CN105384345A - Glass film containing rare earth ion doped K2LaCl5 microcrystal and preparation method thereof - Google Patents

Glass film containing rare earth ion doped K2LaCl5 microcrystal and preparation method thereof Download PDF

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CN105384345A
CN105384345A CN201510783077.5A CN201510783077A CN105384345A CN 105384345 A CN105384345 A CN 105384345A CN 201510783077 A CN201510783077 A CN 201510783077A CN 105384345 A CN105384345 A CN 105384345A
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chloride
rare earth
glass
tri
lacl
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冯治刚
夏海平
盛启国
江东升
王成
张健
何仕楠
汤庆阳
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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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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • 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 K2LaCl5 microcrystal and a preparation method thereof. The glass film is characterized by comprising the following components in percentage by mole: 78 percent of diboron trioxide, 8-15 percent of aluminum oxide, 6-11 percent of K2LaCl5 and 1-3 percent of a rare-earth chloride, wherein the rare-earth chloride refers to one of cerium chloride, europium chloride or terbium chloride. The glass film disclosed by the invention has the advantages that sol-gel refers to a low-temperature wet chemistry method glass preparation technology, and glass is obtained by precursor material hydrolysis and polymerization reaction process, and therefore, a film material can be prepared at a certain liquid viscosity. Moreover, due to low-temperature synthesis condition, decomposition and volatilization of chloride raw materials can be effectively prevented. Due to volatilization and decomposition of solvents, the glass prepared by the sol-gel method generates a certain micro-pores in the materials, and the micro-pores provide a good environment for generating nano chloride microcrystal, so that the phenomenon that non-uniformity of crystallization particles and glass devitrification are caused by chemical constituents of the melted glass and incomplete uniformity of crystallization treatment temperature can be avoided to a certain degree.

Description

Containing rare earth ion doped K 2laCl 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 2laCl 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 2laCl 5crystal is a kind of flicker substrate material of excellence, Ce 3+the K of doping 2laCl 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+the K of doping 2laCl 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 2laCl 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 CN103951217A, then disclose by high temperature melting legal system for SiO 2-B 2o 3-BaF 2-La 2o 3-K 2laCl 5-LnCl 3system glass, then by being incubated near glass transition temperature, separates out rare earth ion doped K 2laCl 5crystallite, is prepared into the rare earth ion doped K of collection glass and single crystal performance 2laCl 5devitrified glass.But there is following defect in the method, first: because at high temperature melting obtains, therefore easily cause the decomposition of muriate 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 2laCl 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 2laCl 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 2laCl 5the glass film of crystallite, its Mole percent consists of: boron trioxide: 78mol%, aluminium sesquioxide: 8-15mol%, K 2laCl 5: 6-11mol%, rare earth chloride: 1-3mol%, wherein rare earth chloride is the one in Cerium II Chloride, Europium trichloride or terbium chloride.
Described contains rare earth ion doped K 2laCl 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: tri-n-butyl borate: aluminium secondary butylate: Repone K: Lanthanum trichloride: rare earth chloride=156: 16-30: 12-22: 6-11: 1-3, and Repone K: the mol ratio of Lanthanum trichloride is 2: 1, rare earth chloride is the one in Cerium II Chloride, Europium trichloride or terbium chloride, take analytically pure each raw materials respectively, stand-by; Repone K, Lanthanum trichloride, Cerium II Chloride, Europium trichloride can replace with the iodide of other crystal water of identical mole with terbium chloride.
The preparation of gel:
(2), the hydrolysis of tri-n-butyl borate: the tri-n-butyl borate of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and tri-n-butyl borate is 2.5: 1, add methyl ethyl diketone fast, the volume ratio of tri-n-butyl borate and methyl ethyl diketone is 0.8: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and tri-n-butyl borate is 0.6: 1, regulate its pH value to 4-5 with concentrated nitric acid, 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 carries out the stirring of strong magnetic power, progressively instills distilled water, the mol ratio of distilled water and aluminium secondary butylate is 0.6: 1, regulate its pH value to 4 ~ 5 with concentrated nitric acid, be hydrolyzed under room temperature reaction 1 hour, makes solution B;
(4), by solution B slowly join in solution A, after abundant mix and blend, then drip a certain amount of distilled water, carry out secondary hydrolysis reaction, the mol ratio of distilled water and tri-n-butyl borate, both aluminium secondary butylates summation is 0.6: 1, and mixed hydrolysis makes solution C after reacting 0.5 hour;
(5), in solution C, add the measured Repone K of scale, Lanthanum trichloride and rare earth chloride in step (1), under vigorous stirring, hydrolysis reaction, after 2 hours, makes solution D;
(6), by after solution D sealing leave standstill 1 day, obtain the solution E of certain viscosity;
The preparation of film:
(7), solution E 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:
(8), the film that step (7) 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 hydrogenchloride high temperature Crystallizing treatment of film:
(9), the film that step (8) 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 hydrogenchloride cylinder valve is opened, pass into dry hydrogen chloride gas, with the speed of 50 DEG C per hour, progressively intensification stove is to 600-620 DEG C, and reaction treatment 2-5 hour at such a temperature, reaction treatment terminates, close hydrogen chloride gas, and with 50 DEG C of rate of temperature fall per hour, Slow cooling tube type resistance furnace is to room temperature, with hydrogen chloride gas residual in nitrogen purge pipeline, all remaining hydrogen chloride gas through pipeline tail end are reclaimed by sodium hydroxide solution, finally obtain containing rare earth ion doped K 2laCl 5the glass film of crystallite.
In described step (1), raw materials is made up of according to following mol ratio following substances: tri-n-butyl borate: aluminium secondary butylate: Repone K: Lanthanum trichloride: Cerium II Chloride=156: 30: 12: 6: 1.
In described step (1), raw materials is made up of according to following mol ratio following substances: tri-n-butyl borate: aluminium secondary butylate: Repone K: Lanthanum trichloride: Europium trichloride=156: 16: 22: 11: 3.
In described step (1), raw materials is made up of according to following mol ratio following substances: tri-n-butyl borate: aluminium secondary butylate: Repone K: Lanthanum trichloride: terbium chloride=156: 24: 16: 8: 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 muriate 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 muriate 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-temp chlorination hydrogen process, rare earth luminous ion easily enters K 2laCl 5lattice position in, obtain the rare earth ion doped and illumination effect of high density.
5, the hydrogenchloride drying treatment of high temperature impels the oxychloride in gel glass, oxyhydroxide and oxide compound etc. to convert muriate to, can carry out the dehydration reaction of muriate raw material, and effectively promotes and control K 2laCl 5generation.
Because this film glass matrix is B 2o 3-Al 2o 3, 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 2laCl 5the aluminium borate glass film material of crystallite, has superior scintillation properties, physical strength, thermal stability characteristics, overcomes K 2laCl 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 2laCl 5crystalline phase, obtained ion doping K 2laCl 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-temp chlorination hydrogen;
Fig. 2 be embodiment one excitation of X-rays containing Ce 3+ion doping K 2laCl 5the fluorescence spectrum of the glass film of crystallite;
Fig. 3 be embodiment two excitation of X-rays containing Eu 3+ion doping K 2laCl 5the fluorescence spectrum of the glass film of crystallite;
Fig. 4 be embodiment three excitation of X-rays containing Tb 3+ion doping K 2laCl 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 2laCl 5the preparation method of the glass film of crystallite, comprises following concrete steps:
(1), by raw materials in molar ratio: tri-n-butyl borate: aluminium secondary butylate: Repone K: Lanthanum trichloride: Cerium II Chloride=156: 30: 12: 6: 1, analytically pure each raw materials that total amount is 30 grams is taken, stand-by;
(2), the hydrolysis of tri-n-butyl borate: the tri-n-butyl borate of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and tri-n-butyl borate is 2.5: 1, add methyl ethyl diketone fast, the volume ratio of tri-n-butyl borate and methyl ethyl diketone is 0.8: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and tri-n-butyl borate is 0.6: 1, regulate its pH value to 4 ~ 5 with concentrated nitric acid, 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 carries out the stirring of strong magnetic power, progressively instills distilled water, the mol ratio of distilled water and aluminium secondary butylate is 0.6: 1, regulate its pH value to 4-5 with concentrated nitric acid, be hydrolyzed under room temperature reaction 1 hour, makes solution B;
(4), by solution B slowly join in solution A, after abundant mix and blend, then drip a certain amount of distilled water, carry out secondary hydrolysis reaction, the mol ratio of distilled water and tri-n-butyl borate, both aluminium secondary butylates summation is 0.6: 1, and mixed hydrolysis makes solution C after reacting 0.5 hour;
(5), in solution C, add the measured Repone K of scale, Lanthanum trichloride and Cerium II Chloride in step (1), under vigorous stirring, hydrolysis reaction, after 2 hours, makes solution D;
(6), by after solution D sealing leave standstill 1 day, obtain the solution E of certain viscosity;
(7), solution E 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;
(8), the film that step (7) 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;
(9), the film that step (8) 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 hydrogenchloride cylinder valve is opened, pass into dry hydrogen chloride gas, with the speed of 50 DEG C per hour, progressively intensification stove is to 600 DEG C, and reaction treatment 5 hours at such a temperature, reaction treatment terminates, close hydrogen chloride gas, and with 50 DEG C of rate of temperature fall per hour, Slow cooling tube type resistance furnace is to room temperature, with hydrogen chloride gas residual in nitrogen purge pipeline, all remaining hydrogen chloride gas through pipeline tail end are reclaimed by sodium hydroxide solution, finally obtain containing Ce 3+ion doping K 2laCl 5the 78B of crystallite 2o 3-15Al 2o 3-6K 2laCl 5-1CeCl 3system glass film.
Ce is contained to what prepare 3+ion doping K 2laCl 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 hydrochlorination: through processing XRD diffraction peak and the K of the sample obtained 2laCl 5the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and what therefore obtain is containing K 2laCl 5the glass film of crystallite.The Ce of excitation of X-rays 3+ion doping K 2laCl 5as shown in Figure 2, with compared with hydrogenchloride Crystallizing treatment, fluorescence intensity significantly strengthens the fluorescence spectrum of devitrified glass film, and fluorescence decay time is 44ns.
Embodiment two
Substantially identical with embodiment one, difference is in step (1), raw materials is according to following mol ratio: tri-n-butyl borate: aluminium secondary butylate: Repone K: Lanthanum trichloride: Europium trichloride=156: 16: 22: 11: 3, takes each raw materials 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 (8), 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 620 DEG C, and reaction treatment 2 hours at such a temperature, finally obtain containing Eu 3+ion doping K 2laCl 5the 78B of crystallite 2o 3-8Al 2o 3-11K 2laCl 5-3EuCl 3system glass film.
Eu is contained to what prepare 3+ion doping K 2laCl 5the glass film of crystallite carries out performance test, and the XRD figure of glass film after hydrochlorination is substantially identical with Fig. 1, and just intensity is different, and what therefore obtain is containing K 2laCl 5the glass film of crystallite.The Eu of excitation of X-rays 3+ion doping K 2laCl 5the B of crystallite 2o 3-Al 2o 3as shown in Figure 3, with compared with hydrogenchloride Crystallizing treatment, fluorescence intensity significantly strengthens the fluorescence spectrum of glass film.
Embodiment three
Substantially identical with embodiment one, difference is that in step (1), raw materials is according to following mol ratio: tri-n-butyl borate: aluminium secondary butylate: Repone K: Lanthanum trichloride: terbium chloride=156: 24: 16: 8: 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 (8), 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 610 DEG C, and reaction treatment 3 hours at such a temperature, finally obtain containing Tb 3+ion doping K 2laCl 5the 78B of crystallite 2o 3-12Al 2o 3-8K 2laCl 5-2TbCl 3system glass film.
Tb is contained to what prepare 3+ion doping K 2laCl 5the glass film of crystallite carries out performance test, and the XRD figure of glass film after hydrochlorination is substantially identical with Fig. 1, and just intensity is different, and what therefore obtain is containing K 2laCl 5the glass film of crystallite.The Tb of excitation of X-rays 3+ion doping K 2laCl 5the B of crystallite 2o 3-Al 2o 3as shown in Figure 4, with compared with hydrogenchloride Crystallizing treatment, fluorescence intensity significantly strengthens the fluorescence spectrum of glass film.

Claims (5)

1. containing rare earth ion doped K 2laCl 5the glass film of crystallite, is characterized in that Mole percent consists of: boron trioxide: 78mol%, aluminium sesquioxide: 8-15mol%, K 2laCl 5: 6-11mol%, rare earth chloride: 1-3mol%, wherein rare earth chloride is the one in Cerium II Chloride, Europium trichloride or terbium chloride.
2. as claimed in claim 1 containing rare earth ion doped K 2laCl 5the preparation method of the glass film of crystallite, is characterized in that comprising following concrete steps:
(1), by raw materials in molar ratio: tri-n-butyl borate: aluminium secondary butylate: Repone K: Lanthanum trichloride: rare earth chloride=156: 16-30: 12-22: 6-11: 1-3, and Repone K: the mol ratio of Lanthanum trichloride is 2: 1, rare earth chloride is the one in Cerium II Chloride, Europium trichloride or terbium chloride, take analytically pure each raw materials respectively, stand-by;
(2), the hydrolysis of tri-n-butyl borate: the tri-n-butyl borate of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and tri-n-butyl borate is 2.5: 1, add methyl ethyl diketone fast, the volume ratio of tri-n-butyl borate and methyl ethyl diketone is 0.8: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and tri-n-butyl borate is 0.6: 1, regulate its pH value to 4 ~ 5 with concentrated nitric acid, 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 carries out the stirring of strong magnetic power, progressively instills distilled water, the mol ratio of distilled water and aluminium secondary butylate is 0.6: 1, regulate its pH value to 4-5 with concentrated nitric acid, be hydrolyzed under room temperature reaction 1 hour, makes solution B;
(4), by solution B slowly join in solution A, after abundant mix and blend, then drip a certain amount of distilled water, carry out secondary hydrolysis reaction, the mol ratio of distilled water and tri-n-butyl borate, both aluminium secondary butylates summation is 0.6: 1, and mixed hydrolysis makes solution C after reacting 0.5 hour;
(5), in solution C, add the measured Repone K of scale, Lanthanum trichloride and rare earth chloride in step (1), under vigorous stirring, hydrolysis reaction, after 2 hours, makes solution D;
(6), by after solution D sealing leave standstill 1 day, obtain the solution E of certain viscosity;
(7), solution E dip-coating method is coated on clean glass substrate, the pull rate of glass substrate in solution E 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;
(8), the film that step (7) 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;
(9), the film that step (8) 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 hydrogenchloride cylinder valve is opened, pass into dry hydrogen chloride gas, with the speed of 50 DEG C per hour, progressively intensification stove is to 600-620 DEG C, and reaction treatment 2-5 hour at such a temperature, reaction treatment terminates, close hydrogen chloride gas, and with 50 DEG C of rate of temperature fall per hour, Slow cooling tube type resistance furnace is to room temperature, with hydrogen chloride gas residual in nitrogen purge pipeline, all remaining hydrogen chloride gas through pipeline tail end are reclaimed by sodium hydroxide solution, finally obtain containing rare earth ion doped K 2laCl 5the glass film of crystallite.
3. as claimed in claim 2 containing rare earth ion doped K 2laCl 5the 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: tri-n-butyl borate: aluminium secondary butylate: Repone K: Lanthanum trichloride: Cerium II Chloride=156: 30: 12: 6: 1.
4. as claimed in claim 2 containing rare earth ion doped K 2laCl 5the 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: tri-n-butyl borate: aluminium secondary butylate: Repone K: Lanthanum trichloride: Europium trichloride=156: 16: 22: 11: 3.
5. as claimed in claim 2 containing rare earth ion doped K 2laCl 5the 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: tri-n-butyl borate: aluminium secondary butylate: Repone K: Lanthanum trichloride: terbium chloride=156: 24: 16: 8: 2.
CN201510783077.5A 2015-11-16 2015-11-16 Glass film containing rare earth ion doped K2LaCl5 microcrystal and preparation method thereof Withdrawn CN105384345A (en)

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JPH05246727A (en) * 1992-02-12 1993-09-24 Hitachi Cable Ltd Production of glass waveguide
CN103011589A (en) * 2012-06-27 2013-04-03 温州大学 Sodium borosilicate glass doped with In2S3 quantum dots and preparation method thereof
CN103951217A (en) * 2014-05-08 2014-07-30 宁波大学 Rare-earth-ion-doped K2LaCl5 microcrystalline glass and preparation method thereof

Patent Citations (3)

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JPH05246727A (en) * 1992-02-12 1993-09-24 Hitachi Cable Ltd Production of glass waveguide
CN103011589A (en) * 2012-06-27 2013-04-03 温州大学 Sodium borosilicate glass doped with In2S3 quantum dots and preparation method thereof
CN103951217A (en) * 2014-05-08 2014-07-30 宁波大学 Rare-earth-ion-doped K2LaCl5 microcrystalline glass and preparation method thereof

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