CN108264234A - One kind is embedded with GYAGG：Flicker devitrified glass of Ce crystallite phases and preparation method thereof - Google Patents

One kind is embedded with GYAGG：Flicker devitrified glass of Ce crystallite phases and preparation method thereof Download PDF

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Publication number
CN108264234A
CN108264234A CN201810027780.7A CN201810027780A CN108264234A CN 108264234 A CN108264234 A CN 108264234A CN 201810027780 A CN201810027780 A CN 201810027780A CN 108264234 A CN108264234 A CN 108264234A
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glass
gyagg
mixture
crystallite
preparation
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阮健
田晨
张越鹏
韩建军
赵修建
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/10—Forming beads
    • C03B19/1005—Forming solid beads
    • C03B19/102—Forming solid beads by blowing a gas onto a stream of molten glass or onto particulate materials, e.g. pulverising
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/10—Forming beads
    • C03B19/1095—Thermal after-treatment of beads, e.g. tempering, crystallisation, annealing
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • 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
    • C03C12/00—Powdered glass; Bead compositions
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/16—Measuring radiation intensity
    • G01T1/20—Measuring radiation intensity with scintillation detectors
    • G01T1/202—Measuring radiation intensity with scintillation detectors the detector being a crystal
    • G01T1/2023—Selection of materials

Abstract

The present invention relates to one kind to be embedded with GYAGG：Flicker devitrified glass of Ce crystallite phases and preparation method thereof.The crystallite phase is GYAGG, active ions Ce3+Uniform Doped is in GYAGG crystallite phases, and GYAGG crystallite phases are uniformly distributed in devitrified glass is flickered；The cation mole of the flicker devitrified glass, which forms, is：Gd3+：3~26%, Y3+：0~23%, Al3+：58.4~68%, Ga3+：5~14.6%, Ce3+：0.2~1%；Wherein Gd3+And Y3+Molar content adds up to 26~27%.Preparation method includes the following steps：Frit mixing, frit tabletting prepare glass and heat treatment four steps of crystallization without container method or flame floating method.GYAGG prepared by the present invention：Ce devitrified glasses have Deliquescence-resistant, and Flouride-resistani acid phesphatase, long wavelength's reddish yellow light transmission rate is high, and passage of scintillation light luminescent properties are excellent.

Description

One kind is embedded with GYAGG：Flicker devitrified glass of Ce crystallite phases and preparation method thereof
Technical field
The present invention relates to scintillator luminescent materials, and in particular to one kind is embedded with GYAGG：The flicker devitrified glass of Ce crystallite phases And preparation method thereof.
Background technology
Scintillation material is a kind of can be sent out under the excitation of high-energy ray such as X ray, gamma-rays or other radioactive particles Go out the optical function material of visible ray, be widely used in nuclear medicine diagnostic, high-energy physics and nuclear physics experiment research, industry and ground The fields such as matter exploration.It is also not quite similar, but scintillation material under normal circumstances according to the different requirements to scintillator of application field Should have following properties：The features such as luminous efficiency is high, fluorescence decay is fast, density is larger, at low cost and radiation resistance is good.It is common Scintillator material have a scintillation crystal and scintillation glass, scintillation crystal generally has the resistance to irradiation, fast attenuation, High Light Output etc. excellent Point, but scintillation crystal there is also it is following serious the shortcomings that：Difficulty is prepared, it is expensive.And rare earth ion doped scintillation glass Although at low cost, large-size glass is easily prepared, it is in light output, number of repetition etc. hardly possible and crystal phase ratio, therefore it should With being also very limited.
Microcrystal glass material is a kind of hybrid material by the way that crystal grain is precipitated in continuous glass phase, if preceding It driving in body glass and adds in active ions, then active ions can be entered in crystal grain during crystal grain is grown, So as to show and adulterate luminescence feature as the crystal phase of identical active ions.Flicker devitrified glass possesses good glitter Energy and anti-radiation performance, and it is easy to large-scale industrial production, manufacture cost can be effectively reduced, before having a vast market Scape.The flicker devitrified glass patent that has been reported that at present is simultaneously few, and 105399334 A of Chinese invention patent CN disclose a kind of embedding There is GdTaO4Flicker devitrified glass of crystallite phase and preparation method thereof is put into fusing in platinum crucible and obtains glass after raw material is ground Glass solution, is poured that after annealing, heating obtains the flicker devitrified glass embedded with crystallite phase again by glass solution, wherein it is to adopt to pour The mode flattened with two pieces of copper coins, the microcrystal glass material transparency which inevitably results in preparation is poor, and Raw materials used Ta2O5Luminescent properties, than there is certain gap, limit its application as scintillation material with FAP crystal phases.
Cerium activated yttrium aluminium garnet (YAG：Ce3+) crystal has that luminous efficiency is high, decay of luminescence is fast, thermomechanical property is excellent The advantages that good, peak luminous wavelength is matched with the reception sensitive wavelength of common photomultiplier and silicon photo diode, is comprehensive Close the fast attenuation scintillation material of function admirable.YAG：Ce3+Monocrystal is suitable for detecting the light band electrochondria such as α particles, electronics and β rays Son, especially YAG：Ce3+Scintillation detector has in the fields such as electron microscope, β and x-ray count, electronics and x-ray imaging screen It is widely applied.102040337 A of Chinese invention patent CN disclose rare-earth-dopping yttrium aluminum garnet microcrystal glass material, The devitrified glass crystallinity and transmitance of preparation are low, its application is made to be only limitted to white light LEDs.
Gd and Ga is mixed into YAG structures and prepares embedded with GYAGG by the present invention simultaneously：The flicker crystallite glass of Ce crystallite phases Glass not only contributes to cation radius adaptation, while the density for increasing devitrified glass improves its resistance for high-energy ray Gear and absorbability, make (Gd, Y)3(Al, Ga)5O12：Ce(GYAGG：Ce) light output of crystal is relative to YAG：Ce has notable increasing Add, meanwhile, GYAGG：Ce devitrified glass X-ray radiationproof abilities get a promotion.
Invention content
The technical problems to be solved by the invention are for above-mentioned deficiency in the prior art, provide one kind and are embedded with GYAGG：Flicker devitrified glass of Ce crystallite phases and preparation method thereof, the flicker devitrified glass microcrystallization degree is high, whole clearing Property good, good luminous performance, while possess good processing performance.
In order to solve the above technical problems, technical solution provided by the invention is：
It provides a kind of embedded with GYAGG：The flicker devitrified glass of Ce crystallite phases, the crystallite phase be GYAGG, active ions Ce3+Uniform Doped is in GYAGG crystallite phases, and GYAGG crystallite phases are uniformly distributed in devitrified glass is flickered；
The cation mole of the flicker devitrified glass, which forms, is：
Gd3+：3~26%
Y3+：0~23%
Al3+：58.4~68%
Ga3+：5~14.6%
Ce3+：0.2~1%；
Wherein Gd3+And Y3+Molar content adds up to 26~27%.
By said program, the Gd3+Source is gadolinium oxide, GAG (Gd3Al5O12)、GGG(Gd3Ga5O12) in one kind or It is a variety of；The Y3+Source is yttrium oxide, YAG (Y3Al5O12) powder, YAlO3It is one or more in powder；The Al3+Source For aluminium oxide, YAG (Y3Al5O12) powder, YAlO3Powder, GAG (Gd3Al5O12) in it is one or more；The Ga3+Source is Gallium oxide, GGG (Gd3Ga5O12One or both of)；The Ce3+Source is oxide, fluoride, chloride or the nitre of cerium One kind in hydrochlorate.
GYAGG is embedded with the present invention also provides above-mentioned：The preparation method of the flicker devitrified glass of Ce crystallite phases, step is such as Under：
1) frit mixes：Raw material is weighed in proportion, and then raw material is placed in mortar and is fully ground mixing, is obtained uniform Glass mixture；
2) frit tabletting：Glass mixture obtained by step 1) is placed in mold, using electronic table tabletting machine, Obtain both bulk glasses mixture；
3) glass is prepared using no container method：Both bulk glasses mixture obtained by step 2) is placed in the nozzle of pneumatic suspension stove On, it is suspended in the air, is not in contact with any utensil with high-purity gas, after suspending stabilized, with laser to bulk Glass mixture, which carries out heating, makes its fusing, treats liquid glass material after mixing, laser is closed, stop heating it, Cooling obtains glass to liquid glass material rapidly；Or
Glass is prepared using the flame method of floating：The both bulk glasses mixture that step 2) suppresses is broken into required granularity, And pass through distributing device and equably put into it in beading stove, melting is heated in thermal-flame air-flow, is made in glass surface tension With the glomerate bead of lower shape, stop being heated with thermal-flame air-flow, cooling obtains glass to liquid glass material rapidly；
4) it is heat-treated crystallization：Glass obtained by step 3) is placed in Muffle furnace and is heat-treated, furnace cooling after heat treatment It is obtained to room temperature transparent embedded with GYAGG：Flicker devitrified glass (the GYAGG of Ce crystallite phases：Ce glass ceramics).
By said program, step 2) uses the pressure of electronic table tabletting machine as 10~30Mpa.
By said program, step 3) is described using no container method to be prepared glass and further includes and mix both bulk glasses obtained by step 2) It closes before material is placed in pneumatic suspension stove and passes through preheating, the specific steps are：Both bulk glasses mixture obtained by step 2) is packed into Crucible, then crucible is placed in Muffle furnace the pre-burning under air atmosphere, it is warming up to 1000 from room temperature with the rate of 2~20 DEG C/min ~1800 DEG C, 1~6 hour then is kept the temperature, finally cools to room temperature with the furnace.
By said program, time that step 3) is described to heat both bulk glasses mixture with laser be 3s~ 3min。
By said program, the step 3) time that melting is heated in thermal-flame air-flow is 3s~3min；The height The temperature of warm flame flow is 2000~2500K.
By said program, the step 4) heat treatment condition is：2~4h is kept the temperature at 700~1300 DEG C.
GYAGG is embedded with the invention also includes above-mentioned：The flicker devitrified glass of Ce crystallite phases should as X-ray detection material With.
By the present invention in that not needing to SiO in glass ingredient with no container method and flame floating method2、B2O3、P2O5Deng Glass network former, using only Gd2O3、Y2O3、Al2O3、Ga2O3Deng available for the component of GYAGG crystal is precipitated or directly uses GYAGG powders etc., so as to make the crystallinity of devitrified glass high.Meanwhile it is high just because of crystallinity, in grain growth, each other Mutual contention ion is so as to the uniformity for limiting the size of crystal grain and maintaining crystal grain distribution.
The present invention enables that glass can not be formed into the component of glass using conventional method by using no container freezing method, Its uniform crystallization is made by subsequent heat treatment, the high devitrified glass of transparency can be obtained.Since the devitrified glass is only with oxygen Change gadolinium, yttrium oxide, aluminium oxide, gallium oxide, YAG (Y3Al5O12) powder, YAlO3Powder, GAG (Gd3Al5O12)、GGG (Gd3Ga5O12) raw material as host glass, and it is also exactly the raw material for forming GYAGG, greatly improves its crystallization rate, thoroughly It crosses rate height and defect significantly reduces, so as to apply in X-ray detection scintillation material, this is conventional GYAGG：Ce devitrified glasses It can not realize.Host glass and GYAGG：The refractive index of Ce matches, and reduces and is scattered caused by refractive index mismatches.
The beneficial effects of the present invention are：What the 1st, prepared by the present invention is embedded with GYAGG：The flicker devitrified glass of Ce crystallite phases because It has a Deliquescence-resistant characteristic for high melting point glass, and it is whole it is uniform, transparency is high, Flouride-resistani acid phesphatase, long wavelength's reddish yellow light penetrates Rate is high, and flashing is had excellent performance.2nd, transparent glass is made by using no container method and flame floating method in the present invention, prepares Journey avoids contact and pollution of the crucible to material surface, inhibits heterogeneous forming core, and transparent glass is carried out hot place under Tg temperature Reason, the spontaneous precipitation GYAGG under the premise of not devitrification is ensured：Ce crystallites obtain transparent GYAGG：Ce devitrified glasses, prepared Journey does not need to addition SiO2、B2O3、P2O5Glass network formers are waited, so as to make the crystallinity of devitrified glass high.
Description of the drawings
Fig. 1 is the GYAGG prepared by the embodiment of the present invention 1：The XRD spectrum of Ce GC；
Fig. 2 is the GYAGG prepared by embodiment 1：The transmitance figure of Ce GC；
Fig. 3 is the GYAGG prepared by embodiment 1：The photoluminescence spectra (PL collection of illustrative plates) of Ce GC；
Fig. 4 is the GYAGG prepared by embodiment 1：The photo of Ce GC；
Fig. 5 is the GYAGG prepared by embodiment 1：Fluorescence emission spectrogram of compound of the Ce GC under excitation of X-rays；
Fig. 6 is the GYAGG prepared by embodiment 1：The high-resolution-ration transmission electric-lens photo of Ce GC.
Specific embodiment
For those skilled in the art is made to more fully understand technical scheme of the present invention, the present invention is made below in conjunction with the accompanying drawings into One step is described in detail.
The purity of powder material used in the embodiment of the present invention is 99.99%.
Embodiment 1
Prepare 8.71Y2O3-17.95Gd2O3-67.81Al2O3-4.99Ga2O3-0.54CeF3Transparent glass ceramics, it is specific to walk It is rapid as follows：
(1) frit mixes：By analytically pure Gd2O3、Y2O3、Al2O3、Ga2O3And CeF3By 8.71Y2O3- 17.95Gd2O3-67.81Al2O3-4.99Ga2O3-0.54CeF3Proportioning accurate weighing be placed in mortar, in agate mortar Mixing is fully ground, obtains uniform glass mixture；
(2) frit tabletting：Glass mixture is placed in mold, using electronic table tabletting machine, pressure is set 10Mpa obtains both bulk glasses mixture；
(3) frit pre-burning：Both bulk glasses mixture is packed into crucible, then crucible is placed in pre-burning in Muffle furnace, from room temperature 1600 DEG C are warming up to the rate of 5 DEG C/min, 1 hour is kept the temperature, finally cools to room temperature with the furnace and obtain block shape glass mixture；
(4) glass is prepared without container method：Block shape glass mixture is placed on the nozzle of pneumatic suspension stove, uses high-purity Ar Sample is suspended in the air by gas, is not in contact with any utensil；After suspending stabilized, CO is used2Laser adds sample Heat simultaneously makes its fusing, and keep 1min, treats liquid glass material after mixing, laser is closed, stop heating it；In wind Liquid glass material cools down rapidly under the action of cold, and glass is made；
(5) it is heat-treated crystallization：Glass obtained is placed in Muffle furnace and is heat-treated, setting muffle furnace is 930 DEG C, is protected The warm time is 2h, cools to room temperature with the furnace after heat preservation, obtains the transparent GYAGG of spontaneous crystallization：Ce glass ceramics.
Transparent GYAGG prepared by the embodiment of the present invention 1 as shown in Figure 1：The XRD spectrum of Ce devitrified glasses, shows GYAGG nanometers of crystalline phases have been precipitated in glass matrix.Sample surfaces measure it thoroughly by polishing with ultraviolet-visible spectrophotometer Cross rate (transmitance figure is as shown in Figure 2), it is seen that sample is more than 35% in 550-800nm wave bands its transmitances, and 430~ 475nm has strong absorption, corresponding with excitation peak.The transparent GYAGG obtained by Fluorescence Spectrometer measures the present embodiment：Ce crystallite glass Glass sample room temperature photoluminescence excitation and emission spectra are as shown in figure 3, in monitoring Ce3+In the excitation spectrum of ion 540nm transmittings, detection To corresponding to Ce3+：The blue wave band (excitation band of 400-500nm) of 4f → 5d transition；In the transmitting that 470nm and 484nm is excited In spectrum, occur corresponding to Ce3+：The strong yellow emission (centre wavelength 540nm) of 5d → 4f transition, with connecing for photomultiplier By Wavelength matched good.GYAGG：Ce devitrified glass photos are as shown in Figure 4.Its fluorescence emission spectrogram of compound under excitation of X-rays As shown in figure 5, dotted line represents the XEL spectral lines of standard BGO crystal, solid line represents the GYAGG prepared by the example：Ce devitrified glasses XEL spectral lines, transmitting peak intensity be higher than BGO crystal, it is seen that its flashing is had excellent performance.In addition, sample is irradiated by X-rays Without blackening, it can be seen that it with anti-radiation performance from this phenomenon later.It is illustrated in figure 6 saturating prepared by the present embodiment Bright GYAGG：Ce devitrified glass high-resolution-ration transmission electric-lens photos, it can be seen that the devitrified glass two phase structure different for contrast, greatly The nanocrystal of amount is distributed evenly in glass phase, and the size of crystal grain is about 5nm-10nm.
Embodiment 2
Prepare 8.71Y2O3-17.95Gd2O3-62.83Al2O3-9.97Ga2O3-0.54CeF3Transparent glass ceramics, it is specific to walk It is rapid as follows：
(1) frit mixes：Pure Gd will be analyzed2O3、Y2O3、Al2O3、Ga2O3And CeF3By 8.71Y2O3-17.95Gd2O3- 62.83Al2O3-9.97Ga2O3-0.54CeF3The proportioning accurate weighing of (molar ratio) is placed in mortar, is filled in agate mortar Divide ground and mixed, obtain uniform glass mixture；
(2) frit tabletting：Glass mixture is placed in mold, using electronic table tabletting machine, pressure is set 20Mpa obtains both bulk glasses mixture；
(3) glass is prepared without container method：Both bulk glasses mixture is placed on the nozzle of pneumatic suspension stove, with high-purity O2Gas Sample is suspended in the air, is not in contact with any utensil；After suspending stabilized, CO is used2Laser heats sample And make its fusing, and keep 1.5min, it treats liquid glass material after mixing, laser is closed, stop heating it；Liquid Frit cools down rapidly, and glass is made；
(4) it is heat-treated crystallization：Glass obtained is placed in Muffle furnace and is heat-treated, setting muffle furnace is 950 DEG C, is protected The warm time is 4h, cools to room temperature after heat preservation with the furnace and obtains the transparent GYAGG of spontaneous crystallization：Ce glass ceramics.
Embodiment 3
Prepare 8.71Y2O3-17.95Gd2O3-58.24Al2O3-14.56Ga2O3-0.54CeF3Transparent glass ceramics, specifically Step is as follows：
(1) frit mixes：Pure Gd will be analyzed2O3、Y2O3、Al2O3、Ga2O3And CeF3By 8.71Y2O3-17.95Gd2O3- 58.24Al2O3-14.56Ga2O3-0.54CeF3The proportioning accurate weighing of (molar ratio) is placed in mortar, is filled in agate mortar Divide ground and mixed, obtain uniform glass mixture；
(2) frit tabletting：Glass mixture is placed in mold, using electronic table tabletting machine, pressure is set 30Mpa obtains both bulk glasses mixture；
(3) frit pre-burning：Both bulk glasses mixture is packed into crucible, then crucible is placed in pre-burning in Muffle furnace, from room temperature 1500 DEG C are warming up to the rate of 5 DEG C/min, 3 hours is kept the temperature, finally cools to room temperature with the furnace and obtain block shape glass mixture；
(4) the flame method of floating prepares glass：Block shape glass mixture obtained by step (3) is broken into required granularity, and It is equably put into beading stove by distributing device, melting is heated in the thermal-flame air-flow of 2000K, in glass surface The lower glomerate bead of shape of power effect, stops being heated with thermal-flame air-flow, and cooling obtains glass to liquid glass material rapidly；
(5) it is heat-treated crystallization：Glass obtained is placed in Muffle furnace and is heat-treated, setting muffle furnace is 1000 DEG C, Soaking time is 4h, cools to room temperature after heat preservation with the furnace and obtains the transparent GYAGG of spontaneous crystallization：Ce glass ceramics.
Embodiment 4
Prepare 24.21Y2O3-2.11GGG-71.57Al2O3-2.11Ce(NO3)3Transparent glass ceramics is as follows：
(1) frit mixes：Pure Y will be analyzed2O3、Al2O3, GGG and Ce (NO3)3By 24.21Y2O3-2.11GGG- 71.57Al2O3-2.11Ce(NO3)3The proportioning accurate weighing of (molar ratio) is placed in mortar, is fully ground in agate mortar Mixing, obtains uniform glass mixture；
(2) frit tabletting：Glass mixture is placed in mold, using electronic table tabletting machine, pressure is set 30Mpa obtains both bulk glasses mixture；
(3) frit pre-burning：Both bulk glasses mixture obtained by step (2) is packed into crucible, then crucible is placed in Muffle furnace Middle pre-burning is warming up to 1800 DEG C from room temperature with the rate of 5 DEG C/min, keeps the temperature 5 hours, finally cool to room temperature with the furnace and obtain block Shape glass mixture；
(4) glass is prepared without container method：Block shape glass mixture is placed on the nozzle of pneumatic suspension stove, uses high-purity N2 Sample is suspended in the air by gas, is not in contact with any utensil；After suspending stabilized, CO is used2Laser adds sample Heat simultaneously makes its fusing, and keep 2min, treats liquid glass material after mixing, laser is closed, stop heating it；Liquid Frit cools down rapidly, and glass is made；
(5) it is heat-treated crystallization：Glass obtained is placed in Muffle furnace and is heat-treated, setting muffle furnace is 860 DEG C, is protected The warm time is 2h, cools to room temperature after heat preservation with the furnace and obtains the transparent GYAGG of spontaneous crystallization：Ce glass ceramics.
Embodiment 5
Prepare 25.74Gd2O3-67.33Al2O3-4.95Ga2O3-1.98CeCl3Transparent glass ceramics is as follows：
(1) frit mixes：Pure Gd will be analyzed2O3、Al2O3、Ga2O3And CeCl3By 25.74Gd2O3-67.33Al2O3- 4.95Ga2O3-1.98CeCl3The proportioning accurate weighing of (molar ratio) is placed in mortar, is fully ground in agate mortar mixed It closes, obtains uniform glass mixture；
(2) frit tabletting：Glass mixture is placed in mold, using electronic table tabletting machine, pressure is set 30Mpa obtains both bulk glasses mixture；
(3) the flame method of floating prepares glass：Both bulk glasses mixture obtained by step (2) is broken into required granularity, and lead to It crosses distributing device equably to put into it in beading stove, melting is heated in the thermal-flame air-flow of 2500K, in glass surface tension The lower glomerate bead of shape of effect, stops being heated with thermal-flame air-flow, and cooling obtains glass to liquid glass material rapidly；
(4) it is heat-treated crystallization：Glass obtained is placed in Muffle furnace and is heat-treated, setting muffle furnace is 1100 DEG C, Soaking time is 2h, cools to room temperature after heat preservation with the furnace and obtains the transparent GYAGG of spontaneous crystallization：Ce glass ceramics.

Claims (9)

1. one kind is embedded with GYAGG：The flicker devitrified glass of Ce crystallite phases, it is characterised in that：The crystallite phase is GYAGG, is activated Ion Ce3+Uniform Doped is in GYAGG crystallite phases, and GYAGG crystallite phases are uniformly distributed in devitrified glass is flickered；
The cation mole of the flicker devitrified glass, which forms, is：
Gd3+：3~26%
Y3+：0~23%
Al3+：58.4~68%
Ga3+：5~14.6%
Ce3+：0.2~1%；
Wherein Gd3+And Y3+Molar content adds up to 26~27%.
2. according to claim 1 be embedded with GYAGG：The flicker devitrified glass of Ce crystallite phases, it is characterised in that：The Gd3+ Source is gadolinium oxide, GAG (Gd3Al5O12)、GGG(Gd3Ga5O12) in it is one or more；The Y3+Source is yttrium oxide, YAG (Y3Al5O12) powder, YAlO3It is one or more in powder；The Al3+Source is aluminium oxide, YAG (Y3Al5O12) powder, YAlO3Powder, GAG (Gd3Al5O12) in it is one or more；The Ga3+Source is gallium oxide, GGG (Gd3Ga5O12) in one Kind or two kinds；The Ce3+Source is one kind in the oxide of cerium, fluoride, chloride or nitrate.
3. it is embedded with GYAGG described in a kind of claims 1 or 2：The preparation method of the flicker devitrified glass of Ce crystallite phases, feature It is that step is as follows：
1) frit mixes：Raw material is weighed in proportion, and then raw material is placed in mortar and is fully ground mixing, obtains uniform glass Glass mixture；
2) frit tabletting：Glass mixture obtained by step 1) is placed in mold, using electronic table tabletting machine, is obtained Both bulk glasses mixture；
3) glass is prepared using no container method：Both bulk glasses mixture obtained by step 2) is placed on the nozzle of pneumatic suspension stove, It is suspended in the air, is not in contact with any utensil with high-purity gas, after suspending stabilized, with laser to both bulk glasses Mixture, which carries out heating, makes its fusing, treats liquid glass material after mixing, laser is closed, stop heating it, liquid Cooling obtains glass to frit rapidly；Or
Glass is prepared using the flame method of floating：The both bulk glasses mixture that step 2) suppresses is broken into required granularity, and lead to It crosses distributing device equably to put into it in beading stove, melting is heated in thermal-flame air-flow, under glass surface tension effect The glomerate bead of shape stops being heated with thermal-flame air-flow, and cooling obtains glass to liquid glass material rapidly；
4) it is heat-treated crystallization：Glass obtained by step 3) is placed in Muffle furnace and is heat-treated, cools to room after heat treatment with the furnace Temperature obtains transparent embedded with GYAGG：The flicker devitrified glass of Ce crystallite phases.
4. preparation method according to claim 3, it is characterised in that step 2) using electronic table tabletting machine pressure Power is 10~30Mpa.
5. preparation method according to claim 3, it is characterised in that step 3) is described to prepare glass also using no container method Including passing through preheating before both bulk glasses mixture obtained by step 2) is placed in pneumatic suspension stove, the specific steps are：It will step Rapid 2) gained both bulk glasses mixture is packed into crucible, then crucible is placed in Muffle furnace the pre-burning under air atmosphere, from room temperature with 2 The rate of~20 DEG C/min is warming up to 1000~1800 DEG C, then keeps the temperature 1~6 hour, finally cools to room temperature with the furnace.
6. preparation method according to claim 3, it is characterised in that step 3) is described to mix both bulk glasses with laser It is 3s~3min to expect the time heated.
7. preparation method according to claim 3, it is characterised in that described heated in thermal-flame air-flow of step 3) is melted The time melted is 3s~3min；The temperature of the thermal-flame air-flow is 2000~2500K.
8. preparation method according to claim 3, it is characterised in that the step 4) heat treatment condition is：700~ 2~4h is kept the temperature at 1300 DEG C.
9. according to claim 1 or 2 be embedded with GYAGG：The flicker devitrified glass of Ce crystallite phases is as X-ray detection material Application.
CN201810027780.7A 2018-01-11 2018-01-11 One kind is embedded with GYAGG：Flicker devitrified glass of Ce crystallite phases and preparation method thereof Pending CN108264234A (en)

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CN111423128A (en) * 2020-05-11 2020-07-17 奕瑞新材料科技（太仓）有限公司 GGAG fluorescent glass ball and preparation method thereof
CN112723749A (en) * 2021-03-03 2021-04-30 哈尔滨工程大学 High-transparency microcrystalline glass containing scintillation nanocrystals and preparation method thereof
CN115710089A (en) * 2022-12-23 2023-02-24 景德镇陶瓷大学 Yellow semitransparent fluorescent glass ceramic and preparation method thereof

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CN111423128A (en) * 2020-05-11 2020-07-17 奕瑞新材料科技（太仓）有限公司 GGAG fluorescent glass ball and preparation method thereof
CN112723749A (en) * 2021-03-03 2021-04-30 哈尔滨工程大学 High-transparency microcrystalline glass containing scintillation nanocrystals and preparation method thereof
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