CN103332748B - Micro/nano potassium yttrium tungstate near-spherical particles and preparation method thereof - Google Patents
Micro/nano potassium yttrium tungstate near-spherical particles and preparation method thereof Download PDFInfo
- Publication number
- CN103332748B CN103332748B CN201310245935.1A CN201310245935A CN103332748B CN 103332748 B CN103332748 B CN 103332748B CN 201310245935 A CN201310245935 A CN 201310245935A CN 103332748 B CN103332748 B CN 103332748B
- Authority
- CN
- China
- Prior art keywords
- tungstate
- micro
- solution
- preparation
- particle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses micro/nano potassium yttrium tungstate near-spherical particles and a preparation method thereof. The preparation method comprises the following steps: regulating the pH value of a soluble tungstate solution to 7-8.5 and the pH value of Y<3+> of the yttrium ion solution to 5-6.5, mixing according to the tungstate ion:yttrium ion mol ratio of 2:1, regulating the pH value of the mixed solution to 5-7.5, uniformly stirring, adding acetylacetone accounting for 10-20 vol% of the mixed solution, and carrying out ultrasonic vibration to obtain a precursor solution; holding the precursor solution by hydrothermal sealing to obtain a white precipitate, wherein the hydrothermal temperature is 140-180 DEG C, and the holding time is 20-24 hours; and centrifuging the white precipitate, and carrying out heat treatment to obtain the micro/nano potassium yttrium tungstate near-spherical particles. The micro/nano potassium yttrium tungstate near-spherical particles are composed of KY(WO4)2 particles, the particle size is 0.100-1 mu m, and the particle shape is near-spherical. The invention enhances the luminescence efficiency of the powder, can be used as a luminescent material, and can be widely used in the fields of road signs, various energy-saving illuminators, biomedical labels, aviation display devices, various meters and computers, and the like.
Description
Technical field
The present invention relates to luminescent material technical field, be specifically related to a kind of phosphor double tungstates and preparation method thereof.
Background technology
The traditional preparation methods of phosphor is high temperature solid-state method, traditional preparation method needs the equipment of high temperature or complexity usually, reaction times is also long, along with the quick renewal of new technology, the raising of luminescent material performance index needs to overcome the intrinsic defect of classical synthetic method, some new methods are arisen at the historic moment, as combustion method, sol-gel processing, hydrothermal deposition method, microwave method etc.But diverse ways has the limitation of oneself, as combustion method shortcoming: react uncontrollable, powder collects difficulty; Costly, some raw material is organism to the cost of material that sol-gel processing uses, insalubrity, and secondly whole sol-gel process required time is longer; The most obvious defect of hydrothermal method is: subject range is limited to oxide material or minority to the preparation of the not very sensitive sulfide of water and process, and the compound of more inapplicable easily hydrolysis, raw material selection range is little.
Existing phosphor main ingredient is compound and the semiconductor material of rare earth metal, very close with non-ferrous metal relation.High purity rare earth oxides has Y
2o
3, Eu
2o
3, Gd
2o
3, La
2o
3, Tb
4o
7; Semiconductive luminescent materials: ZnS, CdS, ZnSe and GaP, GaAs1-xPx, GaAlAs, GaN etc., and some compounds are as molybdate, tungstate etc.In rare earth oxide and semiconductive luminescent materials there is shortage of resources in Cd, Se, Ga element, expensive shortcoming, it is low also to there is rear-earth-doped concentration in semiconductive luminescent materials, molybdate and part tungstate, the phenomenons such as easy generation concentration quenching, luminous efficiency is relatively low, limits the application of above-mentioned materials to a certain extent.And double tungstates AB (WO
4)
2(A is alkaline-earth metal, B=Re=Y, Gd, La, Lu, Yb etc.), especially KY (WO
4)
2have large absorption and launch transition cross section, the active ions of the higher concentration that can adulterate, the features such as quantum defect is low, effectively can improve luminous efficiency; On the other hand, at matrix WO
the efficient stoke that the high-frequency vibration of group produces is changed, and can realize Raman and multiwavelength laser running simultaneously, and this makes its range of application wider, has potential application at wide spectrums such as remote sensing, medical treatment, scientific research and communications
.
For overcoming the shortcoming of above-mentioned technology of preparing, the present invention adopts tensio-active agent methyl ethyl diketone assisting alcohol-hydrothermal method to prepare the nearly spherical particle of Potassium Yttrium Tungstate.Tensio-active agent auxiliary law has more the advantage of its uniqueness in all many-sides: experimental installation is relatively simple, processing ease, without the need to the complex apparatus of high energy consumption and rapid wear; Mode by changing experiment condition controls particle diameter, pattern, and particle dispersion is even; Raw material dosage is few, recoverable; Be easy to realize continuous prodution running, for suitability for industrialized production provides possibility.
Current people mainly concentrate on the aspects such as bulk single crystal growth, spectral quality, waveguide properties aspect to the report of Potassium Yttrium Tungstate, the report of patent aspect relates to the luminescence (200910067493.X, 200910067492.5,200910114933.2 etc.) of tungstate single crystal preparation (02802513.X), the preparation (200810032456.0,200510026632.6) of tungstate nano film, tungstate, and for the research shorter mention of double tungstates low-dimensional nanoscale, the research of morphology control and the synthesis technique of micro-nanometer structural material.
Summary of the invention
The object of the present invention is to provide nearly spherical particle of a kind of micro-nano Potassium Yttrium Tungstate and preparation method thereof, to improve the luminous efficiency of powder, and Simplified flowsheet, with low cost, reproducible, convenient post-treatment, do not produce foreign-matter contamination.
In order to solve above technical problem, this project controls by hydrothermal method mating surface promoting agent the micro-nano KY (WO generating nearly spherical morphology
4)
2powder body material, the concrete technical scheme of employing is as follows:
The nearly spherical particle of a kind of micro-nano Potassium Yttrium Tungstate, is characterized in that: by KY (WO
4)
2granulometric composition, particle scale is between 0.100 ~ 1 μm, and particle shape is closely spherical.
The preparation method of the nearly spherical particle of described micro-nano Potassium Yttrium Tungstate, is characterized in that comprising the following steps:
Step one, the preparation of precursor solution: be that tungstate and the yttrium compound of 2:1 is dissolved in deionized water, dust technology respectively by the mol ratio of tungstate ion and ruthenium ion, WO
4 2-the pH regulator of solution is 7 ~ 8.5, ruthenium ion solution Y
3+the pH of ion is 5 ~ 6.5, regulates pH of mixed to be 5 ~ 7.5, after stirring again, then adds the methyl ethyl diketone of 10% ~ 20% mixeding liquid volume percentage ratio, obtain precursor liquid through ultrasonic vibration after mixing;
Step 2, hydro-thermal is incubated: load in autoclave obtained precursor solution to 60% ~ 70% of still liner volume, precursor solution obtains white precipitate through hydro-thermal sealing thermal insulation, hydrothermal temperature is 140 DEG C ~ 180 DEG C, soaking time is 20 ~ 24 hours, after reaction terminates, reactor is naturally cooled to room temperature;
Step 3, thermal treatment: take out reaction product from reactor, washing, after carrying out centrifugal treating, then heat-treats, 600 DEG C ~ 900 DEG C 4 ~ 8 hours times of thermal treatment temp to white precipitate, the nearly spherical particle of the micro-nano Potassium Yttrium Tungstate of final acquisition.
Described soluble tungstate salt is hydration K
2wO
4, (NH
4)
2wO
4, (NH
4)
10h
2(W
2o
7)
6in any one.
Described ruthenium ion solution is YCl
3with Y (NO
3)
3in any one, the alkali of the adjustment of described pH is KOH.
The present invention has beneficial effect.The present invention utilizes hydrothermal method to prepare Potassium Yttrium Tungstate, carries out hydro-thermal reaction and obtain the nearly spherical particle of micro-nano even nano level Potassium Yttrium Tungstate in autoclave, is controlled the pattern of product by the adjustment of pH and methyl ethyl diketone.Present method mild condition, do not need special process to remove template, be conducive to suitability for industrialized production, the nearly spherical particle even particle size distribution of gained rule, improves the luminous efficiency of powder, has popularizing application prospect widely.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of Potassium Yttrium Tungstate micro-/ nano particle prepared by embodiment 1;
Fig. 2 is the scanning electron microscope diagram of Potassium Yttrium Tungstate micro-/ nano particle prepared by embodiment 2;
Fig. 3 is the scanning electron microscope diagram of Potassium Yttrium Tungstate micro-/ nano particle prepared by embodiment 3;
Fig. 4 is the scanning electron microscope diagram of Potassium Yttrium Tungstate micro-/ nano particle prepared by embodiment 4;
Fig. 5 is the X-ray diffraction comparative analysis figure of Potassium Yttrium Tungstate micro-/ nano particle prepared by embodiment 1,2,3,4.
Embodiment
Embodiment below further illustrates of the present invention, instead of limit the scope of the invention.
Embodiment 1:
Take a certain amount of hydration K
2wO
4, Y
2o
3be dissolved in respectively in deionized water, dust technology, be mixed with WO
4 2-solution and Y
3+solion; Regulate two solution ph, rear mixing, stirring, then regulate mixed solution pH value to be 5, after be that the methyl ethyl diketone of mixed solution 20% to join in mixed solution ultrasonic vibration half an hour, obtained precursor solution by volume fraction.Obtained precursor solution is left standstill insulation 20 hours in the water heating kettle of 180 DEG C, is filtered by the solution be incubated, cleaned screening through hydro-thermal, loading crucible is transferred to 800 DEG C of heating in High Temperature Furnaces Heating Apparatus and within 8 hours, can be obtained micro-nano Potassium Yttrium Tungstate particle.As shown in Figure 1, granular size is between 0.100 ~ 1 μm, and its powder diagram is as shown in example in Fig. 51.
Embodiment 2:
Take a certain amount of hydration K
2wO
4, Y (NO
3)
3be dissolved in respectively in deionized water, dust technology, be mixed with WO
4 2-solution and Y
3+solion; Regulate two solution ph, rear mixing, stirring, then regulate mixed solution pH value to be 6, after be that the methyl ethyl diketone of mixed solution 20% to join in mixed solution ultrasonic vibration half an hour, obtained precursor solution by volume fraction.Obtained precursor solution is left standstill insulation 20 hours in the water heating kettle of 180 DEG C, is filtered by the solution be incubated, cleaned screening through hydro-thermal, loading crucible is transferred to 800 DEG C of heating in High Temperature Furnaces Heating Apparatus and within 8 hours, can be obtained micro-nano Potassium Yttrium Tungstate particle.As shown in Figure 2, granular size is between 0.3 ~ 1 μm, and its powder diagram is as shown in example in Fig. 52.
Embodiment 3:
Take a certain amount of hydration (NH
4)
2wO
4, Y
2o
3be dissolved in respectively in deionized water, dust technology, be mixed with WO
4 2-solution and Y
3+solion; Regulate two solution ph, rear mixing, stirring, then regulate mixed solution pH value to be 7, after be that the methyl ethyl diketone of mixed solution 15% to join in mixed solution ultrasonic vibration half an hour, obtained precursor solution by volume fraction.Obtained precursor solution is left standstill insulation 20 hours in the water heating kettle of 180 DEG C, is filtered by the solution be incubated, cleaned screening through hydro-thermal, loading crucible is transferred to 800 DEG C of heating in High Temperature Furnaces Heating Apparatus and within 4 hours, can be obtained micro-nano Potassium Yttrium Tungstate particle.As shown in Figure 3, granular size is between 0.1 ~ 0.7 μm, and its powder diagram is as shown in example in Fig. 53.
Embodiment 4:
Take a certain amount of hydration (NH
4)
10h
2(W
2o
7)
6, Y (NO
3)
3be dissolved in respectively in deionized water, dust technology, be mixed with WO
4 2-solution and Y
3+solion; Regulate two solution ph, rear mixing, stirring, then regulate mixed solution pH value to be 7.5, after be that the methyl ethyl diketone of mixed solution 10% to join in mixed solution ultrasonic vibration half an hour, obtained precursor solution by volume fraction.Obtained precursor solution is left standstill insulation 24 hours in the water heating kettle of 180 DEG C, is filtered by the solution be incubated, cleaned screening through hydro-thermal, loading crucible is transferred to 800 DEG C of heating in High Temperature Furnaces Heating Apparatus and within 6 hours, can be obtained micro-nano Potassium Yttrium Tungstate particle.As shown in Figure 4, granular size is between 0.1 ~ 0.7 μm, and its powder diagram is as shown in example in Fig. 54.
Claims (3)
1. a preparation method for the nearly spherical particle of micro-nano Potassium Yttrium Tungstate, described particle is by KY (WO
4)
2granulometric composition, particle scale is between 0.100 ~ 1 μm, and closely spherical it is characterized in that comprises the following steps particle shape:
Step one, the preparation of precursor solution: be that tungstate and the yttrium compound of 2:1 is dissolved in deionized water, dust technology respectively by the mol ratio of tungstate ion and ruthenium ion, WO
4 2-the pH regulator of solution is 7 ~ 8.5, ruthenium ion solution Y
3+the pH of ion is 5 ~ 6.5, regulates pH of mixed to be 5 ~ 7.5, after stirring again, then adds the methyl ethyl diketone of 10% ~ 20% mixeding liquid volume percentage ratio, obtain precursor liquid through ultrasonic vibration after mixing;
Step 2, hydro-thermal is incubated: load in autoclave obtained precursor solution to 60% ~ 70% of still liner volume, precursor solution obtains white precipitate through hydro-thermal sealing thermal insulation, hydrothermal temperature is 140 DEG C ~ 180 DEG C, soaking time is 20 ~ 24 hours, after reaction terminates, reactor is naturally cooled to room temperature;
Step 3, thermal treatment: take out reaction product from reactor, washing, after carrying out centrifugal treating, then heat-treats, 600 DEG C ~ 900 DEG C 4 ~ 8 hours times of thermal treatment temp to white precipitate, the nearly spherical particle of the micro-nano Potassium Yttrium Tungstate of final acquisition.
2. a preparation method for the nearly spherical particle of micro-nano Potassium Yttrium Tungstate as claimed in claim 1, is characterized in that: described tungstate is hydration K
2wO
4, (NH
4)
2wO
4, (NH
4)
10h
2(W
2o
7)
6in any one.
3. a preparation method for the nearly spherical particle of micro-nano Potassium Yttrium Tungstate as claimed in claim 1, is characterized in that: described ruthenium ion solution is YCl
3with Y (NO
3)
3in any one, the alkali of the adjustment of described pH is KOH.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310245935.1A CN103332748B (en) | 2013-08-01 | 2013-08-01 | Micro/nano potassium yttrium tungstate near-spherical particles and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310245935.1A CN103332748B (en) | 2013-08-01 | 2013-08-01 | Micro/nano potassium yttrium tungstate near-spherical particles and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103332748A CN103332748A (en) | 2013-10-02 |
| CN103332748B true CN103332748B (en) | 2015-02-11 |
Family
ID=49240977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310245935.1A Active CN103332748B (en) | 2013-08-01 | 2013-08-01 | Micro/nano potassium yttrium tungstate near-spherical particles and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103332748B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104891572B (en) * | 2015-05-19 | 2017-01-18 | 江苏大学 | A micro-nano potassium yttrium tungstate film and a preparing method thereof |
| CN109734120B (en) * | 2018-12-24 | 2021-05-25 | 江苏大学 | Flower-like microsphere structure potassium yttrium tungstate material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995492B (en) * | 2006-12-01 | 2010-06-02 | 暨南大学 | Nd-doped potassium yttrium tungstate laser crystal growth method |
-
2013
- 2013-08-01 CN CN201310245935.1A patent/CN103332748B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103332748A (en) | 2013-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xiong et al. | Luminescent properties and energy transfer mechanism from Tb3+ to Eu3+ in CaMoO4: Tb3+, Eu3+ phosphors | |
| Jin et al. | Fabrication of Eu3+ and Sm3+ codoped micro/nanosized MMoO4 (M= Ca, Ba, and Sr) via facile hydrothermal method and their photoluminescence properties through energy transfer | |
| Pang et al. | A novel approach for preparation of Y2O3: Eu3+ nanoparticles by microemulsion–microwave heating | |
| Chen et al. | Improved red emission by codoping Li+ in ZnWO4: Eu3+ phosphors | |
| Rui et al. | Sol-gel synthesis and photoluminescence of LaPO4: Eu3+ nanorods | |
| Mao et al. | Simultaneous morphology control and upconversion fluorescence enhancement of NaYF4: Yb, Er crystals through alkali ions doping | |
| CN102079541B (en) | Method for preparing doping type hexagonal system nano ZnS at low temperature | |
| Raju et al. | Synthesis and luminescent properties of low concentration Dy3+: GAP nanophosphors | |
| Lin et al. | Effects of multiple irradiations on luminescent materials and energy savings–A case study for the synthesis of BaMO4: Ln3+ (M= W, Mo; Ln= Eu, Tb) phosphors | |
| Zhong et al. | Microwave-assisted synthesis of water-soluble YF3 and YF3: Ln3+ nanocrystals | |
| Che et al. | A facile aqueous strategy for the synthesis of high-brightness LaPO4: Eu nanocrystals via controlling the nucleation and growth process | |
| Liu et al. | Upconversion/Downconversion luminescence and preparation of NIR-to-UV-excited Gd2O2S: Er phosphor | |
| CN103332748B (en) | Micro/nano potassium yttrium tungstate near-spherical particles and preparation method thereof | |
| Wu et al. | Controllable preparation and fluorescence property of spherical nano-phosphor YPO4: Eu3+ | |
| CN109679652A (en) | The method that microwave and the double outfield auxiliary liquid phase synthesis europiums of ultrasonic wave adulterate biradical matter molybdate red phosphor | |
| Wu et al. | Influence of pH on nano-phosphor YPO4: 2% Sm3+ and luminescent properties | |
| CN102320659B (en) | Method for synthesizing lanthanum-vanadate nano material by adopting microwave-radiation method | |
| CN109504381A (en) | The method of microwave and the double outfield auxiliary liquid phase synthesis bismuth europium codope molybdate red phosphors of ultrasonic wave | |
| Gui et al. | Hydrothermally synthesized β-NaGdF4: Eu3+@ β-NaGdF4: Ce3+, Dy3+ phosphors with multicolor luminescence properties via dual-channel excitation and energy migration procedure | |
| Yang et al. | EDTA-mediated morphology and tunable optical properties of Eu 3+-doped NaY (MoO 4) 2 phosphor | |
| Yu et al. | Hydrothermal synthesis and luminescent properties of Y2O3: Eu3+ from waste phosphors | |
| Ji et al. | Synthesis of high quality Ce: YAG nanopowders by graphene oxide nanosheet-assisted co-precipitation method | |
| Wu et al. | Mechanism of morphology formation and energy transfer of NaLa (WO 4) 2: Sm 3+: Eu 3+ phosphors | |
| CN106544019A (en) | A kind of morphology controllable NaGd (MoO4)2:Eu3+The preparation method of luminescent powder | |
| CN107033897B (en) | Fluorine-doped tungsten molybdate luminescent material excited by near ultraviolet light and synthesis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |