CN114162847A - Preparation method of gadolinium oxysulfide powder - Google Patents
Preparation method of gadolinium oxysulfide powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 104
- MCVAAHQLXUXWLC-UHFFFAOYSA-N [O-2].[O-2].[S-2].[Gd+3].[Gd+3] Chemical compound [O-2].[O-2].[S-2].[Gd+3].[Gd+3] MCVAAHQLXUXWLC-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011812 mixed powder Substances 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000012190 activator Substances 0.000 claims abstract description 13
- 238000001291 vacuum drying Methods 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 36
- 239000012298 atmosphere Substances 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 14
- 230000004907 flux Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 229910002637 Pr6O11 Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 description 24
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- -1 rare earth oxysulfide Chemical class 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 229910052771 Terbium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007716 flux method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/288—Sulfides
- C01F17/294—Oxysulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7701—Chalogenides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract
The invention provides a preparation method of gadolinium oxysulfide powder, which comprises the following steps: A) gd is added2O3Mixing the activator, the fluxing agent and the sulfur according to the stoichiometric ratio to obtain mixed powder; B) ball-milling the mixed powder and a mineralizer to obtain precursor powder; C) and calcining the precursor powder to obtain primary powder, carrying out acid washing on the primary powder, and carrying out vacuum drying to obtain gadolinium oxysulfide powder. The preparation method of the gadolinium oxysulfide powder is green and environment-friendly, and the gadolinium oxysulfide powder with fine and uniform particle size can be prepared.
Description
Technical Field
The invention relates to the technical field of preparation of infrared materials, in particular to a preparation method of gadolinium oxysulfide powder.
Background
The rare earth oxysulfide has a hexagonal crystal structure, namely a space group P3m1, is insoluble in water and has a chemical formula of RE2O2S, where RE ═ Y, La, Gd, and Lu are the host of the luminescent material, and are white. Gd (Gd)2O2S, i.e. GOS, has a high melting point (2070 ℃ to 2200 ℃), and a lattice constant
Wide forbidden band (4.6eV) and high density (7.34 g/cm)3) Wherein, the atomic number of Gd is 60, which has high stopping power to X-ray, high luminous efficiency, strong oxidation resistance, high light absorption rate and transmission efficiency and no toxicity. Due to the presence of anisotropy, birefringence exists at grain boundaries, and transparent ceramics are not easily prepared. PhononThe energy is low, the physical and chemical stability is good, so that the material can be widely applied to a plurality of fields as an up-conversion material, a long-afterglow material and a cathode-ray luminescent material.
Doping gadolinium oxysulfide powder with various rare earth ions, such as Tb, Eu, Sm, Yb, Pr and the like, wherein Tb and Pr are doped with Gd2O2S is widely applied to luminescent materials for X-ray intensifying screens and field emission display screens; eu doped Gd2O2S is widely applied to red luminescent materials, and the nano fiber of the red luminescent materials is an important novel red nano luminescent material and plays an important role in the fields of luminescence and display, anti-counterfeiting, biological marking, nano devices and the like.
At present, the gadolinium oxysulfide powder is prepared by various methods such as a solid-gas reaction method, a coprecipitation method, a reduction method, a combustion method, an indirect sulfur source method, a precursor vulcanization method, a flux method, an alcohol solution thermal synthesis method, a microwave radiation method and an electrostatic spinning method. The fluxing method is an optimal way for preparing the rare earth doped luminescent ion sample, has low cost, simple operation, good powder dispersibility and complete crystal growth, and is suitable for large-scale industrial production. However, the method has the defects of high reaction temperature, long reaction time, uneven powder particle size distribution, more impurities, harsh reaction conditions, easy generation of more pollutants, chemical wastes and the like. The sulfuration method can lead the rare earth oxide or the specific precursor to be in a certain S steam or H2S、CS2The sulfur oxides are formed by vulcanization in the same atmosphere, if the sulfur source is sufficient and stable, the phase formation and annealing are synchronously carried out, the size of the particles can be regulated, but the vulcanization medium is a polluted gas and is harmful to the environment. The combustion method can realize the batch synthesis of high-purity nano rare earth oxysulfide at low temperature in a short reaction time, but has an agglomeration phenomenon. The solid-gas reaction method has low reaction temperature, can control the size distribution of the precursor, and obtains the oxysulfide powder with high granularity uniformity, but needs to strictly control the reaction atmosphere parameters.
Disclosure of Invention
The invention aims to provide a preparation method of gadolinium oxysulfide powder, which is environment-friendly and can obtain gadolinium oxysulfide powder with smaller particle size.
In view of the above, the present application provides a method for preparing gadolinium oxysulfide powder, including the following steps:
A) gd is added2O3Mixing the activator, the fluxing agent and the sulfur according to the stoichiometric ratio to obtain mixed powder;
B) ball-milling the mixed powder and a mineralizer to obtain precursor powder;
C) and calcining the precursor powder to obtain primary powder, carrying out acid washing on the primary powder, and carrying out vacuum drying to obtain gadolinium oxysulfide powder.
Preferably, the activator is selected from Tb4O7And Pr6O11The fluxing agent is selected from Na2CO3、K2CO3、Li3PO4、Li2CO3And K2PO3The mineralizer is selected from one or two of KF and KCl.
Preferably, the Gd is2O3The mol ratio of the activator to the sulfur is (0.5-1): (0.01-0.04): 4.
Preferably, the fluxing agent is 0.5-1.5 wt% of the mixed powder, and the mineralizing agent is 0.5-2.5 wt% of the mixed powder.
Preferably, the calcination is carried out in a reducing atmosphere, the calcination temperature is 1000-1500 ℃, and the calcination time is 0.5-1 h.
Preferably, the reducing atmosphere is a mixed atmosphere of nitrogen and hydrogen, and the volume percentage of the nitrogen is 10-90%.
Preferably, SO is generated during said calcining2The gas is recovered by active carbon.
Preferably, the reagent used for acid washing is dilute hydrochloric acid or dilute nitric acid, and the acid washing time is 25-60 min.
Preferably, the pickling and the vacuum drying further comprise: water washing and centrifugal treatment.
Preferably, the temperature of the vacuum drying is 50-100 ℃, and the time is 24-48 h.
The application provides a preparation method of gadolinium oxysulfide powder, which is a new method based on rare earth oxide, added fluxing agent and mineralizer, the method effectively avoids the use of sulfur-containing raw materials harmful to the environment and the discharge of harmful byproducts in the conventional method, is a green and environment-friendly preparation technology, obtains a target product by calcining a precursor, and achieves the purpose of adjusting the morphology of the target product by adjusting the morphology of the precursor.
Drawings
FIG. 1 is a schematic view of the process for preparing ultra-fine gadolinium oxysulfide powder according to the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Aiming at the problem of environmental pollution caused by a vulcanization method for preparing gadolinium oxysulfide powder in the prior art, the application provides a preparation method for preparing gadolinium oxysulfide powder, and the preparation method is green and environment-friendly and has small particle size of gadolinium oxysulfide powder. The preparation process of the gadolinium oxysulfide powder is shown in fig. 1, and the embodiment of the invention specifically discloses a preparation method of gadolinium oxysulfide powder, which comprises the following steps:
A) gd is added2O3Mixing the activator, the fluxing agent and the sulfur according to the stoichiometric ratio to obtain mixed powder;
B) ball-milling the mixed powder and a mineralizer to obtain precursor powder;
C) and calcining the precursor powder to obtain primary powder, carrying out acid washing on the primary powder, and carrying out vacuum drying to obtain gadolinium oxysulfide powder.
In the above preparation process, Gd is first introduced in the present application2O3Mixing the activator, the fluxing agent and the sulfur according to the stoichiometric ratio to obtain mixed powder; in this process, the Gd2O3The molar ratio of the activator to the S is (0.5-1): (0.010.04) 4; the activator may be selected from Tb4O7And Pr6O11The rare earth terbium ion or praseodymium ion is introduced, and the luminous intensity and afterglow time of the powder are influenced, and the luminous transition of the ions is influenced. The melting point of the fluxing agent is 700-1400 ℃, and the fluxing agent is specifically selected from Na2CO3、K2CO3、Li3PO4、Li2CO3And K2PO3The addition amount of one or more of the above components is 0.5-1.5 wt% of the mixed powder. The type and purity of the fluxing agent have direct influence on the luminescence property; the fluxing agent functions as a melting aid and a solvent during the formation of the emitter, which serves to lower the sintering temperature of the host-forming crystal and to drive the activator into the crystal lattice to form the luminescent centers and trap centers.
Carrying out ball milling on the mixed powder and a mineralizer to obtain precursor powder; the mineralizer activates the crystal lattice by interacting with the reactant, thereby enhancing the reactivity and accelerating the solid phase reaction. The mineralizer is specifically selected from one or two of KF and KCl, and is 0.5-2.5 wt% of the mixed powder. In the ball milling process, adding the mixture into a planetary ball mill according to a certain ball-material ratio, and carrying out ball milling and mixing uniformly, wherein the ball milling ratio is (2-16): 1, more specifically 2:1, 4:1, 8:1 or 16:1, polishing zirconia ball grinding beads stabilized by high-density yttria, the diameter of which is 10mm, 8mm or 6mm, and placing mixed powder in a protective atmosphere of inert gas in a ball grinding process according to the mass ratio of 1:5:8 to ensure that the mixed powder is not oxidized in the ball grinding process.
The precursor powder is calcined in a reducing atmosphere to obtain primary powder; in the process, sulfur dioxide gas generated by calcination can be recovered by an activated carbon dry method. The calcining temperature is 1000-1500 ℃, and the time is 0.5-3 h; the reducing atmosphere is a mixed atmosphere of nitrogen and hydrogen, and the volume percentage of the nitrogen is 10-90%. The impurities appear when the calcination is carried out for a long time.
The present application then introduces the above-mentioned primary powder intoAcid washing, specifically adding 6% dilute HCl or dilute HNO3And magnetically stirring for 25-40 min, fully reacting to obtain a solution containing gadolinium oxysulfide, and standing for 8-24 h. And finally, washing the obtained powder for 5-8 times, centrifuging, and drying in vacuum for 24-48 h at the drying temperature of 80-100 ℃ to obtain the nanoscale GOS powder.
In the process of preparing the gadolinium oxysulfide powder, the raw materials are all raw materials with the purity of more than or equal to 4N, so that the nano-grade gadolinium oxysulfide powder can be successfully prepared at one time, the prepared gadolinium oxysulfide powder has good dispersibility, complete crystal development and good crystallization performance, the luminous performance of a sample doped with luminescent ions is better than that of a sample prepared by other ways, the problem of polluting gases is solved, the environment is protected, the ultrafine powder can be produced in batches, nano particles with various shapes are obtained, and the gadolinium oxysulfide powder is suitable for large-scale industrial production.
In order to further understand the present invention, the following detailed description is made on the ultra-fine gadolinium oxysulfide powder provided by the present invention with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
A process for preparing superfine gadolinium oxysulfide powder as ideal matrix material, Gd2O2The preparation method of the S powder comprises the following steps:
(1) 181.3g of Gd2O3、15.312g Tb4O7Or 20.428g Pr6O11One of them, flux Na2CO3128.24g S, proportioning according to the stoichiometric proportion, and preliminarily mixing to obtain mixed powder; the amount of the flux added was 0.5 wt%;
(2) adding mineralizers KF and KCl into the mixed powder in a certain proportion, wherein the addition amount of the mineralizers is 0.5 wt%, adding the mineralizers into a planetary ball mill according to a certain ball-to-material ratio, and uniformly mixing the mineralizers with the planetary ball mill in a ball-to-material ratio of 2:1 to obtain precursor powder;
(3) calcining the obtained precursor powder for 1h at 1100 ℃ in a reducing atmosphere to obtain primary powder; SO generated during calcination2The gas can adopt active carbon dry method to recover SO2(ii) a Reducing gasAtmosphere is N2+H2Mixing in proportion, wherein N210-90% of volume percentage and the balance of H2；
(4) Acid washing the primary powder, adding a certain amount of 6% diluted HCl or diluted HNO3Magnetically stirring for 35min, fully reacting to obtain a solution containing gadolinium oxysulfide, and standing for 8 h;
(5) washing for 5-8 times, centrifuging, and drying for 24 hours in vacuum at 80-100 ℃ to obtain the GOS powder with irregular quadrangle shape and 2-3.5 mu m size.
Example 2
A process for preparing superfine gadolinium oxysulfide powder as ideal matrix material, Gd2O2The preparation method of the S powder comprises the following steps:
(1) 181.3g of Gd2O3、15.312g Tb4O7Or 20.428g Pr6O11One of (1), flux Li2CO3128.24g S, proportioning according to the stoichiometric proportion, and preliminarily mixing to obtain mixed powder; the amount of the flux added was 0.5 wt%;
(2) adding mineralizers KF and KCl into the mixed powder in a certain proportion, wherein the addition amount of the mineralizers is 0.5 wt%, adding the mineralizers into a planetary ball mill according to a certain ball-to-material ratio, and uniformly mixing the mineralizers with the planetary ball mill, wherein the ball-to-material ratio is 8:1, so as to obtain precursor powder;
(3) calcining the obtained precursor powder for 1h at 1100 ℃ in a reducing atmosphere to obtain primary powder; SO generated during calcination2The gas can adopt active carbon dry method to recover SO2(ii) a The reducing atmosphere is N2+H2Mixing in proportion, wherein N210-90% of volume percentage and the balance of H2；
(4) Acid washing the primary powder, adding a certain amount of 6% diluted HCl or diluted HNO3Magnetically stirring for 35min, fully reacting to obtain a solution containing gadolinium oxysulfide, and standing for 8 h;
(5) washing for 5-8 times, centrifuging, and drying for 24 hours in vacuum at 80-100 ℃ to obtain the GOS powder with irregular hexagon shape and 2-4 mu m size.
Example 3
A process for preparing superfine gadolinium oxysulfide powder as ideal matrix material, Gd2O2The preparation method of the S powder comprises the following steps:
(1) will 181.3gGd2O3、15.312gTb4O7Or 20.428gPr6O11One of (1), Li in a molar ratio of 1:12CO3And Na2CO3128.24gS is proportioned according to the stoichiometric proportion and preliminarily mixed to obtain mixed powder; the amount of the flux added was 0.5 wt%;
(2) adding mineralizers KF and KCl into the mixed powder in a certain proportion, wherein the addition amount of the mineralizers is 0.5 wt%, adding the mineralizers into a planetary ball mill according to a certain ball-to-material ratio, and uniformly mixing the mineralizers with the planetary ball mill, wherein the ball-to-material ratio is 8:1, so as to obtain precursor powder;
(3) calcining the obtained precursor powder for 1h at 1100 ℃ in a reducing atmosphere to obtain primary powder; SO generated during calcination2The gas can adopt active carbon dry method to recover SO2(ii) a The reducing atmosphere is N2+H2Mixing in proportion, wherein N210-90% of volume percentage and the balance of H2；
(4) Acid washing the primary powder, adding a certain amount of 6% diluted HCl or diluted HNO3Magnetically stirring for 35min, fully reacting to obtain a solution containing gadolinium oxysulfide, and standing for 8 h;
(5) washing for 5-8 times, centrifuging, and vacuum drying for 24 hours at 80-100 ℃ to obtain the spherical GOS powder.
Example 4
A process for preparing superfine gadolinium oxysulfide powder as ideal matrix material, Gd2O2The preparation method of the S powder comprises the following steps:
(1) gd is added2O3The activator is Tb4O7Or Pr6O11One of them, flux Na2CO3S is primarily mixed according to the molar ratio of 1:0.02:4 to obtain mixed powder; fluxingThe addition amount of the agent is 1.5 wt%;
(2) adding mineralizers KF and KCl into the mixed powder in a certain proportion, wherein the addition amount of the mineralizers is 0.5 wt%, adding the mineralizers into a planetary ball mill according to a certain ball-to-material ratio, and uniformly mixing the mineralizers with the planetary ball mill, wherein the ball-to-material ratio is 8:1, so as to obtain precursor powder;
(3) calcining the obtained precursor powder for 1.5h at 1100 ℃ in a reducing atmosphere to obtain primary powder; SO generated during calcination2The gas can adopt active carbon dry method to recover SO2(ii) a The reducing atmosphere is N2+H2Mixing in proportion, wherein N210-90% of volume percentage and the balance of H2；
(4) Acid washing the primary powder, adding a certain amount of 6% diluted HCl or diluted HNO3Magnetically stirring for 35min, fully reacting to obtain a solution containing gadolinium oxysulfide, and standing for 8 h;
(5) washing for 5-8 times, centrifuging, and vacuum drying for 24h at 80-100 ℃ to obtain GOS powder with uniform and spherical particles and particle size below 1 micron.
Example 5
A process for preparing superfine gadolinium oxysulfide powder as ideal matrix material, Gd2O2The preparation method of the S powder comprises the following steps:
(1) 271.95gGd will be mixed2O3、14.952gTb4O7Or 20.428gPr6O11One of them, flux Na2CO3128.24gS is proportioned according to the stoichiometric proportion and preliminarily mixed to obtain mixed powder; the amount of the flux added was 0.5 wt%;
(2) adding mineralizers KF and KCl into the mixed powder in a certain proportion, wherein the addition amount of the mineralizers is 0.5 wt%, adding the mineralizers into a planetary ball mill according to a certain ball-to-material ratio, and uniformly mixing the mineralizers with the planetary ball mill, wherein the ball-to-material ratio is 8:1, so as to obtain precursor powder;
(3) calcining the obtained precursor powder for 1h at 1000 ℃ in a reducing atmosphere to obtain primary powder; SO generated during calcination2The gas can adopt active carbon dry method to recover SO2(ii) a The reducing atmosphere is N2+H2Mixing in proportion, wherein N210-90% of volume percentage and the balance of H2；
(4) Acid washing the primary powder, adding a certain amount of 6% diluted HCl or diluted HNO3Magnetically stirring for 35min, fully reacting to obtain a solution containing gadolinium oxysulfide, and standing for 8 h;
(5) washing with water for 5-8 times, centrifuging, and vacuum drying for 24h at 80-100 ℃ to obtain 2.5-4.5 μm GOS powder.
Example 6
A process for preparing superfine gadolinium oxysulfide powder as ideal matrix material, Gd2O2The preparation method of the S powder comprises the following steps:
(1) 271.95gGd will be mixed2O3、14.952gTb4O7Or 20.428gPr6O11One of them, flux Na2CO3128.24gS is proportioned according to the stoichiometric proportion and preliminarily mixed to obtain mixed powder; the amount of the flux added was 0.5 wt%;
(2) adding mineralizers KF and KCl into the mixed powder in a certain proportion, wherein the addition amount of the mineralizers is 0.5 wt%, adding the mineralizers into a planetary ball mill according to a certain ball-to-material ratio, and uniformly mixing the mineralizers with the planetary ball mill, wherein the ball-to-material ratio is 8:1, so as to obtain precursor powder;
(3) calcining the obtained precursor powder for 1h at 1300 ℃ in a reducing atmosphere to obtain primary powder; SO generated during calcination2The gas can adopt active carbon dry method to recover SO2(ii) a The reducing atmosphere is N2+H2Mixing in proportion, wherein N210-90% of volume percentage and the balance of H2；
(4) Acid washing the primary powder, adding a certain amount of 6% diluted HCl or diluted HNO3Magnetically stirring for 35min, fully reacting to obtain a solution containing gadolinium oxysulfide, and standing for 8 h;
(5) washing for 5-8 times, centrifuging, and vacuum drying for 24h at 80-100 ℃ to obtain 3-6 μm GOS powder.
Comparative example 1
A process for preparing superfine gadolinium oxysulfide powder as ideal matrix material, Gd2O2The preparation method of the S powder comprises the following steps:
(1) 271.95gGd will be mixed2O3、14.952gTb4O7Or 20.428gPr6O11One of them, flux Na2CO3128.24gS is proportioned according to the stoichiometric proportion and preliminarily mixed to obtain mixed powder; the amount of the flux added was 0.5 wt%;
(2) adding the mixed powder into a planetary ball mill according to a certain ball-material ratio, and ball-milling and uniformly mixing, wherein the ball-milling ratio is 8:1 to obtain precursor powder;
(3) calcining the obtained precursor powder for 1h at 1000 ℃ in a reducing atmosphere to obtain primary powder; SO generated during calcination2The gas can adopt active carbon dry method to recover SO2(ii) a The reducing atmosphere is N2+H2Mixing in proportion, wherein N210-90% of volume percentage and the balance of H2；
(4) Acid washing the primary powder, adding a certain amount of 6% diluted HCl or diluted HNO3Magnetically stirring for 35min, fully reacting to obtain a solution containing gadolinium oxysulfide, and standing for 8 h;
(5) washing for 5-8 times, centrifuging, and vacuum drying for 24h at 80-100 ℃ to obtain GOS powder with the particle size of 4-7 microns.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of gadolinium oxysulfide powder comprises the following steps:
A) gd is added2O3Mixing the activator, the fluxing agent and the sulfur according to the stoichiometric ratio to obtain mixed powder;
B) ball-milling the mixed powder and a mineralizer to obtain precursor powder;
C) and calcining the precursor powder to obtain primary powder, carrying out acid washing on the primary powder, and carrying out vacuum drying to obtain gadolinium oxysulfide powder.
2. The process according to claim 1, wherein the activator is selected from Tb4O7And Pr6O11The fluxing agent is selected from Na2CO3、K2CO3、Li3PO4、Li2CO3And K2PO3The mineralizer is selected from one or two of KF and KCl.
3. The method of claim 1, wherein the Gd is2O3The mol ratio of the activator to the sulfur is (0.5-1): (0.01-0.04): 4.
4. The method according to claim 1, wherein the flux is 0.5 to 1.5 wt% of the mixed powder, and the mineralizer is 0.5 to 2.5 wt% of the mixed powder.
5. The preparation method according to claim 1, wherein the calcination is carried out in a reducing atmosphere, and the calcination temperature is 1000 to 1500 ℃ and the calcination time is 0.5 to 1 hour.
6. The preparation method according to claim 5, wherein the reducing atmosphere is a mixed atmosphere of nitrogen and hydrogen, and the volume percentage of the nitrogen is 10-90%.
7. The method of claim 1, wherein SO generated during the calcining is2The gas is recovered by active carbon.
8. The preparation method of claim 1, wherein the acid washing adopts a reagent of dilute hydrochloric acid or dilute nitric acid, and the acid washing time is 25-60 min.
9. The method of claim 1, wherein the acid washing and then the vacuum drying further comprise: water washing and centrifugal treatment.
10. The preparation method according to claim 1, wherein the temperature of the vacuum drying is 50-100 ℃ and the time is 24-48 h.
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