that: the final firing process in the step (6) is heat preservation for 12 hours at 1400 ℃.
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