CN107629789A - A kind of ZrO2Base samarium tin codope twilight sunset fluorescent material and preparation method thereof - Google Patents

A kind of ZrO2Base samarium tin codope twilight sunset fluorescent material and preparation method thereof Download PDF

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CN107629789A
CN107629789A CN201710977341.8A CN201710977341A CN107629789A CN 107629789 A CN107629789 A CN 107629789A CN 201710977341 A CN201710977341 A CN 201710977341A CN 107629789 A CN107629789 A CN 107629789A
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preparation
fluorescent material
codope
zro
samarium
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李爱民
李景欣
刘慧莹
孙康宁
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Shandong University
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Shandong University
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Abstract

The present invention relates to a kind of ZrO2Base samarium tin codope twilight sunset fluorescent material and preparation method thereof, ZrO prepared by this method2Base samarium tin codope long-afterglow fluorescent material average grain diameter is small, and its luminous intensity, persistence adulterate ZrO relative to samarium list2Fluorescent material is greatly improved；Simultaneously, using polymer-network gel method, not only preparation technology is simple and convenient to operate, preparation cost is low, energy consumption is low, is easy to be mass produced, nontoxic and good biocompatibility long-afterglow fluorescent material can also be prepared, the methods of compared to existing high-temperature solid phase reaction method and sol-gal process, overcomes the shortcomings of technological reaction is complicated, time-consuming, power consumption is big, expensive starting materials, it is easy to be mass produced, great application prospect.

Description

A kind of ZrO2Base samarium-tin codope twilight sunset fluorescent material and preparation method thereof
Technical field
The invention belongs to material science and biomedical crossing domain, more particularly to a kind of ZrO2Base samarium-tin codope Twilight sunset fluorescent material and preparation method thereof.
Background technology
Long-afterglow material is the energy that can store ambient light irradiation, is then being referred at room temperature slowly with the shape of visible ray Formula discharges the material of these storage energies；It can be used as luminous paint, light-emitting film, luminescent ceramic, communications and transportation interior decoration, Safety sign and bio-imaging etc..ZrO2It is swollen with hardness height, high-melting-point, good chemical stability, photo and thermal stability, heat Swollen coefficient height, the dielectric properties that thermal conductivity is low, excellent, high index of refraction, to the transparency of visible ray to infrared light the advantages that, rare earth The ZrO of ion doping2Fluorescent material is shown in optics, medical diagnosis, bioprobe etc. have potential application.Prior art In, the report on the preparation method of long-afterglow fluorescent material is a lot, such as patent CN101935204 B, discloses a kind of super Long afterglow blueness storage light ceramic material and preparation method thereof, aluminosilicate novel blue long afterglow hair is synthesized using sol-gal process Luminescent material, including accurately weigh raw materials of Ca (NO3)2、Pr2O3、Eu2O3、Al(NO3)3、Dy2O3、HBO3And tetraethyl orthosilicate, title Good Pr2O3、Eu2O3、Dy2O3Adding stirring in concentrated nitric acid makes untill oxide is completely dissolved, to add distilled water diluting 3 and be made into again Solution 1, the Ca (NO weighed up3)2With Al (NO3)3Wiring solution-forming 2 in distilled water are dissolved in, tetraethyl orthosilicate is added 0.9 liter Wiring solution-forming 3 in the distilled water of 1.5 liters of addition, is added after solution 1, solution 2 and solution 3 are mixed after absolute ethyl alcohol is mixed 0.15mol boric acid stirs to form settled solution, is 1.5 settled solution regulation pH value, is stirred continuously, treats in 70 DEG C of water-bath Taken out after forming gel, be placed in drying box and dried 10 hours at 130 DEG C, dried gel is ground in agate mortar Uniformly, it is subsequently placed in corundum crucible, 1030 DEG C are calcined 50 minutes in CO reducing atmospheres.
Patent CN102660271 B, disclose polychrome long after glow luminous material of a kind of single-matrix and preparation method thereof, This method prepares long after glow luminous material with use high temperature solid-state method, including calcium carbonate, silicic acid, tin oxide, rare earth oxide are Raw material, according to target the chemical dosage ratio of product weigh each component and it is well mixed after, carried out at 1000~1380 DEG C calcining 3~ Room temperature is naturally cooled to after 6h, that is, polychrome long after glow luminous material is made.Blue light, red can be realized respectively in the single-matrix The long afterglow transmitting of light, green glow and white light, in the discernmible luminosity (0.32mcd/m of human eye2) above continuous illumination.
Patent CN106978177 A, are disclosed a kind of red long afterglow luminous material and its production method, are total to using wet method Mixed-high-temperature solid phase reaction method prepares long after glow luminous material, including：A) by oxidation of the element chemistry metering than weighing respective element Thing/carbonated starting material；B) dispersant is added in the raw material that step a) is weighed up, then carries out wet method blending grinding；C) to step B) raw material being well mixed after wet method blending grinding is dried；D) the dried raw materials of step c) are placed in weakly reducing atmosphere High temperature solid state reaction is carried out, calcining heat is 900~1350 DEG C, and soaking time is 0.5~8h；E) after taking out step d) calcinings Sample is ground to obtain red long afterglow luminous material.
In view of the foregoing it is apparent that the common method for preparing fluorescent material at present be mainly high-temperature solid phase reaction method and colloidal sol- Gel method, but the shortcomings of both preparation technologies react complicated, time-consuming, power consumption is big, expensive starting materials, meanwhile, the fluorescence of preparation The luminosity of material, persistence etc. are inadequate.Therefore, improve twilight sunset fluorescent material preparation method and its luminescent properties into For urgent need to resolve the problem of；And Sm3+A kind of typical red emission center, by with Sn4+Codope, it can effectively improve The luminous intensity and afterglow property of material, great application prospect.
The content of the invention
For above-mentioned problems of the prior art, it is an object of the invention to provide one kind oxidation zirconium base samarium-tin is common Adulterate twilight sunset fluorescent material and preparation method thereof, ZrO prepared by this method2Base samarium (Sm3+)-tin (Sn4+) codope long afterglow is glimmering Luminescent material average grain diameter is small, and its luminous intensity, persistence are relative to Sm3+Single doping ZrO2Fluorescent material is greatly improved；Together When, using polymer-network gel method, not only preparation technology is simple and convenient to operate, and prepares that cost is low, energy consumption is low, is easy to carry out Large-scale production, can also prepare nontoxic and good biocompatibility long-afterglow fluorescent material.
An object of the present invention is to provide a kind of ZrO2The preparation method of base samarium-tin codope twilight sunset fluorescent material.
The second object of the present invention is to provide the application of the twilight sunset fluorescent material of above method preparation.
For achieving the above object, the invention discloses following technical proposals：
A kind of ZrO2The preparation method of base samarium-tin codope twilight sunset fluorescent material, specifically comprises the following steps：
1) by ZrOCl2·8H2O、Sm(NO3)3·6H2O and SnCl4·5H2O weighs a certain amount of in molar ratio, is dissolved in In ionized water, mechanical agitation, it is completely dissolved, treats that solution is clarified, obtain containing three kinds of metal cations：Sm3+、Sn4+、Zr4+ Mixed solution；
2) it is 1 by three kinds of metal cations described in step 1) and complexing agent：1.5 ratio, weigh a certain amount of lemon Lemon acid, is added in the mixed solution of step 1), and mechanical agitation makes it fully be complexed, and is adjusted pH to 4~5 with ammoniacal liquor, is obtained acidity Mixed liquor；
3) using acrylamide as monomer, with N, N '-methylene-bisacrylamide weighs one in molar ratio as crosslinking agent It is quantitative, add in the acid solution of step 2), heating water bath adds initiator, polymerize immediately to design temperature fully after dissolving Obtain wet gel；
4) wet gel obtained in step 3) is placed in baking oven and dried, xerogel is obtained, by xerogel in Muffle furnace Calcining, produces ZrO2Base samarium-tin codope twilight sunset fluorescent material.
In step 1), three kinds of metal cation Zr4+、Sm3+、Sn4+Mol ratio be 100：0.5：0.5~20；
In step 1), the Sm3+Doping concentration is 0.5mol%, concentration quenching under high doping will occur more than this concentration, i.e., Luminous intensity is with Sm3+Concentration increases and reduced；
In step 1), the Sn4+Concentration is 0.5mol%~20mol%；
In step 1), the mechanical agitation time is 30~40min；
In step 2), the complexing agent is citric acid；
In step 2), the mechanical agitation time is 10~30min；
In step 3), the mol ratio of the monomer and crosslinking agent is 8:1；
In step 3), the design temperature is：50~90 DEG C；
Preferably, the design temperature is 70 DEG C, and temperature is too high to trigger implode, too low that polymerisation can be made incomplete, All it is unfavorable for the progress of polymerisation；
In step 3), the initiator is ammonium persulfate；
In step 3), the initiator content is the 1~3% of monomer mass；
In step 4), the drying condition is：Drying temperature：60~100 DEG C, drying time is：8~15h；
Preferably, the drying temperature and time are respectively：80℃、12h；
In step 4), the heating rate during calcining is 5 DEG C/min；
In step 4), the calcining heat is 1000~1300 DEG C, and calcination time is 1~3h；
Preferably, the calcining heat and time are respectively 1200 DEG C, 2h, the luminous intensity of prepared sample at a temperature of this Maximum is attained by with persistence.
In addition, the invention also discloses ZrO prepared by the above method2The application of base samarium-tin codope twilight sunset fluorescent material, The application includes being used for luminous paint, light-emitting film, luminescent ceramic, communications and transportation interior decoration, safety sign and biology Imaging.
The present invention mentality of designing be：Sm3+It is a kind of typical red emission center, and adulterates Sn4+Ion and surrounding ring The interaction in border is different from substituted host's cation Zr4+, the electronegativity of the two and the moon of ionization potential differentia influence material- Cation bond strength and shallow trap depth, and then influence luminous intensity and persistence；Sm simultaneously3+、Sn4+Codope ZrO2Introduce Electronegative Zr4+The Lacking oxygen of room and positively charged can provide carrier traps for afterglow, and therefore, the present invention passes through Sm3+、Sn4+Codope improves the luminous intensity of material and afterglow property.
Compared with prior art, the ZrO that the inventive method provides2Base samarium-tin codope twilight sunset fluorescent material and its preparation Method achieves following beneficial effect：
(1) Sm is passed through3+、Sn4+It is co-doped with, average grain diameter can be made in the subsphaeroidal of 150nm or so and even size distribution Particle；
(2)Sm3+The ZrO singly adulterated2Fluorescent material does not have twilight sunset phenomenon, but the present invention is by ZrO2Codope Sm in matrix3 +And Sn4+So that its luminous intensity, persistence are relative to Sm3+Single doping ZrO2Fluorescent material is greatly improved, and it is luminous Intensity can improve 10 times, persistence most long reachable 1000s；
(3) present invention uses polymer-network gel method, and not only preparation technology is simple and convenient to operate, prepares that cost is low, energy Consume low, nontoxic and good biocompatibility long-afterglow fluorescent material can also be prepared, compared to existing high temperature solid state reaction Method and sol-gel process, the shortcomings of technological reaction is complicated, time-consuming, power consumption is big, expensive starting materials is overcome, is easy to be advised greatly Mould produces, great application prospect.
Brief description of the drawings
The Figure of description for forming the part of the application is used for providing further understanding of the present application, and the application's shows Meaning property embodiment and its illustrate be used for explain the application, do not form the improper restriction to the application.
Fig. 1 a, b are respectively the photoluminescence intensity collection of illustrative plates and decay curve of embodiment 1.
Fig. 2 a, b are respectively the photoluminescence intensity collection of illustrative plates and decay curve of embodiment 2.
Fig. 3 a, b are respectively the photoluminescence intensity collection of illustrative plates and decay curve of embodiment 3.
Fig. 4 a, b are respectively the photoluminescence intensity collection of illustrative plates and decay curve of embodiment 4.
Fig. 5 a, b are respectively the photoluminescence intensity collection of illustrative plates and decay curve of embodiment 5.
Fig. 6 is the photoluminescence intensity collection of illustrative plates of comparative example 1.
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the application.It is unless another Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
As background technology is introduced, existing preparation technology reacts complicated, time-consuming, big, expensive starting materials of power consumption etc. Shortcoming, meanwhile, the luminosity of the fluorescent material of preparation, persistence etc., not enough in order to solve the above problems, the present invention carried A kind of ZrO is supplied2Base samarium-tin codope twilight sunset fluorescent material and preparation method thereof, with reference to specific embodiment to this hair It is bright to be described further.
Embodiment 1：
In the present embodiment, three kinds of metal cations：Sm3+、Sn4+、Zr4+Mol ratio be：0.5：0.5：100.
(1) 3.2225g ZrOCl accurately are weighed2·8H2O is dissolved in 100ml deionized waters, mechanical agitation, then is claimed respectively Take 0.0222g Sm (NO3)3·6H2O and 0.0175g SnCl4·5H2O is added in above-mentioned solution, and stirring 30min makes it completely molten Solution, treat that solution is clarified, obtain containing three kinds of metal cations：Sm3+、Sn4+、Zr4+Mixed solution；
(2) it is 1 by three kinds of metal cations described in step 1) and complexing agent：1.5 ratio, weigh 3.1836g lemons Acid, add in the mixed solution in step 1), mechanical agitation 30min makes it fully be complexed, and ammoniacal liquor regulation pH to 5, obtains acidity Mixed liquor；
(3) 6.4612g acrylamides are weighed respectively and 1.7518g N, N '-methylene-bisacrylamide are added in step 2) Mixed liquor in, fully dissolving after heating water bath be warming up to 70 DEG C, immediately add 0.0646g ammonium persulfate initiated polymerizations, Obtain wet gel；
(4) wet gel in step 3) is placed in 80 DEG C of baking ovens dry 12h and obtains xerogel, by xerogel in Muffle furnace 2h is calcined at 1200 DEG C, produces ZrO2Base Sm3+、Sn4+Codope afterglowing material.
Its photoluminescence spectra and decay curve are respectively as Fig. 1 (a) and (b) are shown.
Embodiment 2：
In the present embodiment, three kinds of metal cations：Sm3+、Sn4+、Zr4+Mol ratio be：0.5：5：100.
(1) 3.2225g ZrOCl accurately are weighed2·8H2O is dissolved in 100ml deionized waters, mechanical agitation, then is claimed respectively Take 0.0222g Sm (NO3)3·6H2O and 0.1753g SnCl4·5H2O is added in above-mentioned solution, and stirring 30min makes it completely molten Solution, treat that solution is clarified, obtain containing three kinds of metal cations：Sm3+、Sn4+、Zr4+Mixed solution；
(2) it is 1 by three kinds of metal cations described in step 1) and complexing agent：1.5 ratio, weigh 3.3255g lemons Acid, add in the mixed liquor in step 2), mechanical agitation 10min makes it fully be complexed, and ammoniacal liquor regulation pH to 5, obtains acid mixed Close liquid；
(3) 6.7490g acrylamides are weighed respectively and 1.8298g N, N '-methylene-bisacrylamide are added in step 2) Mixed liquor in, fully dissolving after heating water bath be warming up to 50 DEG C, immediately add 0.1012g ammonium persulfate initiated polymerizations, Obtain wet gel；
(4) wet gel in step 3) is placed in 60 DEG C of baking ovens dry 15h and obtains xerogel, by xerogel in Muffle furnace In calcine 2h at 1000 DEG C, produce ZrO2Base Sm3+、Sn4+Codope twilight sunset fluorescent material.
Its photoluminescence spectra and persistence are respectively as Fig. 2 (a) and (b) are shown.
Embodiment 3：
In the present embodiment, three kinds of metal cations：Sm3+、Sn4+、Zr4+Mol ratio be：0.5：10：100.
(1) 3.2225g ZrOCl accurately are weighed2·8H2O is dissolved in 100ml deionized waters, mechanical agitation, then is claimed respectively Take 0.0222g Sm (NO3)3·6H2O and 0.3506g SnCl4·5H2O is added in above-mentioned solution, and stirring 30min makes it completely molten Solution, treat that solution is clarified, obtain containing three kinds of metal cations：Sm3+、Sn4+、Zr4+Mixed solution；
(2) it is 1 by three kinds of metal cations described in step 1) and complexing agent：1.5 ratio, weigh 3.4831g lemons Acid, add in the mixed liquor in step 1), mechanical agitation 15min makes it fully be complexed, and ammoniacal liquor regulation pH to 5, obtains acid mixed Close liquid；
(3) 7.0689g acrylamides are weighed respectively and 1.9165g N, N '-methylene-bisacrylamide are added in step 2) Mixed liquor in, fully dissolving after heating water bath be warming up to 60 DEG C, immediately add 0.1414g ammonium persulfate initiated polymerizations, Obtain wet gel；
(4) wet gel in step 3) is placed in 70 DEG C of baking ovens dry 10h and obtains xerogel, by xerogel in Muffle furnace In calcine 2h at 1200 DEG C, produce ZrO2Base Sm3+、Sn4+Codope twilight sunset fluorescent material.
Its photoluminescence spectra and persistence are respectively as Fig. 3 (a) and (b) are shown.
Embodiment 4：
In the present embodiment, three kinds of metal cations：Sm3+、Sn4+、Zr4+Mol ratio be：0.5：15：100.
(1) 3.2225g ZrOCl accurately are weighed2·8H2O is dissolved in 100ml deionized waters, mechanical agitation, then is claimed respectively Take 0.0222g Sm (NO3)3·6H2O and 0.5259g SnCl4·5H2O is added in above-mentioned solution, and stirring 35min makes it completely molten Solution, treat that solution is clarified, obtain containing three kinds of metal cations：Sm3+、Sn4+、Zr4+Mixed solution；
(2) it is 1 by three kinds of metal cations described in step 1) and complexing agent：1.5 ratio, weigh 3.4988g lemons Acid, add in the mixed liquor in step 1), mechanical agitation 20min makes it fully be complexed, and ammoniacal liquor regulation pH to 4, obtains acid mixed Close liquid；
(3) 7.1009g acrylamides are weighed respectively and 1.9252g N, N '-methylene-bisacrylamide are added in step 2) Mixed liquor in, fully dissolving after heating water bath be warming up to 80 DEG C, immediately add 0.1775g ammonium persulfate initiated polymerizations, Obtain wet gel；
(4) wet gel in step 3) is placed in 100 DEG C of baking ovens dry 8h and obtains xerogel, xerogel Muffle furnace 1100 DEG C calcining 2.5h, produce ZrO2Base Sm3+、Sn4+Codope twilight sunset fluorescent material.
Its photoluminescence spectra and persistence are respectively as Fig. 4 (a) and (b) are shown.
Embodiment 5：
In the present embodiment, three kinds of metal cations：Sm3+、Sn4+、Zr4+Mol ratio be：0.5：20：100.
(1) 3.2225g ZrOCl8H accurately are weighed2O is dissolved in 100ml deionized waters, mechanical agitation, then is claimed respectively Take 0.0222g Sm (NO3)3·6H2O and 0.7012g SnCl4·5H2O is added in above-mentioned solution, and stirring 40min makes it completely molten Solution, treat that solution is clarified, obtain containing three kinds of metal cations：Sm3+、Sn4+、Zr4+Mixed solution；
(2) it is 1 by three kinds of metal cations described in step 1) and complexing agent：1.5 ratio, weigh 3.7983g lemons Acid, add in the mixed liquor in step 1), mechanical agitation 30min makes it fully be complexed, and ammoniacal liquor regulation pH to 5, obtains acid mixed Close liquid；
(3) 7.7086g acrylamides are weighed respectively and 2.0899g N, N '-methylene-bisacrylamide are added in step 2) Mixed liquor in, fully dissolving after heating water bath be warming up to 90 DEG C, immediately add 0.2313g ammonium persulfate initiated polymerizations, Obtain wet gel；
(4) wet gel in step 3) is placed in 90 DEG C of baking ovens dry 14h and obtains xerogel, by xerogel in Muffle furnace In calcine 3h at 1300 DEG C, produce ZrO2Base Sm3+、Sn4+Codope twilight sunset fluorescent material.
Its photoluminescence spectra and persistence are respectively as Fig. 5 (a) and (b) are shown.
Comparative example 1：
In the present embodiment, three kinds of metal cations：Sm3+、Sn4+、Zr4+Mol ratio be：0.5：0：100.
(1) 3.2225g ZrOCl accurately are weighed2·8H2O is dissolved in 100ml deionized waters, mechanical agitation, then is weighed 0.0222g Sm(NO3)3·6H2O is added in above-mentioned solution, and stirring 30min is completely dissolved it, is treated that solution is clarified, is contained Two kinds of metal cations：Sm3+、Zr4+Mixed solution；
(2) it is 1 by two kinds of metal cations described in step 1) and complexing agent：1.5 ratio, weigh 3.1678g lemons Acid, add in the mixed liquor in step 1), mechanical agitation 15min makes it fully be complexed, and ammoniacal liquor regulation pH to 5, obtains acid mixed Close liquid；
(3) 6.4292g acrylamides are weighed respectively and 1.7431g N, N '-methylene-bisacrylamide are added in step 2) Mixed liquor in, fully dissolving after heating water bath be warming up to 60 DEG C, immediately add 0.1286g ammonium persulfate initiated polymerizations, Obtain wet gel；
(4) wet gel in step 3) is placed in 70 DEG C of baking ovens dry 10h and obtains xerogel, by xerogel in Muffle furnace In calcine 2h at 1200 DEG C, produce ZrO2Base Sm3+Single doping twilight sunset fluorescent material.
Its photoluminescence spectra is as shown in Figure 6.
Fig. 6 is 0.5mol%Sm3+Single doping ZrO2Photoluminescence spectra figure, compared with Fig. 1~5, Sn4+After codope Luminous intensity be greatly improved, wherein 10mol%Sn4+It is luminous for the sample of codope, i.e. sample prepared by embodiment 3 Intensity with undoped with Sn4+Sample compared to 10 times can be improved；And 0.5mol%Sm3+Single doping ZrO2There is no twilight sunset generation, 10mol%Sn4+The sample of codope reaches most long afterglow 1000s；As can be seen that pass through Sm3+、Sn4+Codope, make material Luminescent properties are greatly improved.
The preferred embodiment of the application is the foregoing is only, is not limited to the application, for the skill of this area For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.

Claims (10)

  1. A kind of 1. ZrO2The preparation method of base samarium-tin codope twilight sunset fluorescent material, it is characterised in that specifically comprise the following steps：
    1) by ZrOCl2·8H2O、Sm(NO3)3·6H2O and SnCl4·5H2O weighs a certain amount of in molar ratio, is dissolved in deionization In water, mechanical agitation, it is completely dissolved, treats that solution is clarified, obtain containing three kinds of metal cations：Sm3+、Sn4+、Zr4+It is mixed Close solution；
    2) it is 1 by three kinds of metal cations described in step 1) and complexing agent：1.5 ratio, a certain amount of citric acid is weighed, is added In the mixed solution for entering step 1), mechanical agitation makes it fully be complexed, and adjusts pH to 4~5 with ammoniacal liquor, obtains acid mixed solution；
    3) using acrylamide as monomer, with N, N '-methylene-bisacrylamide weighs certain in molar ratio as crosslinking agent Amount, add in the acid solution of step 2), fully heating water bath to design temperature, adds initiator, polymerize immediately after dissolving To wet gel；
    4) wet gel obtained in step 3) is placed in baking oven and dried, obtained xerogel, xerogel is calcined in Muffle furnace, Produce ZrO2Base Sm3+、Sn4+Codope twilight sunset fluorescent material；
    In step 1), three kinds of metal cations：Zr4+、Sm3+、Sn4+Mol ratio be 100：0.5：0.5~20；
    In step 1), the Sm3+Doping concentration is 0.5mol%, Sn4+Concentration is 0.5mol%~20mol%；
    In step 3), the initiator is ammonium persulfate；
    In step 3), the initiator content is the 1~3% of monomer mass.
  2. 2. preparation method as claimed in claim 1, it is characterised in that in step 1), the mechanical agitation time be 30~ 40min。
  3. 3. preparation method as claimed in claim 1, it is characterised in that in step 2), the complexing agent is citric acid.
  4. 4. preparation method as claimed in claim 1, it is characterised in that in step 2), the mechanical agitation time be 10~ 30min。
  5. 5. preparation method as claimed in claim 1, it is characterised in that in step 3), the mol ratio of the monomer and crosslinking agent For 8：1.
  6. 6. preparation method as claimed in claim 1, it is characterised in that in step 3), the design temperature is：50~90 DEG C； Preferably, the holding temperature is 70 DEG C.
  7. 7. preparation method as claimed in claim 1, it is characterised in that in step 4), the drying condition is：Drying temperature： 60~100 DEG C, drying time is：8~15h；Preferably, the drying temperature and time are respectively：80℃、12h.
  8. 8. preparation method as claimed in claim 1, it is characterised in that in step 4), the heating rate during calcining is 5 ℃/min。
  9. 9. preparation method as claimed in claim 1, it is characterised in that in step 4), the calcining heat is 1000~1300 DEG C, calcination time is 1~3h；Preferably, the calcining heat and time are respectively 1200 DEG C, 2h.
  10. 10. the ZrO prepared according to any described preparation methods of claim 1-9 and/or this method2Base samarium-tin codope twilight sunset Fluorescent material answering in luminous paint, light-emitting film, luminescent ceramic, communications and transportation interior decoration, safety sign, bio-imaging With.
CN201710977341.8A 2017-10-19 2017-10-19 A kind of ZrO2Base samarium tin codope twilight sunset fluorescent material and preparation method thereof Pending CN107629789A (en)

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CN110452697A (en) * 2019-09-20 2019-11-15 闽南师范大学 It is a kind of to emit simultaneous feux rouges and the luminescent material of blue green light and preparation method thereof
CN111019652A (en) * 2019-12-23 2020-04-17 中国科学院长春光学精密机械与物理研究所 Fluorescent temperature measuring material and preparation method thereof
CN111019652B (en) * 2019-12-23 2021-04-13 中国科学院长春光学精密机械与物理研究所 Fluorescent temperature measuring material and preparation method thereof

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