CN104944433B - The preparation method that a kind of rare earth orthoborate is nanocrystalline - Google Patents
The preparation method that a kind of rare earth orthoborate is nanocrystalline Download PDFInfo
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- CN104944433B CN104944433B CN201510418417.4A CN201510418417A CN104944433B CN 104944433 B CN104944433 B CN 104944433B CN 201510418417 A CN201510418417 A CN 201510418417A CN 104944433 B CN104944433 B CN 104944433B
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Abstract
The invention discloses the preparation method that a kind of rare earth orthoborate is nanocrystalline, rare earth oxide is dissolved in nitric acid and makes rare earth nitrate solution by completely, stirs, and the rare earth element of described rare earth oxide is the one in Y, La, Sm or Gd; Sodium hydroxide solution is utilized to regulate pH value to 9 ~ 10 of rare earth nitrate solution; The rare earth nitrate solution mixing up pH value is placed in hydro-thermal autoclave, and react 20 ~ 40h under 180 ~ 220 DEG C of conditions after, Temperature fall is to room temperature, and reacted product deionized water wash obtains intermediate product; The intermediate product obtained is mixed with boric acid solution, stirs; The mixture stirred is placed in hydro-thermal autoclave, and react 40 ~ 60h under 200 ~ 220 DEG C of conditions after, Temperature fall is to room temperature, and reacted product deionized water wash, dries, obtain rare earth orthoborate nanocrystalline.Synthesis temperature of the present invention is low, only has 180 ~ 220 DEG C, lower than traditional solid reaction process 800 DEG C; Product does not need ball milling, improves luminous intensity and the applicability of material.
Description
Technical field
The present invention relates to the preparation method that a kind of rare earth orthoborate is nanocrystalline, belong to technical field of fine.
Background technology
Rare earth orthoborate material, as the luminescent material that a class is important, there is excellent photoluminescence efficiency, chemical stability and wider light-emitting zone, have the good transparency in ultraviolet and vacuum ultraviolet region, rare earth orthoborate material is had a wide range of applications, as YBO
3: Eu and GdBO
3: Eu is used to the red illuminating material of plasma display device, and YBO
3: Tb is used as green luminescent material.General rare earth orthoborate adopts solid reaction process synthesis, temperature of reaction is more than 1100 DEG C, the loss that excessive boric acid or boron trioxide compensate boron in high-temperature burning process need be added, and high-temperature calcination easily causes caking phenomenon, obtain suitable granularity, the granularity of fluorescent material need be reduced by ball milling, thus the luminous intensity of fluorescent material can be reduced, and be difficult to the pattern controlling fluorescent material.And nano luminescent material is due to surface effects, the crystal field residing for atom on surface is different from inner atom, and symmetry reduces, and just likely produces and the different luminescent properties of body material.Meanwhile, material particle size reduces, homogeneity improves, and will contribute to the coating of fluorescent material, reduces the scattering of light of phosphor surface, contributes to improving luminous efficiency.
Summary of the invention
The present invention seeks to: for above the deficiencies in the prior art, the invention provides that a kind of reaction conditions is relatively gentle, synthesis temperature is low, preparation method that the rare earth orthoborate of product particle size and morphology controllable is nanocrystalline, it is by introducing sodium hydroxide as mineralizer, adopt two step hydro-thermal reaction methods, preparing chemical formula is REBO
3rare earth orthoborate nanocrystalline.
Technical scheme of the present invention is: the preparation method that a kind of rare earth orthoborate is nanocrystalline, and the chemical formula of described rare earth orthoborate is REBO
3, described RE be selected from rare earth element y, La, Sm or Gd any one, this preparation method comprises concrete following steps:
1. stoichiometrically take required material rare earth oxide, be dissolved in nitric acid make rare earth nitrate solution completely, stir, the rare earth element of described rare earth oxide is Y, La, Sm or Gd;
2. sodium hydroxide solution is prepared;
3. utilize the described sodium hydroxide solution prepared, regulate the pH value of described rare earth nitrate solution, until the pH value of rare earth nitrate solution is stablized to 9 ~ 10;
4. the rare earth nitrate solution mixing up pH value is placed in hydro-thermal autoclave, reacts after 20 ~ 40h under 180 ~ 220 DEG C of conditions, Temperature fall to room temperature, by reacted product deionized water wash 3 ~ 5 times;
5. stoichiometrically take required material boric acid, be dissolved in deionized water make boric acid solution completely, product step 4. obtained mixes with described boric acid solution, stirs;
6. the mixture that 5. step stirs is placed in hydro-thermal autoclave, reacts after 40 ~ 60h under 200 ~ 220 DEG C of conditions, Temperature fall to room temperature, reacted product deionized water wash 3 ~ 5 times;
7. the product after step 6. being washed is dried, and obtains rare earth orthoborate nanocrystalline.
The present invention, on the basis of technique scheme, also comprises following preferred version:
Described step 2. in, the concentration of the sodium hydroxide solution prepared is 1 ~ 2mol/L.
Advantage of the present invention is:
1, the rare earth orthoborate LaBO of the present invention's synthesis
3, YBO
3and GdBO
3as the substrate material of luminescent material, by doping Eu
3+or Tb
3+deng light emitting ionic ultraviolet and vacuum ultraviolet-excited under there is good luminescent properties, the present invention synthesis SmBO
3as optical absorbing material, to 1.06 μm, 1.54 μm and 10.6 μm of near infrared lights, there is good optical absorption characteristics.
2, synthesis temperature of the present invention is low, only has 180 ~ 220 DEG C, lower than traditional solid reaction process 800 DEG C; Product does not need ball milling, can improve luminous intensity and the applicability of material.
Embodiment:
The present invention's sodium hydroxide is as mineralizer, and adopt two step hydro-thermal reaction methods, preparative chemistry formula is REBO
34 specific embodiments that the rare earth orthoborate of (wherein RE represents rare earth element, be specifically selected from any one in Y, La, Sm or Gd) is nanocrystalline are as follows:
Embodiment 1:
1. required material is stoichiometrically taken: the Y of 0.3387g
2o
3, and by this Y
2o
3be dissolved in completely in nitric acid and make Y (NO
3)
3solution, stirs;
2. compound concentration is the sodium hydroxide solution of 1mol/L;
3. the sodium hydroxide solution utilizing step 2. to prepare, regulates described Y (NO
3)
3the pH value of solution, until Y (NO
3)
3the pH value of solution is stablized to 9;
4. the solution mixing up pH value is placed in hydro-thermal autoclave, react 20h at 180 DEG C after, Temperature fall to room temperature, reacted product deionized water wash 3 times;
5. stoichiometrically take required material: the boric acid of 0.1855g, and be dissolved in deionized water completely by this boric acid and make boric acid solution, product step 4. obtained mixes with this boric acid solution, stirs;
6. the mixture that 5. step stirs is placed in hydro-thermal autoclave, react 40h at 200 DEG C after, Temperature fall to room temperature, reacted product deionized water wash 3 times;
7. the product after washing is put into constant temperature blast drying oven to dry, obtain rare earth orthoborate nanocrystalline.
This example is as follows to the test result that this rare earth orthoborate is nanocrystalline:
By process 7. in dry after powder carry out crystal species analysis with X-ray diffractometer (XRD, D/Max2500), result display main diffraction peak position all with six side YBO
3corresponding, and there is no the peak of other material phases; Carry out particle size and morphology analysis with transmission electron microscope (TEM, JEM-2010UHR), result display granule-morphology is sheet, even particle distribution.
Embodiment 2:
1. required material is stoichiometrically taken: the La of 0.4887g
2o
3, and by this La
2o
3be dissolved in completely in nitric acid and make La (NO
3)
3solution, stirs;
2. compound concentration is the sodium hydroxide solution of 1.5mol/L;
3. the sodium hydroxide solution utilizing step 2. to prepare, regulates described La (NO
3)
3the pH value of solution, until La (NO
3)
3the pH value of solution is stablized to 9.5;
4. the solution 3. step being mixed up pH value is placed in hydro-thermal autoclave, react 30h at 200 DEG C after, Temperature fall to room temperature, reacted product deionized water wash 4 times;
5. stoichiometrically take required material: the boric acid of 0.1855g, and be dissolved in deionized water completely by this boric acid and make boric acid solution, product step 4. obtained mixes with boric acid solution, stirs;
6. the mixture that 5. step stirs is placed in hydro-thermal autoclave, react 50h at 210 DEG C after, Temperature fall to room temperature, reacted product deionized water wash 4 times;
7. the product after washing is put into constant temperature blast drying oven to dry, obtain rare earth orthoborate nanocrystalline.
This example is as follows to the test result that this rare earth orthoborate is nanocrystalline:
By process 7. in dry after powder carry out crystal species analysis with X-ray diffractometer (XRD, D/Max2500), result display main diffraction peak position all with orthogonal LaBO
3corresponding, and there is no the peak of other material phases; Carry out particle size and morphology analysis with transmission electron microscope (TEM, JEM-2010UHR), result display granule-morphology is sheet, even particle distribution.
Embodiment 3:
1. required material is stoichiometrically taken: the Sm of 0.5231g
2o
3, and by this Sm
2o
3be dissolved in completely in nitric acid and make Sm (NO
3)
3solution, stirs;
2. compound concentration is the sodium hydroxide solution of 2mol/L;
3. the sodium hydroxide solution utilizing step 2. to prepare, regulates described Sm (NO
3)
3the pH value of solution, until Sm (NO
3)
3the pH value of solution is stablized to 10;
4. the solution mixing up pH value is placed in hydro-thermal autoclave, react 40h at 220 DEG C after, Temperature fall to room temperature, reacted product deionized water wash 5 times;
5. stoichiometrically take required material: the boric acid of 0.1855g, be dissolved in deionized water make boric acid solution completely, product step 4. obtained mixes with this boric acid solution, stirs;
6. the mixture that 5. step stirs is placed in hydro-thermal autoclave, react 60h at 220 DEG C after, Temperature fall to room temperature, reacted product deionized water wash 5 times;
7. the product after washing is put into constant temperature blast drying oven to dry, obtain rare earth orthoborate nanocrystalline.
This example is as follows to the test result that this rare earth orthoborate is nanocrystalline:
By process 7. in dry after powder carry out crystal species analysis with X-ray diffractometer (XRD, D/Max2500), result display main diffraction peak position all with six side SmBO
3corresponding, and there is no the peak of other material phases; Carry out particle size and morphology analysis with transmission electron microscope (TEM, JEM-2010UHR), result display granule-morphology is sheet, even particle distribution.
Embodiment 4:
1. required material is stoichiometrically taken: the Gd of 0.5437g
2o
3, and by this Gd
2o
3be dissolved in completely in nitric acid and make Gd (NO
3)
3solution, stirs;
2. compound concentration is the sodium hydroxide solution of 2mol/L;
3. the sodium hydroxide solution utilizing step 2. to prepare, regulates described Gd (NO
3)
3the pH value of solution, until Gd (NO
3)
3the pH value of solution is stablized to 9.5;
4. the solution 3. step being mixed up pH value is placed in hydro-thermal autoclave, react 35h at 200 DEG C after, Temperature fall to room temperature, reacted product deionized water wash 5 times;
5. stoichiometrically take required material: the boric acid of 0.1855g, and be dissolved in deionized water completely by this boric acid and make boric acid solution, product step 4. obtained mixes with this boric acid solution, stirs;
6. the mixture that 5. step stirs is placed in hydro-thermal autoclave, react 50h at 210 DEG C after, Temperature fall to room temperature, reacted product deionized water wash 4 times;
7. the product after washing is put into constant temperature blast drying oven to dry, obtain rare earth orthoborate nanocrystalline.
This example is as follows to the test result that this rare earth orthoborate is nanocrystalline:
By process 7. in dry after powder carry out crystal species analysis with X-ray diffractometer (XRD, D/Max2500), result display main diffraction peak position all with six side GdBO
3corresponding, and there is no the peak of other material phases; Carry out particle size and morphology analysis with transmission electron microscope (TEM, JEM-2010UHR), result display granule-morphology is sheet, even particle distribution.
Certainly, above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to people can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations of doing according to the spirit of main technical schemes of the present invention or modification, all should be encompassed within protection scope of the present invention.
Claims (1)
1. the preparation method that rare earth orthoborate is nanocrystalline, the chemical formula of described rare earth orthoborate is REBO
3, described RE be selected from rare earth element y, La, Sm or Gd any one, it is characterized in that the nanocrystalline preparation method of this rare earth orthoborate comprises the following steps:
1. stoichiometrically take required material rare earth oxide, be dissolved in nitric acid make rare earth nitrate solution completely, stir, the rare earth element of described rare earth oxide is Y, La, Sm or Gd;
2. compound concentration is the sodium hydroxide solution of 1 ~ 2mol/L;
3. utilize the described sodium hydroxide solution prepared, regulate the pH value of described rare earth nitrate solution, until the pH value of rare earth nitrate solution is stablized to 9 ~ 10;
4. the rare earth nitrate solution mixing up pH value is placed in hydro-thermal autoclave, reacts after 20 ~ 40h under 180 ~ 220 DEG C of conditions, Temperature fall to room temperature, by reacted product deionized water wash 3 ~ 5 times;
5. stoichiometrically take required material boric acid, be dissolved in deionized water make boric acid solution completely, product step 4. obtained mixes with described boric acid solution, stirs;
6. the mixture that 5. step stirs is placed in hydro-thermal autoclave, reacts after 40 ~ 60h under 200 ~ 220 DEG C of conditions, Temperature fall to room temperature, reacted product deionized water wash 3 ~ 5 times;
7. the product after step 6. being washed is dried, and obtains rare earth orthoborate nanocrystalline.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972457A (en) * | 2010-07-12 | 2011-02-16 | 泰一和浦（北京）中医药研究院有限公司 | Chinese medicinal composition for treating edema during menstruation and preparation method thereof |
| CN103800881A (en) * | 2014-02-20 | 2014-05-21 | 柳晖 | Traditional Chinese medicine composition for treating heart-spleen deficiency syndrome |
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- 2015-07-16 CN CN201510418417.4A patent/CN104944433B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972457A (en) * | 2010-07-12 | 2011-02-16 | 泰一和浦（北京）中医药研究院有限公司 | Chinese medicinal composition for treating edema during menstruation and preparation method thereof |
| CN103800881A (en) * | 2014-02-20 | 2014-05-21 | 柳晖 | Traditional Chinese medicine composition for treating heart-spleen deficiency syndrome |
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Effective date of registration: 20201130 Address after: 334500 Jiangxi city of Shangrao Province Qianshan County Industrial Park Patentee after: Qianshan qirainbow Crystal Technology Co., Ltd Address before: 224051 Yancheng City hope road, Jiangsu, No. 1 Patentee before: YANCHENG INSTITUTE OF TECHNOLOGY |