CN105481257A - Glass film containing rare-earth-ion-doped K2LaBr5 microcrystalline and preparation method thereof - Google Patents

Glass film containing rare-earth-ion-doped K2LaBr5 microcrystalline and preparation method thereof Download PDF

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CN105481257A
CN105481257A CN201510783082.6A CN201510783082A CN105481257A CN 105481257 A CN105481257 A CN 105481257A CN 201510783082 A CN201510783082 A CN 201510783082A CN 105481257 A CN105481257 A CN 105481257A
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bromide
rare earth
labr
mol ratio
solution
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江东升
夏海平
盛启国
冯治刚
王成
张健
何仕楠
汤庆阳
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Ningbo University
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Ningbo University
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/16—Halogen containing crystalline phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2203/00—Production processes
    • C03C2203/20—Wet processes, e.g. sol-gel process
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2203/00—Production processes
    • C03C2203/20—Wet processes, e.g. sol-gel process
    • C03C2203/26—Wet processes, e.g. sol-gel process using alkoxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2203/00—Production processes
    • C03C2203/50—After-treatment
    • C03C2203/52—Heat-treatment

Abstract

The invention discloses a glass film containing rare-earth-ion-doped K2LaBr5 microcrystalline and a preparation method thereof. The glass film comprises, in percent by mole, 65-74 mol% of phosphorus pentoxide, 5-10 mol% of aluminium oxide, 5-10 mol% of digallium trioxide, 10-15 mol% of K2LaBr5, and 1-5 mol% of a rare-earth bromide, wherein the rare-earth bromide is one of cerium bromide, europium bromide, terbium bromide and praseodymium bromide. The advantages comprise that the sol-gel method is a low-temperature wet chemical glass-preparation technology, the glass is obtained through hydrolysis of a precursor raw material and a polymerization chemical reaction, and therefore a film material can be prepared under a certain liquid viscosity, and the low-temperature synthetic conditions can effectively prevent decomposition and volatilization of the bromide raw materials.

Description

Containing rare earth ion doped K 2laBr 5glass film of crystallite and preparation method thereof
Technical field
The present invention relates to a kind of glass film of rare earth ion doped crystallite, be specifically related to a kind of rare earth ion doped K being used as scintillation material 2laBr 5the glass film of crystallite and process for preparing sol-gel thereof.
Background technology
Scintillation material is a kind of lower optical function material that can send visible ray of exciting at energetic ray (as x-ray, gamma-rays) or other radioactive particle, can be widely used in nuclear medicine diagnostic, safety check, anti-ly to fear, the field such as high energy physics and geological prospecting.In recent years along with the fast development in the field such as medical imaging and safety inspection, the high performance new scintillation material of demand in large quantities.Outstanding scintillation material mainly possesses following performance: luminous efficiency is high, density of material is large, fluorescence decay is fast, radiation resistance is good and the low inferior feature of production cost.
With regard to current scintillation material, primarily of single crystal and glass bi-material.Scintillating monocrystal has the advantage such as resistance to irradiation, fast decay, High Light Output usually, but it exists that technique preparation is complicated, cost value is expensive and the shortcoming such as large size single crystal body difficulty acquisition.What is more, and be doped in rare earth luminous ion in single crystal owing to there is Segregation, the distribution in crystal is very uneven, therefore seriously affects the rate of utilization of its luminescent properties and material.Scintillation glass possess rear-earth-doped evenly, the feature such as cost is low, large-size glass is easy to preparation, chemical composition easily regulates, but its aspect such as light output, multiplicity performance is inferior to single crystal usually, and therefore its application is also severely limited.
K 2laBr 5crystal is a kind of flicker substrate material of excellence, Ce 3+the K of doping 2laBr 5crystal has abnormal high light output, and good energy resolution, can be applicable in low energy physics and the field such as safety check, medical imaging.Eu 3+, Tb 3+, Pr 3+the K of doping 2laBr 5crystal also has High Light Output, and the feature of fast decay, can be used for the fields such as scintillation fluor screen.But K 2laBr 5crystal is deliquescence, poor, the easy cleavage slabbing of mechanical property, its practical application of the large-size crystals growth disadvantages affect such as difficult, expensive very easily.
Notification number is the patent of invention of CN103951218A, then disclose by high temperature melting legal system for B 2o 3-Nb 2o 5-BaF 2-La 2o 3-K 2laBr 5-LnBr 3system glass, then by being incubated near glass transition temperature, separates out rare earth ion doped K 2laBr 5crystallite, is prepared into the rare earth ion doped K of collection glass and single crystal performance 2laBr 5devitrified glass.But there is following defect in the method, first: because at high temperature melting obtains, therefore easily cause decomposition and the volatilization of bromide raw material; Second: its chemical composition of glass of preparation and the incomplete homogeneity of crystallization holding temperature usually, the microcrystallite size of precipitation is very uneven, very easily causes the devitrification of glass; 3rd: in Crystallization Process, rare earth luminous ion K difficult to get access 2laBr 5lattice position in, affect the illumination effect of material.In addition, due to high temperature melting method glass preparation technique, the glass of production is block, is difficult to the material obtaining thin-film state.Along with extensively popularizing of civil nature, small-sized, integrated flash device is the road of the certainty of Future Development.Usual film and fibrous material are the most suitable starting material making such device, and the development of therefore current scintillation material form to device from now on can produce larger restriction.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of physical and chemical performance is stable, physical strength is high, Deliquescence-resistant is strong, optical transmission is high, content of crystallite is high, have simultaneously high light output, fast decay and good energy resolution and temporal resolution characteristic containing rare earth ion doped K 2laBr 5glass film of crystallite and preparation method thereof, this film physical and chemical performance is good, and preparation method has that equipment is simple, production cost is lower, easy to operate, combined coefficient is high, the crystallite size in the glass film of synthesis evenly, the doping content of degree of crystallinity and rare earth ion is high.
The present invention solves the problems of the technologies described above adopted technical scheme: containing rare earth ion doped K 2laBr 5the glass film of crystallite, its Mole percent consists of: Vanadium Pentoxide in FLAKES: 65-74mol%, aluminium sesquioxide: 5-10mol%, Gallium trioxide: 5-10mol%, K 2laBr 5: 10-15mol%, rare earth bromide: 1-5mol%, wherein rare earth bromide is the one in comprise cerium bromide, bromination europium, terbium bromide or praseodymium bromide.
Described contains rare earth ion doped K 2laBr 5the preparation method of the glass film of crystallite, comprises following concrete steps:
The preparation of raw material:
(1), by raw materials in molar ratio: trimethyl phosphite 99: aluminium secondary butylate: ethanol gallium: Potassium Bromide: lanthanum bromide: rare earth bromide=130-148: 10-20: 10-20: 20-30: 10-15: 1-5, and Potassium Bromide: the mol ratio of lanthanum bromide is 2: 1, rare earth bromide is the one in comprise cerium bromide, bromination europium, terbium bromide or praseodymium bromide, take analytically pure each raw materials respectively, stand-by; Potassium Bromide, lanthanum bromide, comprise cerium bromide, bromination europium, terbium bromide can replace with the bromide of other crystal water of identical mole with praseodymium bromide.
The preparation of gel:
(2), tripotassium phosphate ester hydrolysis: the trimethyl phosphite 99 of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and trimethyl phosphite 99 is 2: 1, add methyl ethyl diketone fast, the volume ratio of trimethyl phosphite 99 and methyl ethyl diketone is 1: 0.8, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and trimethyl phosphite 99 is 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution A;
(3), the hydrolysis of aluminium secondary butylate: the aluminium secondary butylate of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and aluminium secondary butylate is 2.5: 1, add methyl ethyl diketone fast, the volume ratio of aluminium secondary butylate and methyl ethyl diketone is 1: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and aluminium secondary butylate is 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution B;
(4), the hydrolysis of ethanol gallium: the ethanol gallium of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and aluminium secondary butylate is 2: 1, add Glacial acetic acid fast, the volume ratio of ethanol gallium and Glacial acetic acid is 1: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and ethanol gallium is 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution C;
(5), solution B is slowly joined in solution A, after abundant mix and blend, again solution C is slowly added in the mixing liquid of above-mentioned A and B, then a certain amount of distilled water is dripped, carry out secondary hydrolysis reaction, the mol ratio of distilled water and trimethyl phosphite 99, aluminium secondary butylate, ethanol gallium three summation is 0.6: 1, and mixed hydrolysis makes solution D after reacting 0.5 hour;
(6), in solution D, add the measured Potassium Bromide of scale, lanthanum bromide and rare earth bromide in step (1), under vigorous stirring, hydrolysis reaction, after 2 hours, forms solution E;
(7), by after solution E sealing leave standstill 1 day, obtain the solution F of certain viscosity;
The preparation of film:
(8), solution F dip-coating method (dip-coating) is coated on clean glass substrate, the pull rate of glass substrate in gelating soln controls in 0.2-1 mm/second, lift 1-5 time can be repeated according to concrete thickness requirement, each lift interval time is 15 minutes, and the film after coating at room temperature dries 4 hours;
The thermal treatment of film:
(9), the film that step (8) is obtained is placed in stove, with the ramp of 30-50 per hour DEG C to 100 DEG C, be incubated 1 hour, to remove remaining water and ethanol, then heat up stove again to 340 DEG C with the speed of 30-50 per hour DEG C, be incubated 20 minutes, to remove organism remaining in film, thermal treatment terminates, and with 50 DEG C of rate of temperature fall per hour, Slow cooling stove is to room temperature;
The high temperature hydrogen bromide Crystallizing treatment of film:
(10), the film that step (9) obtains is put into the quartz pipe of tube type resistance furnace, first the air in quartz pipe is got rid of with nitrogen, then hydrogen bromide cylinder valve is opened, pass into dry bromize hydrogen gas, with the speed of 50 DEG C per hour, progressively intensification stove is to 540-560 DEG C, and reaction treatment 2-5 hour at such a temperature, reaction treatment terminates, close bromize hydrogen gas, and with 50 DEG C of rate of temperature fall per hour, Slow cooling tube type resistance furnace is to room temperature, with bromize hydrogen gas residual in nitrogen purge pipeline, all remaining bromize hydrogen gas through pipeline tail end are reclaimed by sodium hydroxide solution, finally obtain containing rare earth ion doped K 2laBr 5the glass film of crystallite.
In described step (1), raw materials is made up of according to following mol ratio following substances: trimethyl phosphite 99: aluminium secondary butylate: ethanol gallium: Potassium Bromide: lanthanum bromide: comprise cerium bromide=148: 10: 20: 20: 10: 1.
In described step (1), raw materials is made up of according to following mol ratio following substances: trimethyl phosphite 99: aluminium secondary butylate: ethanol gallium: Potassium Bromide: lanthanum bromide: bromination europium=130: 20: 10: 30: 15: 5.
In described step (1), raw materials is made up of according to following mol ratio following substances: trimethyl phosphite 99: aluminium secondary butylate: ethanol gallium: Potassium Bromide: lanthanum bromide: terbium bromide=144: 14: 14: 24: 12: 2.
In described step (1), raw materials is made up of according to following mol ratio following substances: trimethyl phosphite 99: aluminium secondary butylate: ethanol gallium: Potassium Bromide: lanthanum bromide: praseodymium bromide=140: 12: 16: 26: 13: 3.
Compared with prior art, advantage of the present invention is:
1, sol-gel is a kind of Low Temperature Wet chemical method glass making techniques, obtains glass, therefore can be prepared into thin-film material under certain liquid viscosity by the hydrolysis of precursor raw material and polymeric chemical reaction process.
2, the synthesis condition of low temperature can prevent decomposition and the volatilization of bromide raw material effectively.
3, the glass prepared of sol-gel method is due to the volatilization of solvent and decomposition, certain micropore can be generated in the material, the environment that the generation that these micropores are nanometer bromide crystallite provides, thus the incomplete homogeneity of the chemical composition that can to a certain degree overcome due to fusion cast glass and crystallization treatment temp, cause the devitrification of the uneven of crystallization particle and glass.
4, as rare earth and the La of glass network modifier 3+ion, most one is in together in micropore gap, and therefore along with the carrying out of high temperature hydrogen bromide process, rare earth luminous ion easily enters K 2laBr 5lattice position in, obtain the rare earth ion doped and illumination effect of high density.
5, the hydrogen bromide drying treatment of high temperature impels the oxybromide in gel glass, oxyhydroxide and oxide compound etc. to convert bromide to, can carry out the dehydration reaction of bromide raw material, and effectively promotes and control K 2laBr 5generation.
Because this film glass matrix is P 2o 5-Al 2o 3-Ga 2o 3be glass, therefore high in the transmitance of ultraviolet band, according to the actual requirements, alterable component is equipped with and regulates its physical and chemical performance and optical property, containing rare earth ion doped K 2laBr 5the phosphorus aluminic acid gallate glass thin-film material of crystallite, has superior scintillation properties, physical strength, thermal stability characteristics, overcomes K 2laBr 5the single crystal shortcoming such as very easily deliquescence, mechanical property be poor; The experiment proved that: by formula of the present invention and preparation method, separate out rare earth ion doped K 2laBr 5crystalline phase, obtained ion doping K 2laBr 5devitrified glass is transparent, and energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, and have extremely strong light output, decay soon, the performances such as good energy resolution and temporal resolution, can make scintillation detectors efficiency increase substantially.This thin-film material is that the development of small-sized flash device from now on provides material base.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of glass film after the thermal treatment of embodiment one high temperature hydrogen bromide;
Fig. 2 be embodiment one excitation of X-rays containing Ce 3+ion doping K 2laBr 5the fluorescence spectrum of the glass film of crystallite;
Fig. 3 be embodiment two excitation of X-rays containing Eu 3+ion doping K 2laBr 5the fluorescence spectrum of the glass film of crystallite;
Fig. 4 be embodiment three excitation of X-rays containing Tb 3+ion doping K 2laBr 5the fluorescence spectrum of the glass film of crystallite.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment one
Containing rare earth ion doped K 2laBr 5the preparation method of the glass film of crystallite, comprises following concrete steps:
(1), by raw materials in molar ratio: trimethyl phosphite 99: aluminium secondary butylate: ethanol gallium: Potassium Bromide: lanthanum bromide: comprise cerium bromide=148: 10: 20: 20: 10: 1, analytically pure each raw materials that total amount is 30 grams is taken, stand-by;
(2), tripotassium phosphate ester hydrolysis: the trimethyl phosphite 99 of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and trimethyl phosphite 99 is 2: 1, add methyl ethyl diketone fast, the volume ratio of trimethyl phosphite 99 and methyl ethyl diketone is 1: 0.8, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and trimethyl phosphite 99 is 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution A;
(3), the hydrolysis of aluminium secondary butylate: the aluminium secondary butylate of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and aluminium secondary butylate is 2.5: 1, add methyl ethyl diketone fast, the volume ratio of aluminium secondary butylate and methyl ethyl diketone is 1: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and aluminium secondary butylate is 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution B;
(4), the hydrolysis of ethanol gallium: the ethanol gallium of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and aluminium secondary butylate is 2: 1, add Glacial acetic acid fast, the volume ratio of ethanol gallium and Glacial acetic acid is 1: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and ethanol gallium is 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution C;
(5), solution B is slowly joined in solution A, after abundant mix and blend, again solution C is slowly added in the mixing liquid of above-mentioned A and B, then a certain amount of distilled water is dripped, carry out secondary hydrolysis reaction, the mol ratio of distilled water and trimethyl phosphite 99, aluminium secondary butylate, ethanol gallium three summation is 0.6: 1, and mixed hydrolysis makes solution D after reacting 0.5 hour;
(6), in solution D, add the measured Potassium Bromide of scale, lanthanum bromide and comprise cerium bromide in step (1), under vigorous stirring, hydrolysis reaction, after 2 hours, forms solution E;
(7), by after solution E sealing leave standstill 1 day, obtain the solution F of certain viscosity;
(8), solution F dip-coating method (dip-coating) is coated on clean glass substrate, the pull rate of glass substrate in gelating soln controls in 0.2 mm/second, lift 1 time, the film after coating at room temperature dries 4 hours;
(9), the film that step (8) is obtained is placed in stove, with the ramp of 30 DEG C per hour to 100 DEG C, be incubated 1 hour, to remove remaining water and ethanol, then heat up stove again to 340 DEG C with the speed of 30 DEG C per hour, be incubated 20 minutes, to remove organism remaining in film, thermal treatment terminates, and with 50 DEG C of rate of temperature fall per hour, Slow cooling stove is to room temperature;
(10), the film that step (9) obtains is put into the quartz pipe of tube type resistance furnace, first the air in quartz pipe is got rid of with nitrogen, then hydrogen bromide cylinder valve is opened, pass into dry bromination-gas, with the speed of 50 DEG C per hour, progressively intensification stove is to 540 DEG C, and reaction treatment 5 hours at such a temperature, reaction treatment terminates, close bromize hydrogen gas, and with 50 DEG C of rate of temperature fall per hour, Slow cooling tube type resistance furnace is to room temperature, with bromize hydrogen gas residual in nitrogen purge pipeline, all remaining bromize hydrogen gas through pipeline tail end are reclaimed by sodium hydroxide solution, finally obtain containing rare earth ion doped K 2laBr 5the 74P of crystallite 2o 5-5Al 2o 3-10Ga 2o 3-10K 2laBr 5-1CeBr 3system glass film.
Ce is contained to what prepare 3+ion doping K 2laBr 5the glass film of crystallite carries out performance test, scrapes and collects film powder, and as shown in Figure 1, its result is as follows for the XRD figure of glass thin coating materials after hydrogen bromide process: through processing XRD diffraction peak and the K of the sample obtained 2laBr 5the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and what therefore obtain is containing K 2laBr 5the glass film of crystallite.The Ce of excitation of X-rays 3+ion doping K 2laBr 5as shown in Figure 2, with compared with Crystallizing treatment, its fluorescence intensity significantly strengthens the fluorescence spectrum of devitrified glass film, and fluorescence decay time is 41ns.
Embodiment two
Substantially identical with embodiment one, difference is in step (1), raw materials is according to following mol ratio: trimethyl phosphite 99: aluminium secondary butylate: ethanol gallium: Potassium Bromide: lanthanum bromide: bromination europium=130: 20: 10: 30: 15: 5, takes each raw material respectively; In step (7), the pull rate of glass substrate in gelating soln controls in 1 mm/second, repeats lift 5 times, and lift interval time is 15 minutes at every turn; In step (9), with the ramp of 50 DEG C per hour to 100 DEG C, then heat up stove again to 340 DEG C with the speed of 50 DEG C per hour; In step (9), progressively intensification stove is to 560 DEG C, and reaction treatment 2 hours at such a temperature, finally obtain containing Eu 3+ion doping K 2laBr 5the 65P of crystallite 2o 5-10Al 2o 3-5Ga 2o 3-15K 2laBr 5-5EuBr 3system glass film.
Eu is contained to what prepare 3+ion doping K 2laBr 5the glass film of crystallite carries out performance test, and the XRD figure of glass film after hydrogen bromide process is substantially identical with Fig. 1, and just intensity is different, and what therefore obtain is containing K 2laBr 5the glass film of crystallite.The Eu of excitation of X-rays 3+ion doping K 2laBr 5the P of crystallite 2o 5-Al 2o 3-Ga 2o 3as shown in Figure 3, with compared with Crystallizing treatment, its fluorescence intensity significantly strengthens the fluorescence spectrum of glass film.
Embodiment three
Substantially identical with embodiment one, difference is in step (1), raw materials is according to following molar ratio: trimethyl phosphite 99: aluminium secondary butylate: ethanol gallium: Potassium Bromide: lanthanum bromide: terbium bromide=144: 14: 14: 24: 12: 2, takes each raw material respectively; In step (7), the pull rate of glass substrate in gelating soln controls in 0.6 mm/second, repeats lift 3 times, and lift interval time is 15 minutes at every turn; In step (9), with the ramp of 40 DEG C per hour to 100 DEG C, then heat up stove again to 340 DEG C with the speed of 40 DEG C per hour; In step (10), progressively intensification stove is to 550 DEG C, and reaction treatment 3 hours at such a temperature, finally obtain containing Tb 3+ion doping K 2laBr 5the 72P of crystallite 2o 5-7Al 2o 3-7Ga 2o 3-12K 2laBr 5-2EuBr 3system glass film.
Tb is contained to what prepare 3+ion doping K 2laBr 5the glass film of crystallite carries out performance test, and the XRD figure of glass film after hydrogen bromide process is substantially identical with Fig. 1, and just intensity is different, and what therefore obtain is containing K 2laBr 5the glass film of crystallite.The Tb of excitation of X-rays 3+ion doping K 2laBr 5the P of crystallite 2o 5-Al 2o 3-Ga 2o 3as shown in Figure 4, with compared with Crystallizing treatment, its fluorescence intensity significantly strengthens the fluorescence spectrum of glass film.
Embodiment four
Substantially identical with embodiment one, difference is in step (1), raw material is according to following molar ratio: (trimethyl phosphite 99): (aluminium secondary butylate): (ethanol gallium): (Potassium Bromide): (lanthanum bromide): (praseodymium bromide)=140: 12: 16: 26: 13: 3, takes each raw material respectively; In step (7), the pull rate of glass substrate in gelating soln controls in 0.4 mm/second, repeats lift 2 times, and lift interval time is 15 minutes at every turn; In step (9), with the ramp of 35 DEG C per hour to 100 DEG C, then heat up stove again to 340 DEG C with the speed of 35 DEG C per hour; In step (10), progressively intensification stove is to 545 DEG C, and reaction treatment 2.5 hours at such a temperature, finally obtain containing Pr 3+ion doping K 2laBr 5the 70P of crystallite 2o 5-6Al 2o 3-8Ga 2o 3-13K 2laBr 5-3PrBr 3system glass film.
Embodiment four also can obtain preferably containing Pr 3+ion doping K 2laBr 5the glass film of crystallite, concrete film spectrum does not provide one by one.

Claims (6)

1. containing rare earth ion doped K 2laBr 5the glass film of crystallite, is characterized in that its Mole percent consists of: Vanadium Pentoxide in FLAKES: 65-74mol%, aluminium sesquioxide: 5-10mol%, Gallium trioxide: 5-10mol%, K 2laBr 5: 10-15mol%, rare earth bromide: 1-5mol%, wherein rare earth bromide is the one in comprise cerium bromide, bromination europium, terbium bromide or praseodymium bromide.
2. as claimed in claim 1 containing rare earth ion doped K 2laBr 5the preparation method of the glass film of crystallite, is characterized in that comprising following concrete steps:
(1), by raw materials in molar ratio: trimethyl phosphite 99: aluminium secondary butylate: ethanol gallium: Potassium Bromide: lanthanum bromide: rare earth bromide=130-148: 10-20: 10-20: 20-30: 10-15: 1-5, and Potassium Bromide: the mol ratio of lanthanum bromide is 2: 1, rare earth bromide is the one in comprise cerium bromide, bromination europium, terbium bromide or praseodymium bromide, take analytically pure each raw materials respectively, stand-by;
(2), tripotassium phosphate ester hydrolysis: the trimethyl phosphite 99 of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and trimethyl phosphite 99 is 2: 1, add methyl ethyl diketone fast, the volume ratio of trimethyl phosphite 99 and methyl ethyl diketone is 1: 0.8, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and trimethyl phosphite 99 is 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution A;
(3), the hydrolysis of aluminium secondary butylate: the aluminium secondary butylate of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and aluminium secondary butylate is 2.5: 1, add methyl ethyl diketone fast, the volume ratio of aluminium secondary butylate and methyl ethyl diketone is 1: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and aluminium secondary butylate is 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution B;
(4), the hydrolysis of ethanol gallium: the ethanol gallium of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and aluminium secondary butylate is 2: 1, add Glacial acetic acid fast, the volume ratio of ethanol gallium and Glacial acetic acid is 1: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and ethanol gallium is 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution C;
(5), solution B is slowly joined in solution A, after abundant mix and blend, again solution C is slowly added in the mixing liquid of above-mentioned A and B, then a certain amount of distilled water is dripped, carry out secondary hydrolysis reaction, the mol ratio of distilled water and trimethyl phosphite 99, aluminium secondary butylate, ethanol gallium three summation is 0.6: 1, and mixed hydrolysis makes solution D after reacting 0.5 hour;
(6), in solution D, add the measured Potassium Bromide of scale, lanthanum bromide and rare earth bromide in step (1), under vigorous stirring, hydrolysis reaction, after 2 hours, makes solution E;
(7), by after solution E sealing leave standstill 1 day, obtain the solution F of certain viscosity;
(8), solution F dip-coating method is coated on clean glass substrate, the pull rate of glass substrate in solution F controls in 0.2-1 mm/second, lift 1-5 time can be repeated according to concrete thickness requirement, each lift interval time is 15 minutes, and the film after coating at room temperature dries 4 hours;
(9), the film that step (8) is obtained is placed in stove, with the ramp of 30-50 per hour DEG C to 100 DEG C, be incubated 1 hour, to remove remaining water and ethanol, then heat up stove again to 340 DEG C with the speed of 30-50 per hour DEG C, be incubated 20 minutes, to remove organism remaining in film, thermal treatment terminates, and with 50 DEG C of rate of temperature fall per hour, Slow cooling stove is to room temperature;
(10), the film that step (9) obtains is put into the quartz pipe of tube type resistance furnace, first the air in quartz pipe is got rid of with nitrogen, then hydrogen bromide cylinder valve is opened, pass into dry bromize hydrogen gas, with the speed of 50 DEG C per hour, progressively intensification stove is to 540-560 DEG C, and reaction treatment 2-5 hour at such a temperature, reaction treatment terminates, close bromize hydrogen gas, and with 50 DEG C of rate of temperature fall per hour, Slow cooling tube type resistance furnace is to room temperature, with bromize hydrogen gas residual in nitrogen purge pipeline, all remaining bromize hydrogen gas through pipeline tail end are reclaimed by sodium hydroxide solution, finally obtain containing rare earth ion doped K 2laBr 5the glass film of crystallite.
3. as claimed in claim 2 containing rare earth ion doped K 2laBr 5the glass film of crystallite, it is characterized in that in described step (1), raw materials is made up of according to following mol ratio following substances: trimethyl phosphite 99: aluminium secondary butylate: ethanol gallium: Potassium Bromide: lanthanum bromide: comprise cerium bromide=148: 10: 20: 20: 10: 1.
4. as claimed in claim 2 containing rare earth ion doped K 2laBr 5the glass film of crystallite, it is characterized in that in described step (1), raw materials is made up of according to following mol ratio following substances: trimethyl phosphite 99: aluminium secondary butylate: ethanol gallium: Potassium Bromide: lanthanum bromide: bromination europium=130: 20: 10: 30: 15: 5.
5. as claimed in claim 2 containing rare earth ion doped K 2laBr 5the glass film of crystallite, it is characterized in that in described step (1), raw materials is made up of according to following mol ratio following substances: trimethyl phosphite 99: aluminium secondary butylate: ethanol gallium: Potassium Bromide: lanthanum bromide: terbium bromide=144: 14: 14: 24: 12: 2.
6. as claimed in claim 2 containing rare earth ion doped K 2laBr 5the glass film of crystallite, it is characterized in that in described step (1), raw materials is made up of according to following mol ratio following substances: trimethyl phosphite 99: aluminium secondary butylate: ethanol gallium: Potassium Bromide: lanthanum bromide: praseodymium bromide=140: 12: 16: 26: 13: 3.
CN201510783082.6A 2015-11-16 2015-11-16 Glass film containing rare-earth-ion-doped K2LaBr5 microcrystalline and preparation method thereof Withdrawn CN105481257A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101300202A (en) * 2005-10-26 2008-11-05 旭硝子株式会社 Phosphate optical glass
CN103011589A (en) * 2012-06-27 2013-04-03 温州大学 Sodium borosilicate glass doped with In2S3 quantum dots and preparation method thereof
CN103951218A (en) * 2014-05-08 2014-07-30 宁波大学 Rare-earth-ion-doped K2LaBr5 microcrystalline glass and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101300202A (en) * 2005-10-26 2008-11-05 旭硝子株式会社 Phosphate optical glass
CN103011589A (en) * 2012-06-27 2013-04-03 温州大学 Sodium borosilicate glass doped with In2S3 quantum dots and preparation method thereof
CN103951218A (en) * 2014-05-08 2014-07-30 宁波大学 Rare-earth-ion-doped K2LaBr5 microcrystalline glass and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈红兵等: "CuI微晶掺杂硅凝胶玻璃及其薄膜的制备", 《材料研究学报》 *

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