CN102897845B - High-temperature and high-pressure preparation method for cubic phase barium-iron-antimony oxide and product thereof - Google Patents
High-temperature and high-pressure preparation method for cubic phase barium-iron-antimony oxide and product thereof Download PDFInfo
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- CN102897845B CN102897845B CN201210441715.1A CN201210441715A CN102897845B CN 102897845 B CN102897845 B CN 102897845B CN 201210441715 A CN201210441715 A CN 201210441715A CN 102897845 B CN102897845 B CN 102897845B
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Abstract
The invention discloses a high-temperature and high-pressure preparation method for a cubic phase barium-iron-antimony oxide, and belongs to the technical field of preparation of low field magneto-resistance materials. Barium nitrate, ferric nitrate and antimony trioxide are used as raw materials; the method comprises the process of preparation of a precursor and high-temperature and high-pressure synthesis; the precursor is prepared by mixing raw materials through a sol-gel method; and according to the high-temperature and high-pressure synthesis, heat and pressure are preserved for 1 to 2 hours under the pressure of 5GPa and at the temperature of between 1,100 and 1,300 DEG C, and cooling and pressure relief are carried out to obtain a Ba2FeSbO6 material with a cubic structure. According to the method, the precursor is prepared by using the sol-gel method, so that the reactants are mixed uniformly, and the purity of the final product is high; by adopting the conventional high-temperature and high-pressure equipment, the method is easy to operate and can quickly implement industrialization; and the obtained high-quality barium-iron-antimony oxide is a cubic phase material.
Description
Technical field
The invention belongs to technical field prepared by low magnetoresistance material.Be specifically related to the Emission in Cubic of barium Fe-Sb oxide, and with nitrate of baryta (Ba (NO
3)
2), iron nitrate (Fe (NO
3)
3), antimonous oxide (Sb
2o
3) be raw material, utilize the method for the synthetic barium Fe-Sb oxide Emission in Cubic of sol-gel method and High Temperature High Pressure sintering technology.
background technology
Along with social development and progress, people are also more deep to the cognition of material, and perovskite typed iron-based oxide compound becomes a class material that occupies critical role in current widespread use already.Perovskite typed AFeO
3with double-perovskite type A
2feBO
6compound has stable crystalline structure, the electromagnetic performance of uniqueness and very high redox, hydrogenolysis, isomerization, electrocatalysis isoreactivity, in fields such as environment protection and Industrial Catalysis, has very large potentiality to be exploited.As a kind of novel most possible at room temperature magneto-resistor functional materials of practicality, double-perovskite type iron-based oxide compound receives much concern.Due to Fe
3+, Sb
5+ion has different electronic configurations, different ionic radius and have each other dissimilar exchange interaction, and Sb atom has very large ionic radius, shows good spherical symmetry, makes its barium Fe-Sb oxide (Ba
2feSbO
6) application on the research aspect magnetic resistance and low temperature magnetoresistance material has more potentiality.
Barium Fe-Sb oxide (the Ba that under normal condition prepared by (comprising high temperature solid-state method, sol-gel method, hydrothermal synthesis method etc.) at present
2feSbO
6) crystalline structure of material is hexagonal structure.About adopting High Temperature High Pressure preparation, also do not report at present.New texture by research barium Fe-Sb oxide can be described as the kind that has increased this type oxide mutually, and the different new magnetic resistance performance thereupon producing, and can be increased in the application of low-temperature resistance material aspect.
summary of the invention
The technical problem to be solved in the present invention is to adopt new method-High Temperature High Pressure synthetic method of preparing barium Fe-Sb oxide material, the method is mainly adjusted the formation of the high pressure phase structure of barium Fe-Sb oxide by synthesis temperature and pressure, prepare the high pressure phase material of the barium Fe-Sb oxide with brand-new structure; And the method is easy to implement.
Barium Fe-Sb oxide new texture phase of the present invention, component is Ba
2feSbO
6, its structure is cubic structure.
The concrete technical scheme that the new texture of barium Fe-Sb oxide of the present invention is prepared is mutually as described below.
A preparation method for barium Fe-Sb oxide new texture phase, with nitrate of baryta (Ba (NO
3)
2), iron nitrate (Fe (NO
3)
3), antimonous oxide (Sb
2o
3) be raw material, by sol-gel method, obtain precursor, precursor is made to barium Fe-Sb oxide new texture phase material through briquetting, assembling, High Temperature High Pressure technological process synthetic, cooling release; Described precursor, is by the 4:2:1 mixing in molar ratio of nitrate of baryta, iron nitrate, antimonous oxide, by sol-gel method, prepares gained; Described briquetting, is by the precursor obtaining, and by boron nitride (BN) pipe diameter, is pressed into sheet; Said assembling, is to pack sheet-shaped material into boron nitride (BN) pipe, and packs boron nitride tube into carbon tube heating container, then put into pyrophyllite synthetic cavity; Said High Temperature High Pressure is synthetic, is to carry out in very universal existing high temperature high pressure device, and at pressure, be that 5GPa, temperature are heat-insulation pressure keeping 1～2h at 1100～1300 ℃, stop heating, last cooling release.
Above-mentioned technical scheme also can be stated as:
A high temperature and high pressure preparation process for Emission in Cubic barium Fe-Sb oxide synthesizes in high temperature high pressure device; Make precursor, precursor, through the synthetic process of High Temperature High Pressure, makes barium Fe-Sb oxide cubic structured material; The described precursor that makes, is that raw material nitrate of baryta, iron nitrate and antimonous oxide are mixed for 4: 2: 1 in molar ratio, by sol-gel method, makes powdery precursor; Described is synthetic through High Temperature High Pressure, and first by the compression moulding of precursor powder, coated outside boron nitride (BN) layer, packs in pyrophyllite synthetic cavity; It is synthetic that next carries out High Temperature High Pressure, at pressure, is that 5GPa, temperature are heat-insulation pressure keeping 1 ~ 2h at 1100 ~ 1300 ℃, stops heating; Last cooling release.
The described precursor that makes, is to adopt sol-gel method preparation, can produce according to prior art; Also can produce according to the proportioning raw materials of embodiment 1 and process, that is, produce according to the following procedure: first preparing mass concentration is the tartrate (C of 20g/L
4h
6o
6) aqueous solution; Add raw material nitrate of baryta, iron nitrate and antimonous oxide again, stir and to be warming up to 90 ℃, constant temperature is stirred to the solution thickness that becomes, and forms colloidal sol; The colloidal sol shape product obtaining is toasted 12 hours at 100 ℃, obtain dry bulk colloid; By sintering at 800 ℃, colloid 12 hours, obtain the presoma of collosol and gel; Presoma is ground to form to finely powdered, again after sintering, obtain precursor; The add-on of raw material is by adding 0.01 mole of Sb in every liter of aqueous tartaric acid solution
2o
3calculate.
Described nitrate of baryta (Ba (NO
3)
2), iron nitrate (Fe (NO
3)
3), antimonous oxide (Sb
2o
3) be raw material, their quality purity>=99.9%.
Described cooling release can be to stop naturally cooling to release after room temperature after heating; Can also be to stop heating rear first pressurize release after 3 ~ 8 minutes, then naturally cool to room temperature.The latter is conducive to reduce dephasign, is conducive to the service efficiency to the duration of service of the protection of equipment and minimizing press, raising press.
Compound experiment of the present invention can complete on domestic DS029B type six-plane piercer.Synthetic pressure, temperature are the important factors that affects barium Fe-Sb oxide new texture phase purity, and synthesis condition is under pressure 5GPa preferably, and synthesis temperature is 1100 ~ 1200 ℃, heat-insulation pressure keeping 1 ~ 2 hour.
Best synthesis condition is under pressure 5GPa, and synthesis temperature is 1100 ℃, heat-insulation pressure keeping 1 hour (can referring to embodiment 1).
The present invention also asks for protection the product that adopts the high temperature and high pressure preparation process of Emission in Cubic barium Fe-Sb oxide of the present invention to make.
Beneficial effect of the present invention is, the first, and present method first utilizes sol-gel method to prepare precursor, and reactant is mixed, and products therefrom particle diameter is little, and the final product Emission in Cubic barium Fe-Sb oxide purity of gained is high.Second, the high-temperature high-pressure apparatus that the barium Fe-Sb oxide that present method is produced adopts is used for producing diamond at present at home in a large number, it is simple to operate, with its production, can implement quickly industrialization, and can obtain high-quality barium Fe-Sb oxide Emission in Cubic material.
Accompanying drawing explanation
Fig. 1 is Ba prepared by embodiment 1 sol-gel method
2feSbO
6x-ray diffractogram.
Fig. 2 is Ba prepared by the embodiment of the present invention 2 High Temperature High Pressure
2feSbO
6x-ray diffractogram.
Fig. 3 is Ba prepared by the embodiment of the present invention 3 High Temperature High Pressure
2feSbO
6x-ray diffractogram.
Fig. 4 is Ba prepared by the embodiment of the present invention 4 High Temperature High Pressure
2feSbO
6x-ray diffractogram.
Fig. 5 is Ba prepared by the embodiment of the present invention 5 High Temperature High Pressure
2feSbO
6x-ray diffractogram.
Embodiment
Embodiment 1: with sol-gel method, prepare Ba
2feSbO
6:
Weigh 3 grams of C
4h
6o
6(tartrate), is dissolved in the distilled water of 150ml completely as solvent.Then the Sb that adds 0.0015mol
2o
3(0.4373 gram), heats and stirs.Treat Sb
2o
3while being dissolved in tartaric acid solution completely, take respectively the Fe (NO of 0.003mol
3)
3, 0.006mol Ba (NO
3)
2be dissolved in tartaric acid solution, temperature is adjusted to 90 ℃, continues heated and stirred, and the thickness until solution becomes forms colloidal sol.The colloidal sol shape product obtaining is put into baking oven, in the time of 100 ℃, toast approximately 12 hours, be dried and bulk colloid, colloid is put into retort furnace sintering 12 hours (800 ℃), obtain the presoma of collosol and gel.Presoma is ground to form to finely powdered, put into retort furnace again after sintering, obtain final sample (precursor).Hexagonal structure Ba prepared by this condition
2feSbO
6x-ray the results are shown in Figure 1.
Sb as raw material
2o
3, Fe (NO
3)
3, Ba (NO
3)
2quality purity best>=99.9%.
Embodiment 2: by the method for High Temperature High Pressure, prepare Ba
2feSbO
6
Adopt the precursor of preparing gained in embodiment 1, the precursor that pressure can be caused to moulding at its coated outside last layer BN(after precursor powder is molded packs BN pipe into), sample is packed in pyrophyllite synthetic cavity.In synthetic cavity, with graphite, make heating tube, with agalmatolite, do insulation tube, synthesis pressure is 5GPa, and temperature is 1373K, 1 hour pressure-maintaining and heat-preservation time, stops heating rear sample and naturally cools to release after room temperature.Cubic structure Ba prepared by this condition
2feSbO
6crystallization degree is best, and purity is the highest, and X-ray the results are shown in Figure 2.
Embodiment 3: by the method for High Temperature High Pressure, prepare Ba
2feSbO
6
Adopt assembling and the starting material identical with embodiment 2, synthesis pressure is 5GPa, and temperature is 1473K, 1 hour pressure-maintaining and heat-preservation time, stops heating rear sample and naturally cools to release after room temperature, cubic structure Ba prepared by this condition
2feSbO
6contain oxide compound dephasign.Concrete X-ray the results are shown in Figure 3.
Embodiment 4: by the method for High Temperature High Pressure, prepare Ba
2feSbO
6
Adopt assembling and the starting material identical with embodiment 2, synthesis pressure is 5GPa, and temperature is 1473K, and pressure-maintaining and heat-preservation time 2 h stops heating rear sample and naturally cools to release after room temperature, cubic structure Ba prepared by this condition
2feSbO
6contain amorphous dephasign.Concrete X-ray the results are shown in Figure 4.
Embodiment 5: by the method for High Temperature High Pressure, prepare Ba
2feSbO
6
Adopt assembling and the starting material identical with embodiment 2, synthesis pressure is 5GPa, and temperature is 1573K, 1 hour pressure-maintaining and heat-preservation time, stops heating rear sample and naturally cools to release after room temperature, cubic structure Ba prepared by this condition
2feSbO
6crystallinity is the poorest, contains a large amount of dephasigns.Concrete X-ray the results are shown in Figure 5.
Claims (6)
1. a high temperature and high pressure preparation process for Emission in Cubic barium Fe-Sb oxide synthesizes in high temperature high pressure device; By making precursor, precursor, through the synthetic process of High Temperature High Pressure, makes barium Fe-Sb oxide cubic structured material; The described precursor that makes is first to prepare the aqueous tartaric acid solution that mass concentration is 20g/L; Add raw material nitrate of baryta, iron nitrate and antimonous oxide again, stir and to be warming up to 90 ℃, constant temperature is stirred to the solution thickness that becomes, and forms colloidal sol; The colloidal sol shape product obtaining is toasted 12 hours at 100 ℃, obtain dry bulk colloid; By sintering at 800 ℃, colloid 12 hours, obtain the presoma of collosol and gel; Presoma is ground to form to finely powdered, again after sintering, obtain powdery precursor; Wherein, nitrate of baryta, iron nitrate and antimonous oxide are 4: 2: 1 in molar ratio, and the add-on of raw material is by adding 0.01 mole of Sb in every liter of aqueous tartaric acid solution
2o
3calculate; Described is synthetic through High Temperature High Pressure, and first by the compression moulding of powdery precursor, coated outside boron nitride layer, packs in pyrophyllite synthetic cavity; It is synthetic that next carries out High Temperature High Pressure, at pressure, is that 5GPa, temperature are heat-insulation pressure keeping 1～2h at 1100～1300 ℃, stops heating; Last cooling release.
2. the high temperature and high pressure preparation process of Emission in Cubic barium Fe-Sb oxide according to claim 1, is characterized in that, described nitrate of baryta, iron nitrate, antimonous oxide are raw material, their quality purity >=99.9%.
3. the high temperature and high pressure preparation process of Emission in Cubic barium Fe-Sb oxide according to claim 1, is characterized in that, described cooling release is to stop naturally cooling to release after room temperature after heating; Or stop heating rear first pressurize release after 3～8 minutes, then naturally cool to room temperature.
4. according to the high temperature and high pressure preparation process of the Emission in Cubic barium Fe-Sb oxide described in claim 1,2 or 3, it is characterized in that, described High Temperature High Pressure is synthetic, is under pressure 5GPa, and synthesis temperature is 1100～1200 ℃, heat-insulation pressure keeping 1～2 hour.
5. according to the high temperature and high pressure preparation process of the Emission in Cubic barium Fe-Sb oxide described in claim 1,2 or 3, it is characterized in that, described High Temperature High Pressure is synthetic, is under pressure 5GPa, and synthesis temperature is 1100 ℃, heat-insulation pressure keeping 1 hour.
6. the product that the high temperature and high pressure preparation process of a claim 1 Emission in Cubic barium Fe-Sb oxide makes.
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| CN103865532B (en) * | 2014-03-31 | 2016-03-23 | 长安大学 | Stibnate luminescent material of a kind of double ion doping and preparation method thereof |
| CN104355616A (en) * | 2014-10-27 | 2015-02-18 | 吉林大学 | High-temperature and high-pressure preparation method of cubic phase lanthanum, manganese and titanium oxide and product thereof |
| CN104355617B (en) * | 2014-10-27 | 2016-03-30 | 吉林大学 | A kind of high temperature and high pressure preparation process of Emission in Cubic lanthanum iron titanium oxide |
| CN110040778A (en) * | 2019-05-29 | 2019-07-23 | 吉林大学 | A kind of cubic phase lead tantalum pentoxide and its high temperature and high pressure preparation process |
| CN112987158B (en) * | 2021-04-09 | 2022-03-18 | 广东晟铂纳新材料科技有限公司 | Iron-based optically variable pigment and manufacturing method and application thereof |
| CN114214067B (en) * | 2021-12-27 | 2023-04-18 | 东莞理工学院 | Red fluorescent powder, preparation method and application thereof, and LED (light-emitting diode) illumination light source |
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