CN116716106A - Preparation method of gadolinium phosphate and rare earth doped gadolinium phosphate fluorescent powder - Google Patents
Preparation method of gadolinium phosphate and rare earth doped gadolinium phosphate fluorescent powder Download PDFInfo
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- JAOZQVJVXQKQAD-UHFFFAOYSA-K gadolinium(3+);phosphate Chemical compound [Gd+3].[O-]P([O-])([O-])=O JAOZQVJVXQKQAD-UHFFFAOYSA-K 0.000 title claims abstract description 67
- 239000000843 powder Substances 0.000 title claims abstract description 55
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 rare earth ions Chemical class 0.000 claims abstract description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 7
- 150000003077 polyols Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 71
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 52
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 27
- 238000010992 reflux Methods 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 150000005846 sugar alcohols Polymers 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000004020 luminiscence type Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000003837 high-temperature calcination Methods 0.000 abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 abstract description 6
- 239000010452 phosphate Substances 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 235000013339 cereals Nutrition 0.000 description 18
- 239000012071 phase Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001144 powder X-ray diffraction data Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002070 nanowire Substances 0.000 description 4
- 238000000103 photoluminescence spectrum Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 150000000921 Gadolinium Chemical class 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000013421 nuclear magnetic resonance imaging Methods 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- UXBZSSBXGPYSIL-UHFFFAOYSA-N phosphoric acid;yttrium(3+) Chemical compound [Y+3].OP(O)(O)=O UXBZSSBXGPYSIL-UHFFFAOYSA-N 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7795—Phosphates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K11/7709—Phosphates
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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Abstract
A preparation method of gadolinium phosphate and rare earth doped gadolinium phosphate fluorescent powder belongs to the technical field of oxide luminescent powder preparation. Adding nitrate containing rare earth ions into a proper polyol solvent according to a certain mass ratio, dissolving, fully mixing with a polyol solution added with phosphoric acid in a certain proportion, stirring at a certain temperature, and directly synthesizing the phosphate fluorescent powder with a monoclinic structure through washing and drying. The method does not need high-temperature calcination, greatly saves energy consumption, and simultaneously avoids defects caused by high-temperature calcination of fluorescent powder, thereby improving luminous efficiency. The synthesized fluorescent powder has uniform size, and lays a good foundation for the subsequent process of the fluorescent powder, thereby perfectly avoiding the occurrence of color spots in the application of the fluorescent powder.
Description
Technical Field
The invention relates to a preparation technology of oxide luminescent powder, in particular to a novel synthesis method for directly synthesizing rare earth doped gadolinium phosphate luminescent powder with a monoclinic structure through a polyalcohol solution.
Background
The rare earth phosphate material has a series of excellent performances and is widely applied to the aspects of lasers, ceramic sensors, fluorescent powder and the like. The lanthanide orthophosphate crystals have both monoclinic and tetragonal xenotime morphologies, with gadolinium phosphate (GdPO 4 ) Synthesis at low temperatures tends to produce lattice mismatch due to the introduction of hydrogen or atomic defects, which crystallize as hexagonal phases, and removal of defects by heat treatment can convert to a more stable monoclinic phase. Gadolinium ions have magnetic moment as high as 7.94 Bohr magneton and ideal paramagnetic relaxation characteristic, and are applied to nuclear magnetic resonance imaging and electron relaxation time nanoseconds, so gadolinium phosphate has potential to become a difunctional fluorescent magnetic material in materials doped with rare earth luminescent ions.
The Gd element is rare earth element, and the ionic radius size of the Gd element is in the middle position of the ionic radius of each element of the lanthanide series, so gadolinium phosphate is used as a matrix, and the Gd element can be compatible with almost all rare earth elements, so that various rare earth ions can be doped as a luminescence center, and the fluorescent powder in various application scenes, such as white luminescent powder, is designed to have more potential in application.
At present, the method for preparing the gadolinium phosphate nano material mainly comprises a hydrothermal synthesis method, a sol-gel method and a coprecipitation method. The hydrothermal synthesis method is a synthesis method which is carried out by utilizing chemical reaction of substances in aqueous solution under the conditions that the temperature is 100-1000 ℃ and the pressure is 1MPa-1 GPa; the sol-gel method is a method of solidifying a compound containing a high chemical active component through solution, sol and gel, and then performing heat treatment to obtain an oxide or other compound solid; the coprecipitation method is to add a proper precipitant into electrolyte solution dissolved with various component ions, react to generate sediment with uniform composition, and thermally decompose to obtain powder materials; in addition, there are methods such as solid phase synthesis methods, but these methods have disadvantages of high energy consumption, low synthesis efficiency and complicated operation.
Therefore, the research and development of the preparation method of the gadolinium phosphate fluorescent powder has the advantages of less energy consumption, high synthesis efficiency, simple and convenient operation, high material purity and mild reaction conditions, and has good social and economic values and wide application prospect.
Patent CN105271151B discloses a synthesis method of gadolinium phosphate, which synthesizes a water-containing gadolinium phosphate crude product through gadolinium nitrate aqueous solution and diammonium phosphate aqueous solution, and finally purifies the gadolinium phosphate crude product, and calcines at 900 ℃ to obtain monoclinic phase powder. However, the whole process is complex, and finally, high-temperature calcination is needed to finally obtain the finished product, and the granularity and the distribution of the finished product are not detailed.
Patent CN102849711a discloses a synthesis method of gadolinium phosphate nanowire, which comprises mixing gadolinium salt solution and phosphate solution, adjusting pH value to 0.5-6.0, and aging under proper condition to obtain gadolinium phosphate nanowire. The aging process of the preparation method is difficult to master, and the biggest problem is that the obtained gadolinium phosphate nanowire is hexagonal. Synthesis of gadolinium phosphate in aqueous solution mostly results in a hexagonal phase because of lattice mismatch due to hydrogen or atomic defect introduction at low temperature, resulting in crystallization into the hexagonal phase. While the phosphor generally requires nearly spherical particles with good fluidity, nanowires are not suitable for phosphor applications.
Although the preparation of gadolinium phosphate can be realized by the methods, the application of the obtained fluorescent powder is subjected to high-temperature calcination, but the high-temperature calcination can cause grain growth and uneven growth, and the subsequent process of the fluorescent powder is adversely affected. Meanwhile, high-temperature calcination can reduce the luminous efficiency of the fluorescent powder. The method can not only realize direct synthesis of monoclinic phase gadolinium phosphate powder by the solution at low temperature, but also emit light after synthesis if a light-emitting center is introduced at the same time. In addition, the method has uniform morphology particles, and greatly optimizes the subsequent fluorescent powder process. In addition, the invention does not need high-temperature calcination, thereby greatly saving energy.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a method for preparing monoclinic rare earth phosphate, in particular gadolinium phosphate powder, which has the advantages of simple process, low cost and good performance. Nitrate containing rare earth ions is added into a polyalcohol solvent according to the mass ratio to be dissolved, and is fully mixed with a polyalcohol solution added with phosphoric acid according to the proportion, and after stirring and reaction at a set temperature, gadolinium phosphate powder or doped gadolinium phosphate fluorescent powder with luminous performance is directly synthesized through washing and drying.
In order to achieve the above purpose, the invention provides a preparation method of gadolinium phosphate and rare earth doped gadolinium phosphate fluorescent powder, which comprises the following process steps:
1. dissolving phosphoric acid in polyalcohol to prepare solution A;
2. gadolinium nitrate is taken and dissolved in polyalcohol to prepare solution B;
or alternatively
Gadolinium nitrate and nitrate of rare earth ions with luminescence characteristics are taken and dissolved in polyol according to a proportion to prepare liquid B;
3. transferring the solution B into a reaction container, wherein 3 ports are arranged at the top of the reaction container, and transferring the solution A into a dripping device; one port of the reaction container is connected with the drip device of the liquid A, one port is connected with the condensing device for reflux to reflux the water evaporated in the system, the nitrogen oxide generated by the volatilization of nitric acid is removed, and the other port is connected with the temperature measuring device for measuring the temperature;
4. when the temperature of the liquid B in the reaction container reaches a preset value, dropwise adding the liquid A into the liquid B, and stirring at the same time;
5. after the liquid drop A is added and the reflux reaction is carried out, a precipitate is formed, the system temperature is reduced to room temperature, and then the washing and the solid-liquid separation are carried out, thus obtaining powder;
6. and drying the washed powder to obtain gadolinium phosphate or rare earth doped gadolinium phosphate fluorescent powder with nanoscale and luminous performance.
In the preparation method, the polyol refers to glycol, glycerol or a mixed solution of glycol and glycerol.
In the step 1, the mole percentage of phosphoric acid in the polyol is 0.01-30%.
In the step 2, the rare earth ion with luminescence property refers to Ce 3+ 、Eu 3+ 、Eu 2+ 、Pr 3+ 、Nd 3+ 、Tb 3+ 、Dy 3+ 、Ho 3 + 、Er 3+ 、Yb 3+ 、Tm 3+ One or more of the following; the mol percentage of rare earth ions and Gd ions is 0.01-30%.
In the step 3 and the step 5, the reflux temperature is 120-240 ℃.
In the step 3 and the step 5, the reflux reaction time is 10min-30h.
In the step 5, the solid-liquid separation method is centrifugal separation, suction filtration, filtration or pressure filtration.
In the step 5, the washing method is to wash with water, ethanol or a mixed solution of water and ethanol for a plurality of times.
In the step 6, the drying temperature is 50-250 ℃.
The method is simple to operate, does not need a large machine or high-temperature calcination, and can synthesize the rice-grain-shaped monoclinic phase phosphate nano particles with good luminous performance and uniform particle size through a simple reflux method and a low-temperature solution. The monoclinic phase gadolinium phosphate powder directly synthesized under the low-temperature solution has more complete solid solution and uniform morphology particles, not only saves energy sources, but also avoids the growth and uneven growth of crystal grains caused by high-temperature calcination, reduces the defect of luminous efficiency of the luminous powder, and avoids the adverse effect on the follow-up process of the luminous powder.
Drawings
Figure 1 XRD pattern of gadolinium phosphate synthesized in example 1 of the present invention.
FIG. 2 is an SEM image of gadolinium phosphate synthesized in example 1 of the present invention.
Figure 3 XRD pattern of gadolinium phosphate synthesized in example 2 of the present invention.
FIG. 4 is an SEM image of gadolinium phosphate synthesized in example 2 of the present invention.
Figure 5 XRD pattern of gadolinium phosphate synthesized in example 3 of the present invention.
FIG. 6 is an SEM image of gadolinium phosphate synthesized with example 3 of the present invention.
Figure 7 XRD pattern of gadolinium phosphate synthesized in example 4 of the present invention.
FIG. 8 is an SEM image of gadolinium phosphate synthesized with example 4 of the present invention.
Figure 9 XRD pattern of gadolinium phosphate synthesized in example 5 of the present invention.
FIG. 10 is an SEM image of gadolinium phosphate synthesized in example 5 of the present invention.
Figure 11 XRD pattern of gadolinium phosphate synthesized in example 6 of the present invention.
FIG. 12 is an SEM image of gadolinium phosphate synthesized with example 6 of the present invention.
FIG. 13 shows the PL profile of gadolinium phosphate synthesized in example 6 of the present invention.
Figure 14 XRD pattern of gadolinium phosphate synthesized in example 7 of the present invention.
FIG. 15 shows the PL profile of gadolinium phosphate synthesized in example 7 of the present invention.
Detailed Description
The invention is further illustrated by the following examples:
example 1
The preparation method of the gadolinium phosphate powder comprises the following specific operation steps:
0.15ml of concentrated phosphoric acid with the concentration of 85% and 10ml of ethylene glycol are weighed to prepare solution A, 0.45g of gadolinium nitrate is weighed and dissolved in 110ml of ethylene glycol to prepare solution B, the solution B is transferred to a three-neck flask, and the solution A is transferred to a burette. One mouth of the three-mouth flask is connected with a buret filled with A liquid, the other mouth is connected with a condenser tube for reflux to remove the nitrogen oxide generated by volatilization of nitric acid, and the other mouth is connected with a thermometer to measure temperature. Solution B was heated to 160℃and after solution A was added to solution B, the pH of the system was 1. Stirring and refluxing to generate precipitate, reacting for 5h, stopping heating, and naturally cooling to room temperature. 50ml of absolute ethanol was added, shaken, centrifuged and the precipitate was repeatedly washed 3 times with deionized water, dried in an oven at 60℃for 24 hours and its XRD, SEM were measured.
The powder XRD pattern is shown in figure 1, and the product is proved to be monoclinic gadolinium phosphate powder. As shown in FIG. 2, the scanning electron microscope is in the shape of rice grains, the average long axis of the grains is 350nm, the average short axis of the grains is 150nm, the powder dispersibility is good, and the grain size distribution is uniform.
Example 2
The preparation method of the gadolinium phosphate powder comprises the following specific operation steps:
0.1ml of concentrated phosphoric acid with the concentration of 85% and 10ml of ethylene glycol are weighed to prepare solution A, 0.45g of gadolinium nitrate is weighed and dissolved in 110ml of ethylene glycol to prepare solution B, the solution B is transferred to a three-neck flask, and the solution A is transferred to a burette. One mouth of the three-mouth flask is connected with a buret filled with A liquid, the other mouth is connected with a condenser tube for reflux to remove the nitrogen oxide generated by volatilization of nitric acid, and the other mouth is connected with a thermometer to measure temperature. Solution B was heated to 160℃and solution A was added dropwise to solution B at which point the pH of the system was 1.8. Stirring and refluxing to generate precipitate, reacting for 5h, stopping heating, and naturally cooling to room temperature. 50ml of absolute ethanol was added, the reaction mixture was shaken to mix it uniformly, centrifuged and the precipitate was repeatedly washed 3 times with deionized water, dried in an oven at 60℃for 24 hours and then XRD and SEM were measured.
The powder XRD pattern is shown in figure 3, and the product is proved to be monoclinic gadolinium phosphate powder. As shown in FIG. 4, the scanning electron microscope is in the shape of rice grains, the average long axis of the grains is 300nm, the average short axis of the grains is 100nm, the powder dispersibility is good, and the grain size distribution is uniform.
Example 3
The preparation method of the gadolinium phosphate powder comprises the following specific operation steps:
0.07ml of concentrated phosphoric acid with the concentration of 85% and 10ml of ethylene glycol are weighed to prepare solution A, 0.45g of gadolinium nitrate is weighed and dissolved in 110ml of ethylene glycol to prepare solution B, the solution B is transferred to a three-neck flask, and the solution A is transferred to a burette. One mouth of the three-mouth flask is connected with a buret filled with A liquid, the other mouth is connected with a condenser tube for reflux to remove the nitrogen oxide generated by volatilization of nitric acid, and the other mouth is connected with a thermometer to measure temperature. Solution B was heated to 160℃and after addition of solution A to solution B, the pH of the system was 2.5. Stirring and refluxing to generate precipitate, reacting for 5h, stopping heating, and naturally cooling to room temperature. 50ml of absolute ethanol was added, the reaction mixture was shaken to mix it uniformly, centrifuged and the precipitate was repeatedly washed 3 times with deionized water, dried in an oven at 60℃for 24 hours and then XRD and SEM were measured.
The powder XRD pattern is shown in figure 5, and the product is proved to be monoclinic phase gadolinium phosphate powder. The scanning electron microscope is shown in fig. 6. The average long axis of the particles is 200nm, the average short axis is 70nm, the powder dispersibility is good, and the particle size distribution is uniform.
As is clear from examples 1 to 3, the pH value increased and gadolinium phosphate powder particles decreased as the amount of phosphoric acid in the solution A decreased.
Example 4
The preparation method of the gadolinium phosphate powder comprises the following specific operation steps:
0.1ml of concentrated phosphoric acid with the concentration of 85% and 10ml of ethylene glycol are weighed to prepare solution A, 0.45g of gadolinium nitrate is weighed and dissolved in 110ml of ethylene glycol to prepare solution B, the solution B is transferred to a three-neck flask, and the solution A is transferred to a burette. One mouth of the three-mouth flask is connected with a buret filled with A liquid, the other mouth is connected with a condenser tube for reflux to remove the nitrogen oxide generated by volatilization of nitric acid, and the other mouth is connected with a thermometer to measure temperature. Solution B was heated to 170℃and solution A was added to solution B with stirring. The reflux reaction lasts for 5 hours, heating is stopped, and natural cooling is carried out to room temperature. 50ml of absolute ethanol was added, the reaction mixture was shaken to mix it uniformly, centrifuged and the precipitate was repeatedly washed 3 times with deionized water, dried in an oven at 60℃for 24 hours and then XRD and SEM were measured.
The powder XRD patterns are shown in figure 7, and the product is proved to be monoclinic phase. As shown in FIG. 8, the scanning electron microscope is in the shape of rice grains, the average long axis of the grains is 300nm, the average short axis of the grains is 70nm, the powder dispersibility is good, and the grain size distribution is uniform.
Example 5
The preparation method of the gadolinium phosphate powder comprises the following specific operation steps:
0.1ml of concentrated phosphoric acid with the concentration of 85% and 10ml of ethylene glycol are weighed to prepare solution A, 0.45g of gadolinium nitrate is weighed and dissolved in 110ml of ethylene glycol to prepare solution B, the solution B is transferred to a three-neck flask, and the solution A is transferred to a burette. One mouth of the three-mouth flask is connected with a buret filled with A liquid, the other mouth is connected with a condenser tube for reflux to remove the nitrogen oxide generated by volatilization of nitric acid, and the other mouth is connected with a thermometer to measure temperature. Solution B was heated to 190℃and solution A was added to solution B with stirring. The reflux reaction lasts for 5 hours, heating is stopped, and natural cooling is carried out to room temperature. 50ml of absolute ethanol was added, the reaction mixture was shaken to mix it uniformly, centrifuged and the precipitate was repeatedly washed 3 times with deionized water, dried in an oven at 60℃for 24 hours and then XRD and SEM were measured.
The powder XRD pattern of this example is shown in figure 9, demonstrating that the product is monoclinic. As shown in FIG. 10, the scanning electron microscope showed a particle shape, the average of the long axis of the particle was 70nm, and the average of the short axis was 20nm. The powder has good dispersibility and uniform particle size distribution.
When the temperature is raised to 170 ℃ and 175 ℃, the granularity of the product is reduced, when the temperature is raised to 190 ℃, the powder particles are rapidly reduced, the average long axis is 70nm, and the average short axis is 20nm. At the system temperature preferred in this process, XRD showed the product to be monoclinic.
Example 6
A preparation method of terbium-doped gadolinium phosphate fluorescent powder comprises the following specific operation steps:
0.1ml of concentrated phosphoric acid with the concentration of 85% and 10ml of ethylene glycol are weighed to prepare a solution A, 0.43g of gadolinium nitrate and 0.023g of terbium nitrate are weighed and dissolved in 110ml of ethylene glycol to prepare a solution B, the solution B is transferred to a three-neck flask, and the solution A is transferred to a burette. One mouth of the three-mouth flask is connected with a buret filled with A liquid, the other mouth is connected with a condenser tube for reflux to remove the nitrogen oxide generated by volatilization of nitric acid, and the other mouth is connected with a thermometer to measure temperature. Solution B was heated to 160℃and solution A was added to solution B with stirring. The reflux reaction lasts for 5 hours, heating is stopped, and natural cooling is carried out to room temperature. 50ml of absolute ethanol was added, the reaction solution was shaken to mix it uniformly, centrifuged and the precipitate was repeatedly washed 3 times with deionized water, dried in an oven at 60℃for 24 hours and its XRD, SEM and PL spectra were measured.
The powder XRD patterns are shown in figure 11, and the product is proved to be monoclinic phase. As shown in FIG. 12, the scanning electron microscope is in the shape of rice grains, the average long axis of the grains is 300nm, the average short axis of the grains is 70nm, the powder dispersibility is good, and the grain size distribution is uniform. The PL spectrum is shown in fig. 13, and shows a characteristic green color of terbium ion.
Example 7
A preparation method of europium-doped gadolinium phosphate fluorescent powder comprises the following specific operation steps:
0.1ml of concentrated phosphoric acid with the concentration of 85% and 10ml of ethylene glycol are weighed to prepare solution A, 0.43g of gadolinium nitrate and 0.022g of europium nitrate are weighed and dissolved in 110ml of ethylene glycol to prepare solution B, the solution B is transferred to a three-neck flask, and the solution A is transferred to a burette. One mouth of the three-mouth flask is connected with a buret filled with A liquid, the other mouth is connected with a condenser tube for reflux to remove the nitrogen oxide generated by volatilization of nitric acid, and the other mouth is connected with a thermometer to measure temperature. Solution B was heated to 160℃and solution A was added to solution B with stirring. The reflux reaction lasts for 5 hours, heating is stopped, and natural cooling is carried out to room temperature. 50ml of absolute ethanol was added, the reaction solution was shaken to mix it uniformly, centrifuged and the precipitate was repeatedly washed 3 times with deionized water, dried in an oven at 60℃for 24 hours and its XRD, SEM and PL spectra were measured.
The XRD pattern of rare earth europium doped gadolinium phosphate is shown in FIG. 14 as the monoclinic phase. SEM showed that the powder was similar to example 6. The PL spectrum of gadolinium phosphate of rare earth ions europium is shown in fig. 15, and the characteristic red color of europium ions can be seen.
From the above examples 6 to 7, it is known that gadolinium nitrate and nitrate of rare earth ion having specific luminescence property are added into a polyhydric alcohol solvent according to a certain mass ratio to dissolve, and a monoclinic structure phosphate having specific luminescence property can be synthesized after the reaction.
Claims (7)
1. The preparation method of the gadolinium phosphate and rare earth doped gadolinium phosphate fluorescent powder is characterized by comprising the following steps:
(1) Dissolving phosphoric acid in polyalcohol to prepare solution A;
(2) Dissolving gadolinium nitrate in polyalcohol to prepare solution B, or dissolving gadolinium nitrate and nitrate of rare earth ions with luminescence property in the polyalcohol according to a proportion to prepare solution B; the rare earth ion with the luminescence characteristic is Ce 3+ 、Eu 3+ 、Eu 2+ 、Pr 3 + 、Nd 3+ 、Tb 3+ 、Dy 3+ 、Ho 3+ 、Er 3+ 、Yb 3+ 、Tm 3+ One or more of the following;
(3) Transferring the solution B into a reaction container, wherein three ports are arranged at the top of the reaction container, and transferring the solution A into a dripping device; one port of the reaction container is connected with a drip device for A liquid, one port is connected with a condensing device for reflux to reflux water evaporated in the system, nitrogen oxides generated by volatilization of nitric acid are removed, and the other port is connected with a temperature measuring device for measuring temperature;
(4) When the temperature of the solution B in the reaction vessel reaches a preset value of 160-190 ℃, dropwise adding the solution A into the solution B, and stirring at the same time;
(5) After the liquid A is dripped and the reflux reaction is carried out, a precipitate is formed; the reflux temperature of the reflux reaction is 120-240 ℃, and the reflux reaction time is 10min-30h; cooling the system to room temperature, washing, and carrying out solid-liquid separation to obtain powder;
(6) And drying the washed powder to obtain gadolinium phosphate or rare earth doped gadolinium phosphate fluorescent powder with nanoscale and luminous performance.
2. The method for preparing gadolinium phosphate and rare earth doped gadolinium phosphate phosphor according to claim 1, wherein the polyol is ethylene glycol, glycerol or a mixed solution of ethylene glycol and glycerol.
3. The method for preparing gadolinium phosphate and rare earth doped gadolinium phosphate phosphor according to claim 1, wherein the mole percentage of phosphoric acid in the polyol is 0.01-30%.
4. The method for preparing gadolinium phosphate and rare earth doped gadolinium phosphate phosphor according to claim 1, wherein the molar percentage of rare earth ions having luminescence characteristics to Gd ions is 0.01 to 30%.
5. The method for preparing gadolinium phosphate and rare earth doped gadolinium phosphate phosphor according to claim 1, wherein the washing method is one or more times of washing with water, ethanol or a mixed solution of water and ethanol.
6. The method for preparing gadolinium phosphate and rare earth doped gadolinium phosphate phosphor according to claim 1, wherein the solid-liquid separation method is centrifugation, suction filtration, filtration or press filtration.
7. The method for preparing gadolinium phosphate and rare earth doped gadolinium phosphate phosphor according to claim 1, wherein the drying temperature is 50-250 ℃.
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| CN105271151A (en) * | 2015-11-24 | 2016-01-27 | 青岛大学 | Preparing method for gadolinium phosphate nanometer material |
| CN112175618A (en) * | 2020-09-28 | 2021-01-05 | 长春工业大学 | Green simple regulation and control synthesis method of highly uniform gadolinium phosphate micro-nano luminescent material |
| CN112480479A (en) * | 2020-11-30 | 2021-03-12 | 江南大学 | Preparation method of nanocellulose-based fluorescent film |
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| CN105271151A (en) * | 2015-11-24 | 2016-01-27 | 青岛大学 | Preparing method for gadolinium phosphate nanometer material |
| CN112175618A (en) * | 2020-09-28 | 2021-01-05 | 长春工业大学 | Green simple regulation and control synthesis method of highly uniform gadolinium phosphate micro-nano luminescent material |
| CN112480479A (en) * | 2020-11-30 | 2021-03-12 | 江南大学 | Preparation method of nanocellulose-based fluorescent film |
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