CN104479677A - Rare-earth element-containing up-conversion luminescent temperature sensitive material as well as preparation method and application thereof - Google Patents
Rare-earth element-containing up-conversion luminescent temperature sensitive material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a rare-earth element-containing up-conversion luminescent temperature sensitive material as well as a preparation method and application thereof. The luminescent material has a general chemical formula of (A0.5Re0.5)TiO3, wherein A is selected from one or more of Rb, K, Na, Li and Ag, and Re is selected from one or more of Er, Yb, Pr, Eu, Ho, Tm, Tb and Dy. The sensitive material can be used for preparing the material provided by the invention, and the luminescent material prepared by the method provided by the invention has excellent up-conversion luminescent performance and temperature sensitivity, high luminescent intensity, good temperature sensitivity, a wide application temperature range, stable chemical performance and a controllable physical size, is easy to prepare, is relatively low in cost, and has a wide application prospect in the fields of fluorescent temperature sensors, short-wave emission solid lasers, biological molecular fluorescence labeling, infrared detection and anti-counterfeiting, three-dimensional display, photoelectric integrated devices, solar batteries and the like.
Description
Technical field
The present invention relates to a class containing the up-conversion luminescence temperature-sensitive material of rare earth element, preparation method and application thereof, belong to Multifunctional photoelectric processor Material Field.
Background technology
Up-conversion refers to the infrared ray excited lower luminescent material that can send visible ray, infrared light can be converted to the material of visible ray.Because its luminescence process runs counter to Stokes law, therefore be also called anti-Stokes law luminescent material.The Er since Auzel reported first in 1966
3+and Yb
3+codope CaWO
4up-conversion starts, and up-conversion luminescence process and corresponding material thereof receive the concern of more and more scientist.First up-conversion with practical value is Er
3+and Yb
3+the LaF of codoped
3, and within certain section time, become the focus of correlative study, also provide a some effective for obtaining visible waveband laser.Divide according to material system, up-conversion can be divided into rare earth fluorine (rare earth fluorine and rare earth and basic metal complex fluoride), rare earth halide, and rare earth oxide (single rare earth oxide compound and composite rare-earth oxide).Wherein, rare earth oxide is compared other two classes material and is had thermostability and chemical stability is high, and preparation technology is simple, with low cost, and preparation process, to advantages such as environmental damage are little, received the concern of some investigators in recent years.The focus of research mainly concentrates on manages to improve its up-conversion luminescence efficiency.
The temperature variant feature of up-conversion luminescence of material can be used for making temperature sensor.At present, fluorescence temperature sensor is mainly based on following three kinds of technology (see Chinese patent CN200910186444.8).The temperature variant technology of ratio of the temperature variant technology of fluorescence intensity, the temperature variant technology of fluorescence lifetime and fluorescence intensity respectively.Wherein, have not by the impact of input stimulus compared with other two kinds of technology based on the temperature variant technology of fluorescence intensity ratio, not by the impact of fiber stress, the advantages such as data analysis is simple.This temperature sensor material requires that material has following feature: first, material will have at a distance of nearer excited level, and these two energy levels preferably coupling level (be conducive to the interference of sensor from the factor such as exciting power, fiber stress, be also beneficial to theoretical analysis); The second, fluorescence intensity comparison temperature sensitive (being conducive to the sensitivity improving sensor), the 3rd, the physico-chemical property of material is stablized (being conducive to widening between temperature measuring area).
Two parameters of the most critical of such materials application between highly sensitive and wide temperature measuring area.Desirable temperature sensing material should have between highly sensitive and wide temperature measuring area simultaneously.But, be two parameters of vying each other for a pair between sensitivity and temperature measuring area.Usual highly sensitive material often its thermostability is poor.On the contrary, the material of usual Heat stability is good has between wide temperature measuring area, but the ratio variation with temperature of its fluorescence intensity often not significantly (sensitivity is low).Such as, according to document Advanced Materials, 2012,24,1987-1993 report, Yb
3al
5o
12: very wide between the temperature measuring area of Er-Mo material (295-973 K), the maximum value of its sensitivity is 0.0048 K
-1.And document Applied Physics Letters reports BaTiO
3: Er nanocrystalline material has high sensitivity, and (maximum value is 0.0052 K
-1), very narrow between the temperature measuring area of this material (only having 322-466 K).In addition, according to Chinese patent CN201220402520.1, NaYF
3: Yb
3+/ Er
3+material has highly sensitive (0.0137 K
-1), but be only 25-180 DEG C between its temperature measuring area, and its application is not coupling level.Therefore how preferred substrate material, regulates the composition of material, or improves the preparation method of material, such that being balanced between sensitivity and temperature measuring area just seems is even more important.
Owing to containing abundant physical phenomenon and peculiar physical properties, perovskite structure oxide material is that current advanced function Material Field is the most active, most active, and one of the most promising research material.In recent years, this kind of material is in luminescence, and dielectric and piezoelectricity, many iron (ferroelectric, ferromagnetic, iron bullet), huge magnetic impedance, metal-insulator phase transition, solid state ionic conductor, the fields such as superconductor, optical nonlinearity and opto-electronic conversion are paid close attention to all widely.With regard to up-conversion luminescent material, because material structure is stablized, preparation technology is simple, with low cost and advantages such as performance easy-regulating, and perovskite structure oxide material is also quite looked at by the parent of investigator.According to bibliographical information, the CaTiO that rare earth erbium doping or erbium, ytterbium are mixed altogether
3, SrTiO
3, BaTiO
3all show stronger up-conversion luminescence phenomenon, see document Journal of Luminescence, 2008,128:797-799, Journal of Alloys and Compounds, 2006,415:280-283 and Optics Express, 2011,19 (3): 1824-1829, Applied Physics Letters, 2004,84 (23): 4753-4755.But according to Chinese patent CN102321575, this Perovskite-type oxides material is as the up-conversion of matrix, and luminous efficiency is lower, limit its application.Recently, contriver place seminar reports a kind of with Na
0.5la
0.5tiO
3for the up-conversion (see Chinese patent CN102321575) of matrix.This material is with appropriate rare earth element er
3+, Ho
3+, Tm
3+, Yb
3+some substitute La, wherein Er
3+, Ho
3+, or Tm
3+as luminescence center, rare earth element y b is as sensitizing agent, and it is high that the methods such as application solid state reaction, solvent thermal and collosol and gel have prepared a class luminous intensity, and size is controlled, the oxide compound up-conversion luminescent material of Color tunable.
The present invention, on the basis of previous work, upgrades formula, adopts new method to prepare the up-conversion luminescence temperature-sensitive material of a class containing rare earth element.The advantages such as research finds, material has excellent up-conversion luminescence and temperature sensitive performance, and have luminous intensity high, temperature sensitivity is good simultaneously, application wide temperature region.Meanwhile, the stable chemical performance of material, physical size is controlled, and be easy to preparation, cost is lower.Thus, can predict, change material at fluorescence temperature sensor, short wavelength emissions solid laser, biomolecules fluorescent mark, infrared acquisition and false proof, 3 D stereo shows, integrated optoelectronic device, and the field such as solar cell has broad application prospects.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a class containing the up-conversion luminescence temperature-sensitive material of rare earth element, preparation method and application thereof, this materials application is in Multifunctional photoelectric processor Material Field.
For achieving the above object and other object, the present invention adopts following technical scheme to realize:
A class provided by the invention is containing the up-conversion luminescence temperature-sensitive material of rare earth element, and the chemical general formula of described luminescent material is (A
0.5re
0.5) TiO
3, wherein: A is one or more in monovalent base metallic element and transition metal Ag element, and Re is lanthanide series rare-earth elements.
In the present invention, described A is selected from Rb, K, Na, one or more in Li or Ag, and Re is selected from one or more in Er, Yb, Pr, Eu, Ho, Tm, Tb or Dy.
The present invention propose the preparation method of up-conversion luminescence temperature-sensitive material containing rare earth element, adopt any one in high energy ball mill method, molten salt react ion method, solvent thermal reaction method or solid phase reaction method, its detailed step is as follows respectively:
1, high energy ball mill method
(1) the taking of raw material: by chemical general formula (A
0.5re
0.5) TiO
3the stoichiometric ratio of middle A, Re and Ti takes following raw material: in the carbonate of element A, nitrate or oxyhydroxide any one, the oxide compound of rare earth element Re or nitrate, the oxide compound of element ti or muriate;
(2) high-energy ball milling: load weighted raw material is put into Special ball mill tank container, then add a certain amount of stearic acid wherein, add a small amount of Pentyl alcohol (or adding appropriate amount of deionized water and dehydrated alcohol) simultaneously.Finally utilize high energy ball mill ball milling, control high speed ball milling 1-100 hour, speed setting is 100-400 rev/min, rotating mode ball milling, and Ball-milling Time and time-out interval are respectively 10-200 minute and 5-60 minute; Stearic add-on is 0 ~ 300% of compound weight, and the add-on of Pentyl alcohol is 1 ~ 50% of compound weight;
(3) thermal treatment: the mixed material dehydrated alcohol after ball milling is diluted, static rear preliminary removing stearic acid, then apply centrifuge to be separated, take out gained pre-treatment powder, again by this powder 500 ~ 1100 DEG C of thermal treatments 1 ~ 10 hour, namely make described up-conversion luminescence temperature-sensitive material after furnace cooling.
Preferably, high energy ball mill described in step (2) adopts PULVERISETTE 5, speed setting is 100-400 rev/min, ball milling 2-50 hour, Ball-milling Time and time-out interval are respectively 20-180 minute and 10-60 minute, in step (3), during dehydrated alcohol dilution, time of repose is 5-100 minute.
Preferably, in step (1), element A selects its carbonate or nitrate, and Re element selects its oxide compound or nitrate, and element ti selects its oxide compound TiO
2or muriate TiCl
4.Preferably; In step (2), stearic add-on is 0 ~ 300% of compound weight, the add-on of Pentyl alcohol is 1 ~ 50% of compound weight, high energy ball mill utilizes PULVERISETTE 5, speed setting is 100-400 rev/min, ball milling 2-50 hour, Ball-milling Time and time-out interval are respectively 20-180 minute and 10-60 minute.In step (3), during dehydrated alcohol dilution, time of repose is 5-100 minute, and after centrifuge is separated, thermal treatment temp is 500 ~ 1000 DEG C.
Preferably, in step (2), stearic add-on is 10 ~ 200% of compound weight, the add-on of Pentyl alcohol is 1 ~ 100% of compound weight, the speed setting of high energy ball mill is 150-380 rev/min, ball milling 2-50 hour, rotating mode ball milling, Ball-milling Time and time-out interval are respectively 20-100 minute and 10-60 minute.In step (3), during dehydrated alcohol dilution, time of repose is 10-30 minute, and after centrifuge is separated, thermal treatment temp is 500 ~ 1000 DEG C, and the time is 1 ~ 8 hour.
Preferably, in step (2), stearic add-on is 10 ~ 100% of compound weight, the add-on of Pentyl alcohol is 5 ~ 100% of compound weight, the speed setting of high energy ball mill is 300-380 rev/min, ball milling 2-20 hour, rotating mode ball milling, Ball-milling Time and time-out interval are respectively 30 minutes and 20 minutes.In step (3), during dehydrated alcohol dilution, time of repose is 20 minutes, and after centrifuge is separated, thermal treatment temp is 500 ~ 1000 DEG C, and the time is 2 ~ 8 hours.
2 molten-salt growth methods
(1) the taking of raw material: by chemical general formula (A
0.5re
0.5) TiO
3, A, Re and Ti element wherein chooses following raw material respectively: elements A is selected from the muriate of A, and rare earth element Re is selected from any one in the oxide compound of Re, vitriol, nitrate or muriate, and element ti is selected from its oxide compound;
(2) precursor preparation: by chemical general formula (A
0.5re
0.5) TiO
3in the stoichiometric ratio of A, Re and Ti take each initial feed, and the muriate adding appropriate A is wherein as fused salt (mass ratio of initial feed and ACl is 1:0.5-1:10), this mixing raw material is ground in agate mortar and within 1-5 hour, makes it to mix, make the precursor powder of molten-salt growth method reaction.Again this precursor powder is transferred in the corundum crucible of adding a cover, finally 700 ~ 1050 DEG C of thermal treatments 1 ~ 10 hour, after furnace cooling, namely makes the precursor of described up-conversion luminescence temperature-sensitive material;
(3) fused salt is separated: the precursor of step (2) gained is put into deionization warm water (water temperature 50-90 DEG C) immersion (10-100h) and make it soft (period can add deionized water is dried to prevent it).Then constantly change the muriate that water repeatedly washs to remove excessive A, or use filtering apparatus elimination except excessive fused salt.Finally the pressed powder obtained is dried obtained described up-conversion luminescence temperature-sensitive material powder at 100-150 DEG C.
Preferably, in step (1), elements A is selected from the muriate of A, and rare earth element Re is selected from nitrate or the muriate of Re, and element ti is selected from its oxide compound (TiO
2); In step (2), the mass ratio of ACl and initial feed is 1:1-1:2.5, and milling time is 2-3 hour, and thermal treatment temp is 720-990 DEG C, heat treatment time 2 ~ 6 hours; In step (3), deionization warm water temperature is soak (10-72 h) in (water temperature 60-80 DEG C).
Preferably, in step (1), elements A is selected from the muriate of A, and rare earth element Re is selected from the nitrate of Re, and element ti is selected from its oxide compound (TiO
2); In step (2), the mass ratio of ACl and initial feed is 1:1-1:2, and milling time is 2-3 hour, and thermal treatment temp is 720-990 DEG C, heat treatment time 2 ~ 4 hours; In step (3), deionization warm water temperature is soak (10-72 h) in (water temperature 60-80 DEG C).
Preferably, in step (1), elements A is selected from the muriate of A, and rare earth element Re is selected from the nitrate of Re, and element ti is selected from its oxide compound (TiO
2); In step (2), the mass ratio of ACl and initial feed is 1:1.5-1:2, and milling time is 2 hours, and thermal treatment temp is 730-990 DEG C, heat treatment time 4 hours; In step (3), deionization warm water temperature is soak (24-72 h) in (water temperature 60-80 DEG C).
3 solvent thermal reaction methods
(1) the choosing of raw material: by chemical general formula (A
0.5re
0.5) TiO
3, A, Re and Ti element wherein chooses following raw material respectively: elements A is selected from the oxyhydroxide of A, and rare earth element Re is selected from nitrate or the muriate of Re, and element ti is selected from titanium tetrachloride, four n-butyl titaniums (tetrabutyl titanate) or titanium tetraisopropylate.Deionized water chosen by solvent, in dehydrated alcohol or ethylene glycol any one;
(2) precursor power: by chemical general formula (A
0.5re
0.5) TiO
3in the stoichiometric ratio of A, Re and Ti take each initial feed, and add deionized water after being mixed by this raw material, fully stir and make it to dissolve in one or more mixed solvents in dehydrated alcohol and ethylene glycol.Then the mol ratio adding appropriate AOH(AOH and Ti element in mixing solutions is 1:1-20:1) and make it fully dissolve.Be transferred in water heating kettle by mixed solution again, carry out solvent thermal reaction, temperature of reaction is 120 DEG C-250 DEG C, and the reaction times is 2 hours-48 hours;
(3) thermal treatment: after solvent heat treatment, upper solution is gone, and repeatedly rinse precipitation powder to go out excessive RbOH with deionized water, finally take out gained pre-treatment powder, again by this powder 400 ~ 1000 DEG C of thermal treatments 1 ~ 10 hour, namely make described up-conversion luminescence temperature-sensitive material after furnace cooling.
Preferably, in step (1), rare earth element Re is selected from the nitrate of Re, and element ti is selected from titanium tetrachloride or four n-butyl titaniums (tetrabutyl titanate); Deionized water chosen by solvent, in dehydrated alcohol or ethylene glycol any one; In step (2), the mol ratio of AOH and Ti element is 1:1-15:1; Temperature of reaction is 120-250 DEG C, and the reaction times is 6-36 hour; In step (3), powder thermal treatment temp is 400 ~ 1000 DEG C, and the time is 1 ~ 10 hour.
Preferably, in step (1), rare earth element Re is selected from the nitrate of Re, and element ti is selected from titanium tetrachloride, four n-butyl titaniums (tetrabutyl titanate); Deionized water chosen by solvent, in dehydrated alcohol or ethylene glycol any one; In step (2), the mol ratio of AOH and Ti element is 1:1-15:1, and temperature of reaction is 180-230 DEG C, and the reaction times is 12-36 hour; In step (3), powder thermal treatment temp is 600 ~ 980 DEG C, and the time is 1 ~ 10 hour.
Preferably, in step (1), rare earth element Re is selected from the nitrate of Re, and element ti is selected from four n-butyl titaniums (tetrabutyl titanate); Deionized water chosen by solvent, in dehydrated alcohol or ethylene glycol any one; In step (2), the mol ratio of AOH and Ti element is 1:1-15:1, and temperature of reaction is 180-230 DEG C, and the reaction times is 12-36 hour; In step (3), powder thermal treatment temp is 600 ~ 980 DEG C, and the time is 1 ~ 10 hour.
4 solid phase reaction methods
(1) the choosing of raw material: by chemical general formula (A
0.5re
0.5) TiO
3, A, Re and Ti element wherein chooses following raw material respectively: elements A is selected from the carbonate of A, and rare earth element Re is selected from the oxide compound of Re, nitrate or muriate, and element ti is selected from titanium dioxide (rutile, anatase octahedrite or brookite);
(2) raw material takes and mixes: by chemical general formula (A
0.5re
0.5) TiO
3in the stoichiometric ratio of A, Re and Ti take each initial feed, wherein volatile A raw material needs suitably excessive (1-10%), and enters in agate mortar by load weighted starting material side, adds alcohol and mixes rear grinding 2-5 hour;
(3) preheating: the blended stock after grinding is put into retort furnace thermal treatment, and thermal treatment temp is 700 ~ 1000 DEG C, and heat treatment time is 1 ~ 10 hour, then makes preburning powdered material with stove cooling down;
(4) double sintering: preburning powdered material is added dehydrated alcohol, grinds 2-5 hour again, then the powder after this being ground was 800 ~ 1200 DEG C of thermal treatments 1 ~ 20 hour, namely made described up-conversion luminescence temperature-sensitive material powder after furnace cooling.
Preferably, in step (1), elements A is selected from the carbonate of A, and rare earth element Re is selected from oxide compound or the nitrate of Re, and element ti is selected from titanium dioxide (rutile, anatase octahedrite or brookite).
Preferably, A raw material excessive (1-5%) in step (2), grinding 2-3 hour.
Preferably, in step (3), thermal treatment temp is 800 ~ 950 DEG C, and heat treatment time is 4 ~ 6 hours.
Preferably, step (4) again milling time is 2-3 hour, and thermal treatment temp is 900 ~ 1100 DEG C, and heat treatment time is 4 ~ 10 hours.
The up-conversion luminescence temperature-sensitive material that the present invention proposes is applied to prepares stupalith, target, and described target is for the preparation of thick film or thin-film material.
The preparation method of the described stupalith that the present invention proposes, concrete steps are as follows:
(1) described up-conversion luminescence temperature-sensitive material is put into agate mortar and grinds 1-2 hour, add wherein concentration be the polyvinyl alcohol of 1 ~ 15% as binding agent, fully stir, seasoning, granulation, cross screen cloth, make spherical powder;
(2) spherical powder is put into grinding tool, the green compact of certain thickness and diameter are made at 10 ~ 100MPa pressure, again green compact are put into retort furnace 500-600 DEG C of insulation 2-10 hour row sticky, finally sample is sintered 1 ~ 10 hour at 950 ~ 1350 DEG C, after being cooled to certain temperature, powered-down cools, and namely obtains described up-conversion luminescence temperature sensitive ceramic block material.
Preferably, adding polyvinyl alcohol concentration in step (1) is 2 ~ 10%, crosses 60 orders and 160 mesh sieves.
Preferably, 500-600 DEG C of insulation 10 hours when in step (2), row is sticky, during sintering, temperature is 950 ~ 1350 DEG C, and sintering time is 2 ~ 8 hours.
In the present invention, described up-conversion luminescence temperature-sensitive material fluorescence temperature sensor, short wavelength emissions solid laser, biomolecules fluorescent mark, infrared acquisition and false proof, 3 D stereo shows, the application of integrated optoelectronic device or area of solar cell.
Up-conversion luminescence temperature-sensitive material prepared by the present invention has excellent luminescent properties, and luminous intensity is high, and temperature sensitivity is good, the stable chemical performance of material, physical size is controlled, is easy to preparation, cost is lower, at fluorescence temperature sensor, short wavelength emissions solid laser, biomolecules fluorescent mark, infrared acquisition and false proof, 3 D stereo shows, integrated optoelectronic device, and the field such as solar cell has broad application prospects.Preparation method of the present invention has that technique is simple, process stabilizing, be easy to the advantages such as industrialization promotion.
Accompanying drawing explanation
Fig. 1 is embodiment 4, (Na prepared by embodiment solid phase reaction method
0.5er
0.5) TiO
3, (Na
0.5eu
0.5) TiO
3, (Na
0.5ho
0.5) TiO
3and (Na
0.5yb
0.5) TiO
3the XRD figure spectrum of powdered sample;
Fig. 2 is different time high-energy ball milling method preparation (Na in embodiment 1
0.5er
0.5) TiO
3the up-conversion luminescence collection of illustrative plates of sample, excitation light source is 980 nanometers;
Fig. 3 and Fig. 4 is respectively the up-conversion luminescence spectrum of product in embodiment 2, and excitation light source is 980 nanometers;
Fig. 5 is the up-conversion luminescence spectrum of product in embodiment 3, and excitation light source is 980 nanometers;
Fig. 6 is the up-conversion luminescence spectrum of product in embodiment 4, and excitation light source is 980 nanometers;
Fig. 7 is product up-conversion luminescence spectrum at different temperatures in embodiment 4;
Fig. 8 is the temperature variant curve of fluorescence intensity ratio of the up-conversion luminescence of product in embodiment 4;
Fig. 9 is the temperature variant curve of sensitivity of the up-conversion luminescence of product in embodiment 4;
Figure 10 ~ 13 are respectively the up-conversion luminescence spectral line of product in embodiment 5 ~ 8, and excitation light source is 980 nanometers;
Figure 14 and Figure 15 is respectively the up-conversion luminescence spectrum of product under differing temps in embodiment 12, and excitation light source is 980 nanometers;
Figure 16 and Figure 17 is respectively the up-conversion luminescence spectrum of product under differing temps in embodiment 16, and excitation light source is 980 nanometers;
Figure 18 is the up-conversion luminescence spectrum of product in embodiment 20, and excitation light source is 980 nanometers;
Figure 19 is the up-conversion luminescence spectrum of product in embodiment 22, and excitation light source is 980 nanometers;
Figure 20 is the up-conversion luminescence spectrum of product in embodiment 30, and excitation light source is 980 nanometers.
Embodiment
Below by way of specific specific examples, embodiments of the present invention are described, those skilled in the art the content described by this specification sheets can understand other advantage of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this specification sheets also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Embodiment 1
High-energy ball milling method preparation (Na
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
Adopt high pure sodium carbonate (99.8%), Erbium trioxide powder (99.9%), titania powder (99.9%), for raw material, stoichiometrically take raw material, load weighted raw material is put into Special ball grinding jar, add a certain amount of stearic acid wherein again, add a small amount of Pentyl alcohol simultaneously.Finally utilize PULVERISETTE 5 high energy ball mill, high speed ball milling 4 hours, speed setting is 350 revs/min, rotating mode ball milling, and Ball-milling Time and time-out interval are respectively 20 minutes and 20 minutes.Again the mixed material dehydrated alcohol after ball milling is diluted, static rear preliminary removing stearic acid, then applies centrifuge and is separated, take out gained pre-treatment powder, again by this powder 800 DEG C of thermal treatments 10 hours, namely make described up-conversion luminescence temperature-sensitive material powder after furnace cooling; The up-conversion luminescence spectrum (excitaton source: 980 nm infrared lasers) of different time high-energy ball milling sample as shown in Figure 2.Luminescent material prepared by the present invention has good luminescent properties and temperature sensitive performance, is especially applicable to doing temperature sensor application.
Embodiment 2
Molten-salt growth method preparation (Na
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
By chemical general formula (Na
0.5er
0.5) TiO
3, initial feed is respectively high pure sodium chloride (NaCl, 98%), Erbium trioxide powder (Er
2o
3, 99.9%), titania powder (TiO
2, 99.9%); And take each initial feed by its stoichiometric ratio, and add lithium chloride wherein as fused salt (mass ratio of initial feed and LiCl is 1:1.2), this mixing raw material is ground in agate mortar and within 3 hours, makes it to mix, make the precursor powder of molten-salt growth method reaction.Be transferred to by this precursor powder in the corundum crucible of adding a cover, finally 750 DEG C of thermal treatments 10 hours, (36 h) make it soft (period can add deionized water is dried to prevent it) to put into deionization warm water (water temperature 80 DEG C) immersion after furnace cooling again.Then constantly change water repeatedly to wash to remove excess chlorination lithium, or use the elimination of suction filtration instrument except excessive fused salt.Finally the pressed powder obtained is dried obtained described up-conversion luminescence temperature-sensitive material powder at 120 DEG C.Under 980 nanometer optical excitation, (the Na of preparation
0.5er
0.5) TiO
3the up-conversion luminescence spectrum of luminescent material as shown in Figures 3 and 4.Luminescent material prepared by the present invention has excellent luminescent properties, and luminous intensity is higher.
Embodiment 3
Solvent-thermal method preparation (Na
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
By chemical formula (Na
0.5er
0.5) TiO
3, wherein initial feed is respectively High Purity Hydrogen potassium oxide (NaOH, 99%), Erbium trinitrate [Er (NO
3)
35H
2o, 99.9%], four n-butyl titaniums (tetrabutyl titanate) liquid (C
16h
36o
4ti, 98%); Each initial feed is taken by its stoichiometric ratio.Deionized water chosen by solvent, dehydrated alcohol, and ethylene glycol; Add after this raw material is mixed in ethylene glycol also fully to stir and make it to dissolve completely.Then in mixing solutions, add appropriate NaOH and make it fully dissolve.Finally be transferred in water heating kettle by mixed solution, carry out solvent thermal reaction, temperature of reaction is 180 DEG C, and the reaction times is 24 hours; After solvent heat treatment, upper solution is gone, and repeatedly rinses precipitation powder to go out excessive NaOH with deionized water, finally take out gained pre-treatment powder, again by this powder 750 DEG C of thermal treatments 4 hours, namely make described up-conversion luminescence temperature-sensitive material powder after furnace cooling.(the Na prepared
0.5er
0.5) TiO
3the up-conversion luminescence spectrum of luminescent material under 980 nanometer optical excitation as shown in Figure 5.Luminescent material prepared by the present invention has excellent luminescent properties, and luminance conversion efficiency is high.
Embodiment 4
Solid phase method preparation (Na
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
Adopt high-purity salt of wormwood (Na
2cO
3, 99.8%), Erbium trioxide powder (Er
2o
3, 99.9%), titania powder (TiO
2, 99.9%) and be raw material, stoichiometrically take raw material, putting into agate mortar, is after solvent Homogeneous phase mixing with alcohol, the dry post-drying powder of alcohol mill, the powder obtained to be placed in corundum boat in 750 DEG C of pre-burnings 4 hours in atmosphere, after cooling, to grind oven dry in the same fashion.Again powder is placed in after oven dry corundum boat in atmosphere 1100 DEG C calcining 10 hours.The XRD spectrum of the luminescent material prepared as shown in Figure 1, Fig. 6 gives the up-conversion luminescence spectrum under this material room temperature (excitaton source: 980 nm infrared lasers), during as temperature sensing material, as shown in Figure 7, its fluorescence intensity when susceptibility variation with temperature curve provides up-conversion luminescence spectrum under differing temps respectively in figs. 8 and 9.Luminescent material prepared by the present invention has excellent luminescent properties, and luminous intensity is high, temperature sensing excellent performance.
Embodiment 5
Solid phase method preparation (Na
0.5pr
0.5) TiO
3powder body material, preparation method is as follows:
Adopt high-purity salt of wormwood (Na
2cO
3, 99.8%), Praseodymium trioxide powder (Pr
5o
11, 99.9%), titania powder (TiO
2, 99.9%) and be raw material, stoichiometrically take raw material, putting into agate mortar, is after solvent Homogeneous phase mixing with alcohol, the dry post-drying powder of alcohol mill, the powder obtained to be placed in corundum boat in 750 DEG C of pre-burnings 4 hours in atmosphere, after cooling, to grind oven dry in the same fashion.Again powder is placed in after oven dry corundum boat in atmosphere 1100 DEG C calcining 10 hours.As shown in Figure 1, Figure 10 gives the up-conversion luminescence spectrum (excitaton source: 980 nm infrared lasers) of this material to the XRD spectrum of the luminescent material prepared.
Embodiment 6
Solid phase method preparation (Na
0.5yb
0.5) TiO
3powder body material, preparation method is as follows:
Adopt high-purity salt of wormwood (Na
2cO
3, 99.8%), yttrium oxide powder (Yb
2o
3, 99.9%), titania powder (TiO
2, 99.9%) and be raw material, stoichiometrically take raw material, putting into agate mortar, is after solvent Homogeneous phase mixing with alcohol, the dry post-drying powder of alcohol mill, the powder obtained to be placed in corundum boat in 750 DEG C of pre-burnings 4 hours in atmosphere, after cooling, to grind oven dry in the same fashion.Again powder is placed in after oven dry corundum boat in atmosphere 1000 DEG C calcining 10 hours.The XRD spectrum of the luminescent material prepared as shown in Figure 1, Figure 11 gives (Na
0.5yb
0.5) TiO
3the up-conversion luminescence spectrum (excitaton source: 980 nm infrared lasers) of powder body material.
Embodiment 7
Solid phase method preparation (Na
0.5eu
0.5) TiO
3powder body material, preparation method is as follows:
Adopt high-purity salt of wormwood (Na
2cO
3, 99.8%), europium sesquioxide powder (Eu
2o
3, 99.9%), titania powder (TiO
2, 99.9%) and be raw material, stoichiometrically take raw material, putting into agate mortar, is after solvent Homogeneous phase mixing with alcohol, the dry post-drying powder of alcohol mill, the powder obtained to be placed in corundum boat in 750 DEG C of pre-burnings 4 hours in atmosphere, after cooling, to grind oven dry in the same fashion.Again powder is placed in after oven dry corundum boat in atmosphere 900 DEG C calcining 10 hours.As shown in Figure 1, Figure 12 gives the up-conversion luminescence spectrum (excitaton source: 980 nm infrared lasers excite) of this material to the XRD spectrum of the luminescent material prepared.
Embodiment 8
Solid phase method preparation (Na
0.5ho
0.5) TiO
3powder body material, preparation method is as follows:
Adopt high-purity salt of wormwood (Na
2cO
3, 99.8%), Holmium trioxide powder (Ho
2o
3, 99.9%), titania powder (TiO
2, 99.9%) and be raw material, stoichiometrically take raw material, putting into agate mortar, is after solvent Homogeneous phase mixing with alcohol, the dry post-drying powder of alcohol mill, the powder obtained to be placed in corundum boat in 750 DEG C of pre-burnings 4 hours in atmosphere, after cooling, to grind oven dry in the same fashion.Again powder is placed in after oven dry corundum boat in atmosphere 1100 DEG C calcining 10 hours.As shown in Figure 1, Figure 13 gives the up-conversion luminescence spectrum (excitaton source: 980 nm infrared lasers excite) of this material to the XRD spectrum of the luminescent material prepared.
Embodiment 9
High-energy ball milling method preparation (K
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
Adopt high-purity salt of wormwood (99.8%), Erbium trioxide powder (99.9%), titania powder (99.9%), for raw material, stoichiometrically take raw material, load weighted raw material is put into Special ball grinding jar, add a certain amount of stearic acid wherein again, add a small amount of Pentyl alcohol simultaneously.Finally utilize PULVERISETTE 5 high energy ball mill, high speed ball milling 4 hours, speed setting is 350 revs/min, rotating mode ball milling, and Ball-milling Time and time-out interval are respectively 20 minutes and 20 minutes.Again the mixed material dehydrated alcohol after ball milling is diluted, static rear preliminary removing stearic acid, then applies centrifuge and is separated, take out gained pre-treatment powder, again by this powder 900 DEG C of thermal treatments 10 hours, namely make described up-conversion luminescence temperature-sensitive material powder after furnace cooling.
Embodiment 10
Molten-salt growth method preparation (K
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
By chemical general formula (K
0.5er
0.5) TiO
3, initial feed is respectively high purity potassium chloride (KCl, 99.8%), Erbium trioxide powder (Er
2o
3, 99.9%), titania powder (TiO
2, 99.9%); And take each initial feed by its stoichiometric ratio, and add Repone K wherein as fused salt (mass ratio of initial feed and KCl is 1:1.2), this mixing raw material is ground in agate mortar and within 3 hours, makes it to mix, make the precursor powder of molten-salt growth method reaction.Again this precursor powder is transferred in the corundum crucible of adding a cover, finally 950 DEG C of thermal treatments 10 hours, puts into deionization warm water (water temperature 80 DEG C) immersion (36h) after furnace cooling and make it soft (period can add deionized water is dried to prevent it).Then constantly change water repeatedly to wash to remove excess chlorination potassium, or use filtering apparatus elimination except excessive fused salt.Finally the pressed powder obtained is dried obtained described up-conversion luminescence temperature-sensitive material powder at 120 DEG C.
Embodiment 11
Solvent-thermal method preparation (K
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
By chemical formula (K
0.5er
0.5) TiO
3, wherein initial feed is respectively High Purity Hydrogen potassium oxide (KOH, 99.8%), Erbium trinitrate [Er (NO
3)
35H
2o, 99.9%], four n-butyl titaniums (tetrabutyl titanate) liquid (C
16h
36o
4ti, 98%); Each initial feed is taken by its stoichiometric ratio.Deionized water chosen by solvent, dehydrated alcohol, and ethylene glycol; Add after this raw material is mixed in ethylene glycol also fully to stir and make it to dissolve completely.Then in mixing solutions, add appropriate KOH and make it fully dissolve.Finally be transferred in water heating kettle by mixed solution, carry out solvent thermal reaction, temperature of reaction is 180 DEG C, and the reaction times is 24 hours; After solvent heat treatment, upper solution is gone, and repeatedly rinses precipitation powder to go out excessive KOH with deionized water, finally take out gained pre-treatment powder, again by this powder 850 DEG C of thermal treatments 4 hours, namely make described up-conversion luminescence temperature-sensitive material powder after furnace cooling.
Embodiment 12
Solid phase method preparation (K
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
Adopt high-purity salt of wormwood (K
2cO
3, 99.8%), Erbium trioxide powder (Er
2o
3, 99.9%), titania powder (TiO
2, 99.9%) and be raw material, stoichiometrically take raw material, putting into agate mortar, is after solvent Homogeneous phase mixing with alcohol, the dry post-drying powder of alcohol mill, the powder obtained to be placed in corundum boat in 750 DEG C of pre-burnings 4 hours in atmosphere, after cooling, to grind oven dry in the same fashion.Again powder is placed in after oven dry corundum boat in atmosphere 800-1050 DEG C calcining 10 hours.Namely described up-conversion luminescence temperature-sensitive material powder is made after furnace cooling.Figure 14 and Figure 15 sets forth the up-conversion luminescence spectral line of 850 DEG C and 900 DEG C calcining 10 hr sample.
Embodiment 13
High-energy ball milling method preparation (Li
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
Adopt pure Lithium Carbonate (99.8%), Erbium trioxide powder (99.9%), titania powder (99.9%), for raw material, stoichiometrically take raw material, load weighted raw material is put into Special ball grinding jar, add a certain amount of stearic acid wherein again, add a small amount of Pentyl alcohol simultaneously.Finally utilize PULVERISETTE 5 high energy ball mill, high speed ball milling 4 hours, speed setting is 350 revs/min, rotating mode ball milling, and Ball-milling Time and time-out interval are respectively 20 minutes and 20 minutes.Again the mixed material dehydrated alcohol after ball milling is diluted, static rear preliminary removing stearic acid, then apply centrifuge to be separated, take out gained pre-treatment powder, again by this powder 700-900 DEG C of thermal treatment 10 hours, namely make described up-conversion luminescence temperature-sensitive material powder after furnace cooling; Namely described up-conversion luminescence temperature-sensitive material powder is made after furnace cooling.
Embodiment 14
Molten-salt growth method preparation (Li
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
By chemical general formula (Li
0.5er
0.5) TiO
3, initial feed is respectively industrial grade methanol (LiCl, 98%), Erbium trioxide powder (Er
2o
3, 99.9%), titania powder (TiO
2, 99.9%); And take each initial feed by its stoichiometric ratio, and add lithium chloride wherein as fused salt (mass ratio of initial feed and LiCl is 1:1.2), this mixing raw material is ground in agate mortar and within 3 hours, makes it to mix, make the precursor powder of molten-salt growth method reaction.Again this precursor powder is transferred in the corundum crucible of adding a cover, finally 750 DEG C of thermal treatments 10 hours, puts into deionization warm water (water temperature 80 DEG C) immersion (36h) after furnace cooling and make it soft (period can add deionized water is dried to prevent it).Then constantly change water repeatedly to wash to remove excess chlorination lithium, or use filtering apparatus elimination except excessive fused salt.Finally the pressed powder obtained is dried obtained described up-conversion luminescence temperature-sensitive material powder at 120 DEG C.
Embodiment 15
Solvent-thermal method preparation (Li
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
By chemical formula (Li
0.5er
0.5) TiO
3, wherein initial feed is respectively High Purity Hydrogen potassium oxide (LiOH, 99%), Erbium trinitrate [Er (NO
3)
35H
2o, 99.9%], four n-butyl titaniums (tetrabutyl titanate) liquid (C
16h
36o
4ti, 98%); Each initial feed is taken by its stoichiometric ratio.Deionized water chosen by solvent, dehydrated alcohol, and ethylene glycol; Add after this raw material is mixed in ethylene glycol also fully to stir and make it to dissolve completely.Then in mixing solutions, add appropriate LiOH and make it fully dissolve.Finally be transferred in water heating kettle by mixed solution, carry out solvent thermal reaction, temperature of reaction is 180 DEG C, and the reaction times is 24 hours; After solvent heat treatment, upper solution is gone, and repeatedly rinses precipitation powder to go out excessive LiOH with deionized water, finally take out gained pre-treatment powder, again by this powder 750 DEG C of thermal treatments 4 hours, namely make described up-conversion luminescence temperature-sensitive material powder after furnace cooling.
Embodiment 16
Solid phase method preparation (Li
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
Adopt high-purity salt of wormwood (Li
2cO
3, 99.8%), Erbium trioxide powder (Er
2o
3, 99.9%), titania powder (TiO
2, 99.9%) and be raw material, stoichiometrically take raw material, putting into agate mortar, is after solvent Homogeneous phase mixing with alcohol, the dry post-drying powder of alcohol mill, the powder obtained to be placed in corundum boat in 750 DEG C of pre-burnings 4 hours in atmosphere, after cooling, to grind oven dry in the same fashion.Again powder is placed in after oven dry corundum boat in atmosphere 750-1000 DEG C calcining 10 hours.Figure 16 and Figure 17 sets forth 850 DEG C and 900 DEG C of calcinings, 10 hours (Li
0.5er
0.5) TiO
3the up-conversion luminescence spectral line of powder sample.
Embodiment 17
High-energy ball milling method preparation (Rb
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
Adopt high-purity rubidium carbonate (99.8%), Erbium trioxide powder (99.9%), titania powder (99.9%), for raw material, stoichiometrically take raw material, load weighted raw material is put into Special ball grinding jar, add a certain amount of stearic acid wherein again, add a small amount of Pentyl alcohol simultaneously.Finally utilize PULVERISETTE 5 high energy ball mill, high speed ball milling 4 hours, speed setting is 350 revs/min, rotating mode ball milling, and Ball-milling Time and time-out interval are respectively 20 minutes and 20 minutes.Again the mixed material dehydrated alcohol after ball milling is diluted, static rear preliminary removing stearic acid, then applies centrifuge and is separated, take out gained pre-treatment powder, again by this powder 900 DEG C of thermal treatments 10 hours, namely make described up-conversion luminescence temperature-sensitive material powder after furnace cooling;
Embodiment 18
Molten-salt growth method preparation (Rb
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
By chemical general formula (Rb
0.5er
0.5) TiO
3, initial feed is respectively High Purity Rbcl (RbCl, 99.8%), Erbium trioxide powder (Er
2o
3, 99.9%), titania powder (TiO
2, 99.9%); And take each initial feed by its stoichiometric ratio, and add rubidium chloride wherein as fused salt (mass ratio of initial feed and RbCl is 1:1.2), this mixing raw material is ground in agate mortar and within 3 hours, makes it to mix, make the precursor powder of molten-salt growth method reaction.Again this precursor powder is transferred in the corundum crucible of adding a cover, finally 950 DEG C of thermal treatments 10 hours, puts into deionization warm water (water temperature 80 DEG C) immersion (36h) after furnace cooling and make it soft (period can add deionized water is dried to prevent it).Then constantly change water repeatedly to wash to remove excess chlorination rubidium, or use the elimination of suction filtration instrument except excessive fused salt.Finally the pressed powder obtained is dried obtained described up-conversion luminescence temperature-sensitive material powder at 120 DEG C.
Embodiment 19
Solvent-thermal method preparation (Rb
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
By chemical formula (Rb
0.5er
0.5) TiO
3, wherein initial feed is respectively High Purity Hydrogen rubidium oxide (RbOH, 99.8%), Erbium trinitrate [Er (NO
3)
35H
2o, 99.9%], four n-butyl titaniums (tetrabutyl titanate) liquid (C
16h
36o
4ti, 98%); Each initial feed is taken by its stoichiometric ratio.Deionized water chosen by solvent, dehydrated alcohol, and ethylene glycol; Add after this raw material is mixed in ethylene glycol also fully to stir and make it to dissolve completely.Then in mixing solutions, add appropriate RbOH and make it fully dissolve.Finally be transferred in water heating kettle by mixed solution, carry out solvent thermal reaction, temperature of reaction is 180 DEG C, and the reaction times is 24 hours; After solvent heat treatment, upper solution is gone, and repeatedly rinses precipitation powder to go out excessive RbOH with deionized water, finally take out gained pre-treatment powder, again by this powder 850 DEG C of thermal treatments 4 hours, namely make described up-conversion luminescence temperature-sensitive material powder after furnace cooling.
Embodiment 20
Solid phase method preparation (Rb
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
Adopt high-purity rubidium carbonate (Rb
2cO
3, 99.8%), Erbium trioxide powder (Er
2o
3, 99.9%), titania powder (TiO
2, 99.9%) and be raw material, stoichiometrically take raw material, putting into agate mortar, is after solvent Homogeneous phase mixing with alcohol, the dry post-drying powder of alcohol mill, the powder obtained to be placed in corundum boat in 750 DEG C of pre-burnings 4 hours in atmosphere, after cooling, to grind oven dry in the same fashion.Again powder is placed in after oven dry corundum boat in atmosphere 900 DEG C calcining 10 hours.Figure 18 gives (Rb
0.5er
0.5) TiO
3the up-conversion luminescence spectral line of powder sample.
Embodiment 21
High-energy ball milling method preparation (Ag
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
Adopt high purity silver nitrate (99.8%), Erbium trioxide powder (99.9%), titania powder (99.9%), for raw material, stoichiometrically take raw material, load weighted raw material is put into Special ball grinding jar, add a certain amount of stearic acid wherein again, add a small amount of Pentyl alcohol simultaneously.Finally utilize PULVERISETTE 5 high energy ball mill, high speed ball milling 4 hours, speed setting is 350 revs/min, rotating mode ball milling, and Ball-milling Time and time-out interval are respectively 20 minutes and 20 minutes.Again the mixed material dehydrated alcohol after ball milling is diluted, static rear preliminary removing stearic acid, then applies centrifuge and is separated, take out gained pre-treatment powder, again by this powder 950 DEG C of thermal treatments 10 hours, namely make described up-conversion luminescence temperature-sensitive material powder after furnace cooling.
Embodiment 22
Solid phase method preparation (Ag
0.5er
0.5) TiO
3powder body material, preparation method is as follows:
Adopt high purity silver nitrate (AgNO
3, 99.8%), Erbium trioxide powder (Er
2o
3, 99.9%), titania powder (TiO
2, 99.9%) and be raw material, stoichiometrically take raw material, putting into agate mortar, is after solvent Homogeneous phase mixing with alcohol, the dry post-drying powder of alcohol mill, the powder obtained to be placed in corundum boat in 750 DEG C of pre-burnings 4 hours in atmosphere, after cooling, to grind oven dry in the same fashion.Again powder is placed in after oven dry corundum boat in atmosphere 1050 DEG C calcining 10 hours.Figure 19 gives (Ag
0.5er
0.5) TiO
3the up-conversion luminescence spectral line of powder sample.
Embodiment 23
High-energy ball milling method preparation [(Na
xk
1-x)
0.5er
0.5] TiO
3powder body material, preparation method is as follows:
Adopt high pure sodium carbonate (99.8%), salt of wormwood (99.8%), Erbium trioxide powder (99.9%), titania powder (99.9%), for raw material, stoichiometrically take raw material, load weighted raw material is put into Special ball grinding jar, add a certain amount of stearic acid wherein again, add a small amount of Pentyl alcohol simultaneously.Finally utilize PULVERISETTE 5 high energy ball mill, high speed ball milling 4 hours, speed setting is 350 revs/min, rotating mode ball milling, and Ball-milling Time and time-out interval are respectively 20 minutes and 20 minutes.Again the mixed material dehydrated alcohol after ball milling is diluted, static rear preliminary removing stearic acid, then applies centrifuge and is separated, take out gained pre-treatment powder, again by this powder 900 DEG C of thermal treatments 10 hours, namely make described up-conversion luminescence temperature-sensitive material powder after furnace cooling.
Embodiment 24
Molten-salt growth method preparation [(Na
xk
1-x)
0.5er
0.5] TiO
3powder body material, preparation method is as follows:
First prepare (K respectively by the method for embodiment 2 and embodiment 10
0.5er
0.5) TiO
3(Na
0.5er
0.5) TiO
3, then press chemical general formula [(Na
xk
1-x)
0.5er
0.5] TiO
3stoichiometric ratio take two kinds of powder, this mixing raw material is ground in agate mortar and within 3 hours, makes it to mix.Again this powder is transferred in the corundum crucible of adding a cover, finally 950 DEG C of thermal treatments 10 hours, namely furnace cooling obtains [(Na
xk
1-x)
0.5er
0.5] TiO
3up-conversion luminescence temperature-sensitive material powder.
Embodiment 25
Solvent-thermal method preparation [(Na
xk
1-x)
0.5er
0.5] TiO
3powder body material, preparation method is as follows:
First prepare (K respectively by the method for example 3 and example 11
0.5er
0.5) TiO
3(Na
0.5er
0.5) TiO
3, then press chemical general formula [(Na
xk
1-x)
0.5er
0.5] TiO
3stoichiometric ratio take two kinds of powder, this mixing raw material is ground in agate mortar and within 3 hours, makes it to mix.Again this powder is transferred in the corundum crucible of adding a cover, finally 950 DEG C of thermal treatments 10 hours, namely furnace cooling obtains [(Na
xk
1-x)
0.5er
0.5] TiO
3up-conversion luminescence temperature-sensitive material powder.
Embodiment 26
Solid phase method preparation [(Na
xk
1-x)
0.5er
0.5] TiO
3powder body material, preparation method is as follows:
Adopt high pure sodium carbonate (99.8%), salt of wormwood (K
2cO
3, 99.8%), Erbium trioxide powder (Er
2o
3, 99.9%), titania powder (TiO
2, 99.9%) and be raw material, stoichiometrically take raw material, putting into agate mortar, is after solvent Homogeneous phase mixing with alcohol, the dry post-drying powder of alcohol mill, the powder obtained to be placed in corundum boat in 750 DEG C of pre-burnings 4 hours in atmosphere, after cooling, to grind oven dry in the same fashion.Again powder is placed in after oven dry corundum boat in atmosphere 1050 DEG C calcining 10 hours.
Embodiment 27
High-energy ball milling method preparation (Na
0.5ho
0.5) TiO
3powder body material, preparation method is as follows:
Adopt high pure sodium carbonate (99.8%), Holmium trioxide powder (99.9%), titania powder (99.9%), for raw material, stoichiometrically take raw material, load weighted raw material is put into Special ball grinding jar, add a certain amount of stearic acid wherein again, add a small amount of Pentyl alcohol simultaneously.Finally utilize PULVERISETTE 5 high energy ball mill, high speed ball milling 4 hours, speed setting is 350 revs/min, rotating mode ball milling, and Ball-milling Time and time-out interval are respectively 20 minutes and 20 minutes.Again the mixed material dehydrated alcohol after ball milling is diluted, static rear preliminary removing stearic acid, then applies centrifuge and is separated, take out gained pre-treatment powder, again by this powder 900 DEG C of thermal treatments 10 hours, namely make described up-conversion luminescence temperature-sensitive material powder after furnace cooling.
Embodiment 28
Molten-salt growth method preparation (Na
0.5ho
0.5) TiO
3powder body material, preparation method is as follows:
By chemical general formula (Na
0.5er
0.5) TiO
3, initial feed is respectively high pure sodium chloride (NaCl, 99.8%), Holmium trioxide powder (Ho
2o
3, 99.9%), titania powder (TiO
2, 99.9%); And take each initial feed by its stoichiometric ratio, and add sodium-chlor wherein as fused salt (mass ratio of initial feed and NaCl is 1:1.2), this mixing raw material is ground in agate mortar and within 3 hours, makes it to mix, make the precursor powder of molten-salt growth method reaction.Again this precursor powder is transferred in the corundum crucible of adding a cover, finally 950 DEG C of thermal treatments 10 hours, puts into deionization warm water (water temperature 80 DEG C) immersion (36h) after furnace cooling and make it soft (period can add deionized water is dried to prevent it).Then constantly change water repeatedly to wash to remove excess chlorination sodium, or use filtering apparatus elimination except excessive fused salt.Finally the pressed powder obtained is dried obtained described up-conversion luminescence temperature-sensitive material powder at 120 DEG C.
Embodiment 29
Solvent-thermal method preparation (Na
0.5ho
0.5) TiO
3powder body material, preparation method is as follows:
By chemical formula (Na
0.5ho
0.5) TiO
3, wherein initial feed is respectively high purity sodium hydroxide (NaOH, 99.8%), holmium nitrate [Er (NO
3)
35H
2o, 99.9%], four n-butyl titaniums (tetrabutyl titanate) liquid (C
16h
36o
4ti, 98%); Each initial feed is taken by its stoichiometric ratio.Deionized water chosen by solvent, dehydrated alcohol, and ethylene glycol; Add after this raw material is mixed in ethylene glycol also fully to stir and make it to dissolve completely.Then in mixing solutions, add appropriate NaOH and make it fully dissolve.Finally be transferred in water heating kettle by mixed solution, carry out solvent thermal reaction, temperature of reaction is 180 DEG C, and the reaction times is 24 hours; After solvent heat treatment, upper solution is gone, and repeatedly rinses precipitation powder to go out excessive NaOH with deionized water, finally take out gained pre-treatment powder, again by this powder 850 DEG C of thermal treatments 4 hours, namely make described up-conversion luminescence temperature-sensitive material powder after furnace cooling.
Embodiment 30
Preparation (Na
0.5er
0.5) TiO
3stupalith, its preparation method is as follows:
By any one (Na of preparation in embodiment 1 to 4
0.5er
0.5) TiO
3powder puts into agate mortar, is that solvent grinds oven dry in 2 hours with alcohol.Add wherein appropriate concentration be the polyvinyl alcohol (PVA) of 5% as binding agent, fully stir, granulation, cross 60 orders and 160 eye mesh screens, make spherical powder; Then spherical powder is put into grinding tool, the green compact of certain thickness and diameter are made at 10 ~ 100MPa pressure, again green compact are put into retort furnace 550 DEG C insulation 10 hours rows sticky, finally by sample at 950 ~ 1350 DEG C of (high-energy ball milling method 1000-1200 DEG C, molten-salt growth method 1050-1250 DEG C, solvent-thermal method 980-1180 DEG C, solid reaction process 1050-1300 DEG C) sinter 2 ~ 6 hours, after being cooled to certain temperature, powered-down cools, and namely obtains described up-conversion luminescence temperature sensitive ceramic block material.Figure 20 gives the up-conversion luminescence spectral line of these 1250 degrees Celsius lower sintered ceramic samples under 980 nanometer lasers excite.
Embodiment 31
Preparation [(Na
xk
1-x)
0.5er
0.5] TiO
3stupalith, its preparation method is as follows:
By any one [(Na of preparation in embodiment 23 to 26
xk
1-x)
0.5er
0.5] TiO
3powder puts into agate mortar, is that solvent grinds oven dry in 2 hours with alcohol.Add wherein appropriate concentration be the polyvinyl alcohol (PVA) of 5% as binding agent, fully stir, granulation, cross 60 orders and 160 eye mesh screens, make spherical powder; Then spherical powder is put into grinding tool, the green compact of certain thickness and diameter are made at 10 ~ 100MPa pressure, again green compact are put into retort furnace 550 DEG C insulation 10 hours rows sticky, finally by sample at 950 ~ 1350 DEG C of (high-energy ball milling method 1000-1200 DEG C, molten-salt growth method 1050-1250 DEG C, solvent-thermal method 980-1180 DEG C, solid reaction process 1050-1300 DEG C) sintering 2 ~ 6 hours one-tenth porcelain, after being cooled to certain temperature, powered-down cools, and namely obtains described up-conversion luminescence temperature sensitive ceramic block material.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (17)
1. a class is containing the up-conversion luminescence temperature-sensitive material of rare earth element, it is characterized in that the chemical general formula of described luminescent material is (A
0.5re
0.5) TiO
3, wherein: A is selected from Rb, K, Na, one or more in Li or Ag, Re is selected from one or more in Er, Yb, Pr, Eu, Ho, Tm, Tb or Dy.
2. a preparation method for the up-conversion luminescence temperature-sensitive material containing rare earth element as claimed in claim 1, is characterized in that described sensitive material preparation method is any one in high energy ball mill method, molten-salt reaction method, solvent thermal reaction method or solid reaction process.
3. preparation method according to claim 2, is characterized in that, the concrete steps of described high-energy ball milling method are as follows:
(1) the taking of raw material: by chemical general formula (A
0.5re
0.5) TiO
3the stoichiometric ratio of A, Re and Ti takes following raw material: the carbonate of element A, nitrate or oxyhydroxide any one, the oxide compound of rare earth element Re or nitrate, the oxide compound of element ti or muriate;
(2) high-energy ball milling: load weighted raw material is put into Special ball mill tank container, add stearic acid, Pentyl alcohol to it again or add deionized water and dehydrated alcohol, finally utilize high energy ball mill ball milling, control high speed ball milling 1-100 hour, speed setting is 100-400 rev/min, rotating mode ball milling, Ball-milling Time and time-out interval are respectively 10-200 minute and 5-60 minute; Stearic add-on is 0 ~ 300% of compound weight, and the add-on of Pentyl alcohol is 1 ~ 50% of compound weight;
(3) thermal treatment: the mixed material dehydrated alcohol after ball milling is diluted, then apply centrifuge to be separated, take out gained pre-treatment powder, then by this powder 500 ~ 1100 DEG C of thermal treatments 1 ~ 10 hour, after furnace cooling, namely make described up-conversion luminescence temperature-sensitive material.
4. preparation method according to claim 3, it is characterized in that, in step (2), stearic add-on is 10 ~ 200% of compound weight, the add-on of Pentyl alcohol is 1 ~ 100% of compound weight, the speed setting of high energy ball mill is 150-380 rev/min, ball milling 2-50 hour, rotating mode ball milling, Ball-milling Time and time-out interval are respectively 20-100 minute and 10-60 minute; In step (3), during dehydrated alcohol dilution, time of repose is 10-30 minute, and after centrifuge is separated, thermal treatment temp is 500 ~ 1000 DEG C, and the time is 1 ~ 8 hour.
5. preparation method according to claim 3, it is characterized in that, in step (2), stearic add-on is 10 ~ 100% of compound weight, the add-on of Pentyl alcohol is 5 ~ 100% of compound weight, the speed setting of high energy ball mill is 300-380 rev/min, ball milling 2-20 hour, rotating mode ball milling, Ball-milling Time and time-out interval are respectively 30 minutes and 20 minutes; In step (3), during dehydrated alcohol dilution, time of repose is 20 minutes, and after centrifuge is separated, thermal treatment temp is 500 ~ 1000 DEG C, and the time is 2 ~ 8 hours.
6. preparation method according to claim 2, is characterized in that, the concrete steps of described molten-salt reaction method are as follows:
(1) the taking of raw material: by chemical general formula (A
0.5re
0.5) TiO
3, its A, Re and Ti element chooses following raw material respectively: elements A is selected from the muriate of A, and rare earth element Re is selected from the oxide compound of Re, vitriol, nitrate or muriate any one, element ti is selected from its oxide compound;
(2) precursor preparation: by chemical general formula (A
0.5re
0.5) TiO
3the stoichiometric ratio of A, Re and Ti take each initial feed, and to the muriate of its another addition element A as fused salt, the mass ratio of control ACl and initial feed summation is 1:0.5-1:5, this mixing raw material is made it to mix in agate mortar grinding for 1-5 hour, makes the precursor powder of molten-salt growth method reaction; Again this precursor powder is transferred to the corundum crucible of adding a cover, 700 ~ 1050 DEG C of thermal treatments 1 ~ 10 hour, after furnace cooling, namely makes the precursor of described up-conversion luminescence temperature-sensitive material;
(3) fused salt is separated: the precursor of step (2) gained is put into deionization warm water soaking, and control water temperature is 50-90 DEG C, and soak time is 10-100h, makes it soft, and period can add deionized water is dried to prevent it; Then constantly change the muriate that water repeatedly washs to remove excessive elements A, or use filtering apparatus elimination except excessive fused salt, finally the pressed powder obtained is dried obtained described up-conversion luminescence temperature-sensitive material at 100-150 DEG C.
7. preparation method according to claim 6, is characterized in that, in step (1), elements A is selected from the muriate of A, and rare earth element Re is selected from the nitrate of Re, and element ti is selected from TiO
2; In step (2), the mass ratio of ACl and initial feed is 1:1-1:2, and milling time is 2-3 hour, and thermal treatment temp is 720-990 DEG C, heat treatment time 2 ~ 4 hours; In step (3), control water temperature is 60-80 DEG C, and soak time is 10-72 h.
8. preparation method according to claim 6, is characterized in that, in step (1), elements A is selected from the muriate of A, and rare earth element Re is selected from the nitrate of Re, and element ti is selected from TiO
2; In step (2), the mass ratio of ACl and initial feed is 1:1.5-1:2, and milling time is 2 hours, and thermal treatment temp is 730-990 DEG C, heat treatment time 4 hours; Controlling water temperature in step (3) is 60-80 DEG C, and soak time is 24-72 h.
9. preparation method according to claim 3, is characterized in that, the concrete steps of described solvent thermal reaction method are as follows:
(1) the choosing of raw material: by chemical general formula (A
0.5re
0.5) TiO
3its A, Re and Ti element chooses following raw material respectively: elements A is selected from the oxyhydroxide of A, rare earth element Re is selected from nitrate or the muriate of Re, element ti is selected from titanium tetrachloride, four n-butyl titaniums (tetrabutyl titanate) or titanium tetraisopropylate, solvent choose deionized water, dehydrated alcohol or ethylene glycol any one;
(2) precursor power: by chemical general formula (A
0.5re
0.5) TiO
3the stoichiometric ratio of A, Re and Ti take each initial feed, and add deionized water after being mixed by this raw material, one or more mixed solvents of dehydrated alcohol and ethylene glycol also fully stir and make it to dissolve; Then add AOH to mixing solutions, the mol ratio of control AOH and Ti element is 5:1-15:1, and makes it fully dissolve; Finally mixed solution is transferred to hydro-thermal axe, carries out solvent thermal reaction, temperature of reaction is 120 DEG C-250 DEG C, and the reaction times is 2 hours-40 hours;
(3) thermal treatment: the mixed material dehydrated alcohol after ball milling is diluted, then apply centrifuge to be separated, take out gained pre-treatment powder, then by this powder 500 ~ 1000 DEG C of thermal treatments 1 ~ 10 hour, after furnace cooling, namely make described up-conversion luminescence temperature-sensitive material.
10. preparation method according to claim 9, is characterized in that, in step (1), rare earth element Re is selected from the nitrate of Re, and element ti is selected from titanium tetrachloride, four n-butyl titaniums (tetrabutyl titanate); Deionized water chosen by solvent, dehydrated alcohol or ethylene glycol any one; In step (2), the mol ratio of AOH and Ti element is 1:1-15:1, and temperature of reaction is 180-230 DEG C, and the reaction times is 12-36 hour; In step (3), powder thermal treatment temp is 600 ~ 980 DEG C, and the time is 1 ~ 10 hour.
11. preparation methods according to claim 9, is characterized in that, in step (1), rare earth element Re is selected from the nitrate of Re, and element ti is selected from four n-butyl titaniums (tetrabutyl titanate); Deionized water chosen by solvent, dehydrated alcohol or ethylene glycol any one; In step (2), the mol ratio of AOH and Ti element is 1:1-15:1, and temperature of reaction is 180-230 DEG C, and the reaction times is 12-36 hour; In step (3), powder thermal treatment temp is 600 ~ 980 DEG C, and the time is 1 ~ 10 hour.
12. preparation methods according to claim 2, is characterized in that, the concrete steps of described solid reaction process are as follows:
(1) the choosing of raw material: by chemical general formula (A
0.5re
0.5) TiO
3, its A, Re and Ti element chooses following raw material respectively: elements A is selected from the carbonate of A, and rare earth element Re is selected from the oxide compound of Re, nitrate or muriate, and element ti is selected from titanium dioxide (rutile, anatase octahedrite or brookite);
(2) raw material takes and mixes: by chemical general formula (A
0.5re
0.5) TiO
3the stoichiometric ratio of A, Re and Ti take each initial feed, its volatile A raw material needs excessive 1-10wt%, and load weighted starting material side is entered agate mortar, adds alcohol and mixes rear grinding 2-5 hour;
(3) preheating: the blended stock after grinding is put into retort furnace thermal treatment, and thermal treatment temp is 700 ~ 1000 DEG C, and heat treatment time is 1 ~ 10 hour, then makes preburning powdered material with stove cooling down;
(4) double sintering: preburning powdered material is added appropriate dehydrated alcohol, grinds 2-5 hour again, then the powder after this being ground was 800 ~ 1200 DEG C of thermal treatments 1 ~ 10 hour, namely made described up-conversion luminescence temperature-sensitive material after furnace cooling.
13. preparation methods according to claim 12, is characterized in that, in step (1), elements A is selected from the carbonate of A, and rare earth element Re is selected from oxide compound or the nitrate of Re, and element ti is selected from titanium dioxide (rutile, anatase octahedrite or brookite); The excessive 1-5% of A raw material in step (2), grinding 2-3 hour; In step (3), thermal treatment temp is 800 ~ 950 DEG C, and heat treatment time is 4 ~ 6 hours; In step (4), milling time is 2-3 hour again, and thermal treatment temp is 900 ~ 1100 DEG C, and heat treatment time is 4 ~ 10 hours.
14. 1 kinds of up-conversion luminescence temperature-sensitive materials as claimed in claim 1 are applied to and prepare stupalith, target, and described target is for the preparation of thick film or thin-film material.
15. application according to claim 14, it is characterized in that the preparation method of described stupalith, concrete steps are as follows:
(1) up-conversion luminescence temperature-sensitive material powder is put into agate mortar grinding 1-2 hour, its add concentration be the polyvinyl alcohol of 1 ~ 15% as binding agent, fully stir, seasoning, granulation, cross screen cloth, make spherical powder;
(2) spherical powder is put into grinding tool, the green compact of certain thickness and diameter are made at 10 ~ 100MPa pressure, again green compact are put into retort furnace 500-600 DEG C of insulation 2-10 hour row sticky, finally sample is sintered 1 ~ 10 hour at 950 ~ 1350 DEG C, after being cooled to certain temperature, powered-down cools, and namely obtains described up-conversion luminescence temperature sensitive ceramic block material.
16. application according to claim 15, is characterized in that, adding polyvinyl alcohol concentration in step (1) is 2 ~ 10%, cross 60 orders and 160 mesh sieves, 500-600 DEG C of insulation 10 hours when in step (2), row is sticky, during sintering, temperature is 950 ~ 1350 DEG C, and sintering time is 2 ~ 8 hours.
17. 1 kinds of up-conversion luminescence temperature-sensitive materials as claimed in claim 1 fluorescence temperature sensor, short wavelength emissions solid laser, biomolecules fluorescent mark, infrared acquisition and false proof, 3 D stereo shows, the application of integrated optoelectronic device or area of solar cell.
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| CN111117617A (en) * | 2019-12-31 | 2020-05-08 | 同济大学 | Tungstate-based up-conversion luminescence temperature sensing material and preparation method thereof |
| CN112110724A (en) * | 2020-10-09 | 2020-12-22 | 中国民航大学 | Cogeneration layered perovskite material with reversible regulation and control performance and preparation method thereof |
| CN116064036A (en) * | 2023-01-16 | 2023-05-05 | 海南大学 | Up-conversion luminescent material and preparation method thereof |
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