CN105384349A - Glass film containing rare earth ion doped KA12Br7 microcrystal and preparation method thereof - Google Patents

Glass film containing rare earth ion doped KA12Br7 microcrystal and preparation method thereof Download PDF

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CN105384349A
CN105384349A CN201510783343.4A CN201510783343A CN105384349A CN 105384349 A CN105384349 A CN 105384349A CN 201510783343 A CN201510783343 A CN 201510783343A CN 105384349 A CN105384349 A CN 105384349A
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bromide
rare earth
kal
glass
crystallite
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汤庆阳
夏海平
冯治刚
王成
盛启国
何仕楠
江东升
张健
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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

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  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses a glass film containing rare earth ion doped KA12Br7 microcrystal, which is characterized by comprising the following components in mole ratio: 76mol% of silicon dioxide, 6-10mol% of aluminum oxide, 3-5mol% of gallium oxide, 8-12mol% of KAl2Br7 and 1-3mol% of rare earth bromide, wherein the rare earth bromide is one of cerium bromide, europium bromide or terbium bromide. The glass film has the advantages that a sol-gel method is a low-temperature low-humidity chemical method glass preparation technology, and glass is obtained by virtue of hydrolysis of a precursor raw material and a process of polymerization chemical reaction, so that the glass can be prepared into a film material under a certain liquid viscosity, and a low-temperature synthetic condition can effectively prevent decomposition and volatilization of a bromide raw material; and the glass prepared by the sol-gel method, due to volatilization and decomposition of a solvent, can generate certain micropores in a material, and the micropores provide a good environment for generation of nano bromide microcrystals, so that nonuniformity of crystallization particles and devitrification of the glass caused by incomplete uniformity of chemical components and crystallization treatment temperature for smelting glass can be overcome to a certain extent.

Description

Containing rare earth ion doped KAl 2br 7glass film of crystallite and preparation method thereof
Technical field
The present invention relates to containing a kind of rare earth ion doped devitrified glass film, be specifically related to a kind of be used as scintillation material containing rare earth ion doped KAl 2br 7the glass film of crystallite and so-gel wet chemical preparation method 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.
Rare-earth-ion-doped KAl 2br 7crystal is a kind of material with excellent scintillation properties, due to Al 3+with other rare earth ion, there is analogous ionic radius size and identical ionic valence condition, other multiple luminescence rare earth ion that can adulterate relatively large.Such as, Ce 3+the KAl of doping 2br 7it is high that crystal has light output, decays soon, good energy resolution, temporal resolution and linear response, has than rare earth ion doped crystal of fluoride and the higher luminous efficiency of oxide crystal, scintillation detectors efficiency can be made to increase substantially.Eu 3+, Tb 3+the KAl of doping 2br 7the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But KAl 2br 7the defects such as poor, the easy cleavage of the mechanical property of host crystal and very easily deliquescence, and large-size crystals grows its practical applications of disadvantages affect such as difficult and expensive.
Glass containing crystallite is a kind of material integrating glass and single crystal performance, therefore containing rare earth ion doped KAl 2br 7the glass of crystallite is expected to the respective different defect solving above-mentioned materials.Traditional glass material preparation process containing crystallite is: first adopting high temperature melting legal system standby one-tenth glass, then by being incubated near glass transition temperature, separating out crystallite at inside glass.But there is following defect in the method, first: because at high temperature melting obtains, therefore easily cause the decomposition 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, in the lattice position of rare earth luminous ion crystallite difficult to get access, affect the illumination effect of material.What is more, and due to high temperature melting method glass preparation technique, the glass of production is block, can not obtain the material of 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 thin-film material makes the most suitable starting material of 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 KAl 2br 7glass film of crystallite and preparation method thereof, this glass film has that physical and chemical performance is stable, preparation method has that equipment is simple, production cost is lower, easy to operate, combined coefficient is high, and 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 KAl 2br 7the glass film of crystallite, its Mole percent consists of: silicon-dioxide: 76mol%, aluminium sesquioxide: 6-10mol%, Gallium trioxide: 3-5mol%, KAl 2br 7: 8-12mol%, rare earth bromide: 1-3mol%, wherein rare earth bromide is the one in comprise cerium bromide, bromination europium or terbium bromide.
Described contains rare earth ion doped KAl 2br 7the glass film of crystallite, is characterized in that its Mole percent consists of: silicon-dioxide: 76mol%, aluminium sesquioxide: 10mol%, Gallium trioxide: 5mol%, KAl 2br 7: 8mol%, comprise cerium bromide: 1mol%.
Described contains rare earth ion doped KAl 2br 7the glass film of crystallite, is characterized in that its Mole percent consists of: silicon-dioxide: 76mol%, aluminium sesquioxide: 6mol%, Gallium trioxide: 3mol%, KAl 2br 7: 12mol%, bromination europium: 3mol%.
Described contains rare earth ion doped KAl 2br 7the glass film of crystallite, is characterized in that its Mole percent consists of: silicon-dioxide: 76mol%, aluminium sesquioxide: 8mol%, Gallium trioxide: 4mol%, KAl 2br 7: 10mol%, terbium bromide: 2mol%.
Described contains rare earth ion doped KAl 2br 7the preparation method of the glass film of crystallite, comprises following concrete steps:
The preparation of raw material:
(1), by raw materials in molar ratio: tetraethoxy: aluminium secondary butylate: ethanol gallium: Potassium Bromide: aluminum bromide: rare earth bromide=76: 12-20: 6-10: 16-24:8-12: 1-3, and Potassium Bromide: the mol ratio of aluminum bromide is 1: 2, rare earth bromide is the one in comprise cerium bromide, bromination europium or terbium bromide, take analytically pure each raw materials respectively, stand-by; Potassium Bromide, aluminum bromide, comprise cerium bromide, bromination europium can replace with the bromide of other crystal water of identical mole with terbium bromide.
The preparation of gel:
(2), the hydrolysis of tetraethoxy: the tetraethoxy of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and tetraethoxy is 2.5: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and tetraethoxy is 0.9: 1, and be 4-5 by the pH value of concentrated nitric acid regulator solution, 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: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and aluminium secondary butylate is 0.7: 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 0.5: 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 ethanol gallium is 2.5: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and ethanol gallium is 0.6: 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 and C are slowly joined in solution A respectively, after abundant mix and blend, drip a certain amount of distilled water again, carry out secondary hydrolysis reaction, the mol ratio of distilled water and tetraethoxy, aluminium secondary butylate, ethanol gallium three summation is 0.6: 1, mixed hydrolysis makes solution D after reacting 0.5 hour:
(6), in solution D, add the measured Potassium Bromide of scale, aluminum bromide and each raw material of 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;
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 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;
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 micritization process 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 610-630 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 KAl 2br 7the glass film of crystallite.
In described step (1), raw materials is made up of according to following mol ratio following substances: tetraethoxy: aluminium secondary butylate: ethanol gallium: Potassium Bromide: aluminum bromide: comprise cerium bromide=76: 20: 10: 8: 16: 1.
In described step (1), raw materials is made up of according to following mol ratio following substances: tetraethoxy: aluminium secondary butylate: ethanol gallium: Potassium Bromide: aluminum bromide: bromination europium=76: 12: 6: 12: 24: 3.
In described step (1), raw materials is made up of according to following mol ratio following substances: tetraethoxy: aluminium secondary butylate: ethanol gallium: Potassium Bromide: aluminum bromide: terbium bromide=76: 16: 8: 10: 20: 2.
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 Al 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 KAl 2br 7lattice 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 KAl 2br 7the generation of crystallite.
Because this film glass matrix is SiO 2-Al 2o 3-Ga 2o 3three-phase system forms, and therefore according to actual needs, can regulate its optics and physical and chemical performance by changing chemical composition.The glass film of this component is high in the transmitance of ultraviolet band, has superior scintillation properties, physical strength, thermal stability characteristics, overcomes KAl 2br 7the 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 KAl 2br 7crystalline phase, obtained contains rare earth ion doped KAl 2br 7the glass film of crystallite is transparent, 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 the scanning electron microscope diagram (SEM) of embodiment one high temperature hydrogen bromide micritization thermal treatment rear film sample;
Fig. 2 be embodiment one excitation of X-rays containing Ce 3+ion doping KAl 2br 7the fluorescence spectrum of the glass film of crystallite;
Fig. 3 be embodiment two excitation of X-rays containing Eu 3+ion doping KAl 2br 7the fluorescence spectrum of the glass film of crystallite;
Fig. 4 be embodiment three excitation of X-rays containing Tb 3+ion doping KAl 2br 7the 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 KAl 2br 7the preparation method of the glass film of crystallite, comprises following concrete steps:
(1), by raw materials in molar ratio: tetraethoxy: aluminium secondary butylate: ethanol gallium: Potassium Bromide: aluminum bromide: comprise cerium bromide=76: 20: 10: 8: 16: 1, analytically pure each raw materials that total amount is 30 grams is taken, stand-by;
(2), the hydrolysis of tetraethoxy: the tetraethoxy of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and tetraethoxy is 2.5: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and tetraethoxy is 0.9: 1, and be 4-5 by the pH value of concentrated nitric acid regulator solution, 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: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and aluminium secondary butylate is 0.7: 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 0.5: 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 ethanol gallium is 2.5: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and ethanol gallium is 0.6: 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 and C are slowly joined in solution A respectively, after abundant mix and blend, drip a certain amount of distilled water again, carry out secondary hydrolysis reaction, the mol ratio of distilled water and tetraethoxy, aluminium secondary butylate, ethanol gallium three summation is 0.6: 1, mixed hydrolysis makes solution D after reacting 0.5 hour;
(6), in solution D, add the measured Potassium Bromide of scale, aluminum bromide and comprise cerium 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), by solution F dip-coating method (dip-coating) be coated on clean glass substrate, the pull rate of glass substrate in solution F controls in 0.2 mm/second, and 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 bromize hydrogen gas, with the speed of 50 DEG C per hour, progressively intensification stove is to 610 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 KAl 2br 7the 76SiO of crystallite 2-10Al 2o 3-5Ga 2o 3-8KAl 2br 7-1CeBr 3system glass film.
Ce is contained to what prepare 3+ion doping KAl 2br 7the glass film of crystallite carries out sem test, obtains the scanning electron microscope diagram of glass film after the process of high temperature hydrogen bromide micritization as shown in Figure 1, and in particle shape in photo is the nano microcrystalline of separating out, and rest part is glassy phase.The test of X-ray diffraction shows that crystalline phase is KAl 2br 7phase, the material therefore obtained is KAl 2br 7the devitrified glass of crystallization phase.Excitation of X-rays containing Ce 3+ion doping KAl 2br 7as shown in Figure 2, fluorescence peak intensity is comparatively large, and be obviously better than the sample without hydrogen bromide high temperature Crystallizing treatment, fluorescence decay time is 37ns for the fluorescence spectrum of the glass film of crystallite.
Embodiment two
Substantially identical with embodiment one, difference is in step (1), raw materials is according to following mol ratio: tetraethoxy: aluminium secondary butylate: ethanol gallium: Potassium Bromide: aluminum bromide: bromination europium=76: 12: 6: 12: 24: 3, takes each raw materials respectively; In step (8), 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 (10), progressively intensification stove is to 630 DEG C, and reaction treatment 2 hours at such a temperature, obtain containing Eu 3+ion doping KAl 2br 7the 76SiO of crystallite 2-6Al 2o 3-3Ga 2o 3-12KAl 2br 7-3EuBr 3system glass film.
Eu is contained to what prepare 3+ion doping KAl 2br 7the spectral quality test of devitrified glass, excitation of X-rays containing Eu 3+ion doping KAl 2br 7the fluorescence spectrum of the glass film of crystallite as shown in Figure 3, its result shows that after the process of hydrogen bromide thermal crystallisation, produce crystallite luminous intensity compared with untreated significantly improves, illustrate that high temperature Crystallizing treatment is conducive to improving and optimizing fluorescence intensity, simultaneously above-mentioned prepare containing rare earth ion doped KAl 2br 7the glass film of crystallite is transparent and physical and chemical performance is excellent.
Embodiment three
Substantially identical with embodiment one, difference is in step (1), raw materials is according to following mol ratio: tetraethoxy: aluminium secondary butylate: ethanol gallium: Potassium Bromide: aluminum bromide: terbium bromide=76: 16: 8: 10: 20: 2, takes each raw materials respectively; In step (8), 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 620 DEG C, and reaction treatment 3 hours at such a temperature, obtain containing Tb 3+ion doping KAl 2br 7the 76SiO of crystallite 2-8Al 2o 3-4Ga 2o 3-10KAl 2br 7-2TbBr 3system glass film.
Tb is contained to what prepare 3+ion doping KAl 2br 7the spectral quality test of devitrified glass, excitation of X-rays containing Tb 3+ion doping KAl 2br 7the fluorescence spectrum of the glass film of crystallite as shown in Figure 4, its result shows that after the process of hydrogen bromide thermal crystallisation, produce crystallite luminous intensity compared with untreated significantly improves, illustrate that high temperature Crystallizing treatment is conducive to improving and optimizing fluorescence intensity, simultaneously above-mentioned prepare containing rare earth ion doped KAl 2br 7the glass film of crystallite is transparent and physical and chemical performance is excellent.

Claims (8)

1. containing rare earth ion doped KAl 2br 7the glass film of crystallite, is characterized in that its Mole percent consists of: silicon-dioxide: 76mol%, aluminium sesquioxide: 6-10mol%, Gallium trioxide: 3-5mol%, KAl 2br 7: 8-12mol%, rare earth bromide: 1-3mol%, wherein rare earth bromide is the one in comprise cerium bromide, bromination europium or terbium bromide.
2. as claimed in claim 1 containing rare earth ion doped KAl 2br 7the glass film of crystallite, is characterized in that its Mole percent consists of: silicon-dioxide: 76mol%, aluminium sesquioxide: 10mol%, Gallium trioxide: 5mol%, KAl 2br 7: 8mol%, comprise cerium bromide: 1mol%.
3. as claimed in claim 1 containing rare earth ion doped KAl 2br 7the glass film of crystallite, is characterized in that its Mole percent consists of: silicon-dioxide: 76mol%, aluminium sesquioxide: 6mol%, Gallium trioxide: 3mol%, KAl 2br 7: 12mol%, bromination europium: 3mol%.
4. as claimed in claim 1 containing rare earth ion doped KAl 2br 7the glass film of crystallite, is characterized in that its Mole percent consists of: silicon-dioxide: 76mol%, aluminium sesquioxide: 8mol%, Gallium trioxide: 4mol%, KAl 2br 7: 10mol%, terbium bromide: 2mol%.
5. as claimed in claim 1 containing rare earth ion doped KAl 2br 7the preparation method of the glass film of crystallite, is characterized in that comprising following concrete steps:
(1), by raw materials in molar ratio: tetraethoxy: aluminium secondary butylate: ethanol gallium: Potassium Bromide: aluminum bromide: rare earth bromide=76: 12-20: 6-10: 16-24: 8-12: 1-3, and Potassium Bromide: the mol ratio of aluminum bromide is 1: 2, rare earth bromide is the one in comprise cerium bromide, bromination europium or terbium bromide, take analytically pure each raw materials respectively, stand-by;
(2), the hydrolysis of tetraethoxy: the tetraethoxy of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and tetraethoxy is 2.5: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and tetraethoxy is 0.9: 1, and be 4-5 by the pH value of concentrated nitric acid regulator solution, 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: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and aluminium secondary butylate is 0.7: 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 0.5: 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 ethanol gallium is 2.5: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and ethanol gallium is 0.6: 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 and C are slowly joined in solution A respectively, after abundant mix and blend, drip a certain amount of distilled water again, carry out secondary hydrolysis reaction, the mol ratio of distilled water and tetraethoxy, aluminium secondary butylate, ethanol gallium three summation is 0.6: 1, mixed hydrolysis makes solution D after reacting 0.5 hour;
(6), in solution D, add the measured Potassium Bromide of scale, aluminum bromide and each raw material of 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 610-630 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 KAl 2br 7the glass film of crystallite.
6. as claimed in claim 5 containing rare earth ion doped KAl 2br 7the preparation method of the 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: tetraethoxy: aluminium secondary butylate: ethanol gallium: Potassium Bromide: aluminum bromide: comprise cerium bromide=76: 20: 10: 8: 16: 1.
7. as claimed in claim 5 containing rare earth ion doped KAl 2br 7the preparation method of the 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: tetraethoxy: aluminium secondary butylate: ethanol gallium: Potassium Bromide: aluminum bromide: bromination europium=76: 12: 6: 12: 24: 3.
8. as claimed in claim 5 containing rare earth ion doped KAl 2br 7the preparation method of the 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: tetraethoxy: aluminium secondary butylate: ethanol gallium: Potassium Bromide: aluminum bromide: terbium bromide=76: 16: 8: 10: 20: 2.
CN201510783343.4A 2015-11-16 2015-11-16 Glass film containing rare earth ion doped KA12Br7 microcrystal and preparation method thereof Withdrawn CN105384349A (en)

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JP5087450B2 (en) * 2008-03-28 2012-12-05 三井造船株式会社 Rotary distributor
CN103011589A (en) * 2012-06-27 2013-04-03 温州大学 Sodium borosilicate glass doped with In2S3 quantum dots and preparation method thereof
CN103951251A (en) * 2014-05-08 2014-07-30 宁波大学 Rare-earth-ion-doped LiBaBr3 microcrystalline glass and preparation method thereof

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JP5087450B2 (en) * 2008-03-28 2012-12-05 三井造船株式会社 Rotary distributor
CN103011589A (en) * 2012-06-27 2013-04-03 温州大学 Sodium borosilicate glass doped with In2S3 quantum dots and preparation method thereof
CN103951251A (en) * 2014-05-08 2014-07-30 宁波大学 Rare-earth-ion-doped LiBaBr3 microcrystalline glass and preparation method thereof

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