CN104926122A - Lithium silicate doped scintillating glass and preparation method thereof - Google Patents

Lithium silicate doped scintillating glass and preparation method thereof Download PDF

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CN104926122A
CN104926122A CN201510370304.1A CN201510370304A CN104926122A CN 104926122 A CN104926122 A CN 104926122A CN 201510370304 A CN201510370304 A CN 201510370304A CN 104926122 A CN104926122 A CN 104926122A
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glass
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corundum crucible
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crucible
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陈艳平
罗德礼
李强
王伟
谢金华
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Institute of Materials of CAEP
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Abstract

The objective of the invention is to provide scintillating glass with high fluorescent emission efficiency, and in particular to provide lithium silicate doped scintillating glass and a preparation method thereof. The chemical formula of the scintillating glass is A6MgAlD6O17.5:xCe or A6MgAlD6O17.5:yTb or A6MgAlD6O17.5:xCeyTb. According to the chemical formula, the A is one or any of Li, Na and K, the D is one or any of Si, B and P, wherein 0<x<=1.024 and 0<y<=0.16. It is determined that fluorescence emission efficiency of the A6MgAlD6O17.5:xCeyTb under excitation of X-ray and cathode ray is equivalent to 33.6% and 460% of that of Bi4Ge3O12 crystal, respectively. The glass can be used in the fields such as nuclear reactors, particle physics, radiation safety and cosmic ray detecting, can achieve thermal neutron detection, and has good application prospect. The invention also provides a preparation method of the glass. The method is completed via one-time casting by melting-quenching. The method has the advantages that glass scintillators of large sizes and various shapes can be prepared, the operability is high, and requirement for commercial large-scale production is met.

Description

A kind of elements doped lithium silicate scintillation glass and preparation method thereof
Technical field
The present invention relates to Material Field, especially rare earth ion doped scintillation material field, be specially a kind of elements doped lithium silicate scintillation glass and preparation method thereof.
Background technology
Scintillation material is the photoconductivity luminescent material that a kind of ionization energy by high-energy photon (X-ray, gamma-rays) or particle (neutron, electronics, proton, alpha-particle etc.) is converted into ultraviolet or optical photon, is a kind of energy transfer medium, also claims scintillator.Scintillator kind is a lot, according to chemical composition, can be divided into organic scintillator and inorganic scintillator; By crystalline state, crystal scintillator, glass scintillator and transparent ceramic scintillator can be divided into.
At present, the preparation method of glass scintillation material generally includes melt quenching method and sol-gel method, and these two kinds of methods are the main preparation methods being intended for scientific research, the industrial glass scintillator detected.Material prepared by sol-gel method has that component tolerance range is high, the feature of good uniformity, can obtain very pure glass material, be very suitable for the preparation of high melting temperature glass at far below the temperature of glass melting.And the thermal stability that melt-quenching method prepares, chemical stability are good, transparency is high, and Medium Culture pore, the microdefect such as to be mingled with few, and fluorescent emission efficiency is high.
In recent years, a large amount of research work mainly concentrates on batching, the casting forming technique of oxide compound composition, doping concentration of rare earth ion and the glass optimizing glass matrix, thus improves the fluorescent emission efficiency of material.For this reason, the invention provides a kind of elements doped lithium silicate scintillation glass with high-efficiency fluorescence emission efficiency and preparation method thereof.
Summary of the invention
Goal of the invention of the present invention is: provide a kind of scintillation glass with high fluorescent emission efficiency, is specially a kind of elements doped lithium silicate scintillation glass and preparation method thereof.Scintillation glass of the present invention has high-efficiency fluorescence emission efficiency, after measured, and A 6mgAlD 6o 17.5: xce ythe fluorescent emission efficiency of Tb under X-ray, cathode-ray exciting is equivalent to Bi respectively 4ge 3o 1233.6%, 460% of crystal, can be used for the fields such as nuclear reactor, particle physics, radiation safety, Millikan's rays detection.The present invention can also realize the detection to thermal neutron, has good application prospect.Simultaneously, the present invention also provides the preparation method of aforementioned scintillation glass, and the method is completed by melting-quenching method once-cast, can prepare the glass scintillator of large size, different shape, there is the advantage of strong operability, the needs that industrialization generates on a large scale can be met.
To achieve these goals, the present invention adopts following technical scheme:
A kind of elements doped lithium silicate scintillation glass, its chemical molecular formula is A 6mgAlD 6o 17.5: xce or A 6mgAlD 6o 17.5: ytb or A 6mgAlD 6o 17.5: xce ytb, in this chemical molecular formula, A is one or more in Li, Na, K, and D is one or more of Si, B, P, 0 < x≤1.024,0 < y≤0.16.
X is 0.001 ~ 1.024, y is 0.001 ~ 0.16.
0.0025≤x≤1.024，0.04≤y≤0.16。
Described A is 6li or D is 10b.
The preparation method of abovementioned dopant lithium silicates scintillation glass, comprises the steps:
(1) pre-treatment
Get raw material by chemical molecular formula atomic molar score another name, raw material is mixed through ball milling, after drying, obtain the first mixture;
(2) presintering
The first mixture obtained is placed in crucible, and by crucible at 900 ~ 1200 DEG C of calcining 3 ~ 6h, after cooling, presintering product is ground to powdery, obtains the second mixture;
(3) melting
Prepare large corundum crucible, little corundum crucible that energy is nested, little corundum crucible is placed in large corundum crucible, and places nano-carbon powder between little corundum crucible and large corundum crucible, then large corundum crucible is heated to 1200 ~ 1600 DEG C, constant temperature 1 ~ 5h, obtains glass metal;
(4) cast, anneal
After step 3 completes, the glass metal obtained is cast in mould, then the foliated glass cycle annealing 1 ~ 4h at 400 ~ 620 DEG C will obtained in mould, be then cooled to room temperature, obtain glass sample.
In described step 1, A is one or more in Li, Na, K, D is one or more of Si, B, P, 0 < x≤1.024,0 < y≤0.16, A raw material is the oxide compound of A or its carbonate or its nitrate, Mg raw material is the oxide compound of Mg or its carbonate or its nitrate, Al raw material is oxide compound or its nitrate of Al, D raw material is the oxide compound of D or sour or ammonium salt, Ce raw material is oxide compound or the nitrate of Ce, and Tb raw material is oxide compound or the nitrate of Tb.
A raw material adopts Li 2o, Na 2o, K 2o, Li 2cO 3, Na 2cO 3, K 2cO 3, LiNO 3, NaNO 3, KNO 3in one or more, Mg raw material adopt MgO, 4MgCO 3mg (OH) 25H 2one or more in O, Al raw material adopts Al 2o 3or Al (NO 3) 39H 2o, D adopt SiO 2or B 2o 3or H 3bO 3or P 2o 5or (NH 4) 2hPO 4or (NH 4) H 2pO 4in one or more, Ce raw material adopt CeO 2or Ce (NO 3) 36H 2o, Tb raw material adopts Tb 4o 7or Tb (NO 3) 35H 2o.
In described step 1, after being mixed by the raw material taken, put into planetary ball mill and carry out ball milling, adopt dehydrated alcohol as medium, the material after ball milling is even is dry in air atmosphere, obtains the first mixture.
Material after ball milling is even is dry in air atmosphere, and drying temperature is 100 ~ 150 DEG C, and time of drying is 1 ~ 10h, obtains the first mixture.
In described step 1, adopt agate grinding pot, agate ball as the ball-milling medium of planetary ball mill.
In described step 2, the first mixture obtained is placed in high-purity corundum crucible, and crucible is put into the inherent 1000 DEG C of calcining at constant temperature 4h of retort furnace, after cooling, presintering product agate mortar is ground to powdery, obtains the second mixture.
In described step 3, little corundum crucible is placed in large corundum crucible, and places nano-carbon powder between little corundum crucible and large corundum crucible, then after large corundum crucible being added a cover corundum ceramic piece, put into silicon molybdenum rod furnace and be heated to 1550 ~ 1600 DEG C, constant temperature 2 ~ 3h, obtains glass metal.
Described mould is stainless steel mould.
In described step 4, after step 3 completes, large corundum crucible is taken out, and glass metal in little corundum crucible is wherein cast in mould, again the foliated glass obtained in mould is transferred in electrical heater, at 580-620 DEG C, constant temperature 2 ~ 3h carries out anneal, is then cooled to room temperature, obtains glass sample.
Also comprise the steps:
(5) aftertreatment
Step 4 is obtained glass sample and is cut to desired size, through abrasive paper for metallograph polishing, after diamond paste polishing, obtain the glass scintillator detected for optical property.
The goal of the invention of the application is to provide a kind of elements doped lithium silicate scintillation glass and preparation method thereof, and this scintillation glass has high fluorescent emission efficiency.In the present invention, the molecular formula of elements doped lithium silicate scintillation glass is A 6mgAlD 6o 17.5: xce or A 6mgAlD 6o 17.5: ytb or A 6mgAlD 6o 17.5: xce ytb, wherein, A is one or more in Li, Na, K, D is Si(silicon), B(boron), P(phosphorus) one or more, 0 < x≤1.024,0 < y≤0.16, further, 0.0025≤x≤1.024,0.04≤y≤0.16.
After measured, scintillation glass of the present invention under UV-light, X-ray and cathode-ray exciting, its fluorescence distribution of launching at UV-blue to the wider scope of ruddiness (300nm ~ 650nm), wherein, A 6mgAlD 6o 17.5: xce ythe fluorescent emission efficiency of Tb under X-ray, cathode-ray exciting is equivalent to Bi respectively 4ge 3o 1233.6%, 460% of crystal.Compared with other scintillation material such as crystal etc., rare earth ion doped glass scintillation material of the present invention has shorter fall time (ns magnitude) and the feature of higher photoyield concurrently.Meanwhile, scintillation glass homogeneity of structure of the present invention is good, can pour into different shape, is easy to realize in enormous quantities, large size suitability for industrialized production; Scintillation glass of the present invention is drawn into glass fibre, the position resolution of detectable signal can be improved significantly.To sum up, scintillation glass of the present invention has the rare earth ion (Ce of short fall time, high photoyield 3+, Tb 3+) ion doping, have broad application prospects and major and immediate significance.
Further, A is 6li or D is 10b.The present invention in scintillation glass matrix, can introduce thermal neutron absorption cross section larger 6li, 10b nucleic, can realize the detection for thermal neutron.
The present invention also provides a kind of preparation method of abovementioned dopant lithium silicates scintillation glass, the method completes the preparation of scintillation glass by melting-quenching method once-cast, workable, the glass scintillator of large size, different shape can be prepared, the fields such as nuclear reactor, particle physics, radiation safety, Millikan's rays detection can be widely used in, there is good application prospect.
Further, in the present invention, adopt agate ball, agate tank as grinding medium, can avoid introducing other impurity any, significantly improve the homogeneity of glass, shape stability, transparency.In step 1, raw mixture is using dehydrated alcohol, agate ball, agate grinding pot as grinding medium, and after planetary ball mill mixes, then in air atmosphere, 120 DEG C of constant temperature 2h are dried, and obtain the first mixture.In step 4, fully melt until raw material powder, glass metal evenly after, the glass metal obtained is cast in the stainless steel mould of preheating, then the foliated glass obtained is proceeded to rapidly in the electrical heater of preheated accurate temperature controlling, 600 DEG C of constant temperature 2 ~ 3h anneal, eliminate the internal stress formed in glass casting cycle; Then slow cooling is to room temperature, obtains glass sample.After obtaining glass sample, adopt diamond metal composite saw blade that glass sample is cut to desired size, polish step by step through 500#, 800#, 1000#, 1200# abrasive paper for metallograph again, then adopt granularity to be about the diamond paste polishing of 5 μm, obtain the glass scintillator that can be used for optical property detection.
To sum up, the present invention prepares scintillation glass by Ce, Tb codoped, this scintillation glass is the trivalent rare earth ions co-doped material that a class has high-efficiency fluorescence emission efficiency, can be used for the fields such as nuclear reactor, particle physics, radiation safety, Millikan's rays detection, has good application prospect.Meanwhile, the present invention is also for the preparation of efficient rear-earth-doped luminous material, scintillation material provides important references.
Accompanying drawing explanation
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein:
Fig. 1 is Li when doping x is different value in embodiment 1 6mgAlSi 6o 17.5: the XRD figure spectrum of xCe scintillation glass.
Fig. 2 is Li when doping y is different value in embodiment 2 6mgAlSi 6o 17.5: the XRD figure spectrum of yTb scintillation glass.
Fig. 3 is Li in embodiment 3 6mgAlSi 6o 17.5: 0.06Ce sample, Li 6mgAlSi 6o 17.5: 0.08Tb sample, Li 6mgAlSi 6o 17.5: the XRD figure spectrum of 0.06Ce0.08Tb sample.
Fig. 4 is typical Ce in (two) experimental data (2) 3+doping, Tb 3+doping, Ce 3+/ Tb 3+codoped Li 6mgAlSi 6o 17.5scintillation glass and Bi 4ge 3o 12the fluorescence emission spectrum of crystal under ultraviolet excites.
Fig. 5 is that ultraviolet excites lower luminous glass sample figure.
Fig. 6 is Li in (two) experimental data (3) 6mgAlSi 6o 17.5: 0.06Ce sample, Li 6mgAlSi 6o 17.5: 0.08Tb sample, Li 6mgAlSi 6o 17.5: 0.06Ce0.08Tb sample, Bi 4ge 3o 12the fluorescence emission spectrogram of crystal under cathode-ray exciting.
Fig. 7 is Li in (two) experimental data (4) 6mgAlSi 6o 17.5: 0.06Ce sample, Li 6mgAlSi 6o 17.5: 0.08Tb sample, Li 6mgAlSi 6o 17.5: 0.06Ce0.08Tb sample, Bi 4ge 3o 12utilizing emitted light spectrogram under the excitation of X-rays of crystal.
Embodiment
All features disclosed in this specification sheets, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Arbitrary feature disclosed in this specification sheets, unless specifically stated otherwise, all can be replaced by other equivalences or the alternative features with similar object.That is, unless specifically stated otherwise, each feature is an example in a series of equivalence or similar characteristics.
Embodiment 1
Ce 3+doping scintillation glass Li 6mgAlSi 6o 17.5: xCe(x=0.0025,0.025,0.06,0.08,0.089,0.1,0.512,1.024) preparation, concrete steps are as follows.
(1) according to scintillation glass Li 6mgAlSi 6o 17.5: xCe(x=0.0025,0.025,0.06,0.08,0.089,0.1,0.512,1.024) chemical formula, according to its mole metering ratio, take Li 2cO 3, MgO, Al 2o 3, SiO 2, CeO 2powder, and tentatively mix.
(2) powder step 1 be mixed to get adopts dehydrated alcohol, agate ball, agate tank as grinding medium, adopt that rotating speed is 300 revs/min, Ball-milling Time 30 minutes, the mode planetary ball mill of 12 minutes intermittent times 24 hours, obtain uniform color, dense thick mixture.This ball-milled mixtures is placed in air atmosphere together with ball grinder, and at 120 DEG C, constant temperature 5h is dried, and obtains dry mixture powder, i.e. the first mixture.
(3) the first mix powder step 2 prepared is inserted and is of a size of in the high-purity corundum crucible of φ 70mm × 80mm, and crucible is put into retort furnace, 1000 DEG C of calcining at constant temperature 4h in retort furnace, after cooling, take out product, and grind in agate mortar, until obtain even-grained raw material powder, i.e. the second mixture.
(4) large and small two high-purity corundum crucibles that preparation can be nested, second mixture is loaded in the little corundum crucible of φ 70mm × 80mm, then little corundum crucible is inserted in the large corundum crucible of φ 90mm × 110mm, appropriate high-purity nm carbon dust is placed in advance bottom large corundum crucible, corundum ceramic piece is added a cover on large corundum crucible surface, obtains nested crucible.Again nested crucible is proceeded in silicon molybdenum rod furnace, be warming up to 1550 DEG C by 5 ~ 10 DEG C/min of temperature rise rates, at 1550 DEG C of insulation 3h, obtain glass metal.
(5) fully melt until glass metal, evenly after, by the oven door opening of silicon molybdenum rod furnace, with long handle crucible tongs, large corundum crucible is taken out, immediately glass metal in little corundum crucible is cast in preheated stainless steel mould, then the sample obtained is proceeded to rapidly in the electrical heater of preheated accurate temperature controlling, anneal is carried out, to eliminate the internal stress formed in glass casting cycle at 600 DEG C of constant temperature 2 ~ 3h; Then, slow cooling, to room temperature, obtains glass sample.
(6) the glass sample cutting adopting diamond metal composite saw blade step 5 to be obtained, obtain being of a size of φ 20mm × 2mm chip sample, polish step by step through 500#, 800#, 1000#, 1200# abrasive paper for metallograph, then employing granularity is the diamond paste polishing of 5 μm, obtains being of a size of the glass scintillator that can be used for optical property and detect.
PE company LS55 spectrophotofluorometer is adopted to detect different concentration of Ce 3+ion doping scintillation glass Li 6mgAlSi 6o 17.5: xCe(x=0.0025,0.025,0.06,0.08,0.089,0.1,0.512,1.024) ultraviolet light induced emmission spectrum.When testing, setting excitation wavelength is 273nm, excites slit, launches slit and be respectively 8nm, 10nm, relatively with the group fluorescent emission intensity of sample under identical ultraviolet light source effect, obtain the Ce of the best in this oxide compound composition glass matrix 3+ion doping concentration.
Li when Fig. 1 gives doping x different value 6mgAlSi 6o 17.5: the XRD figure spectrum of xCe, yTb scintillation glass.
Embodiment 2
Tb 3+doping scintillation glass Li 6mgAlSi 6o 17.5: yTb(y=0.04,0.08,0.12,0.16) preparation
(1) according to scintillation glass Li 6mgAlSi 6o 17.5: yTb(y=0.04,0.08,0.12,0.16) chemical formula, according to its mole metering ratio, take Li 2cO 3, MgO, Al 2o 3, SiO 2, Tb 4o 7powder also tentatively mixes.
(2) powder step 1 be mixed to get adopts dehydrated alcohol, agate ball, agate tank as grinding medium, adopt that rotating speed is 300 revs/min, Ball-milling Time 30 minutes, the mode planetary ball mill of 12 minutes intermittent times 24 hours, obtain uniform color, dense thick mixture.The dense fused mixture obtained is placed in air atmosphere together with ball grinder, dries at 120 DEG C of constant temperature 5h, obtain dry mixture powder, be i.e. the first mixture.
(3) the first mixture step 2 prepared is placed in and is of a size of in the high-purity corundum crucible of φ 70mm × 80mm, and in retort furnace, 1000 DEG C of constant temperature 4h calcine, after cooling, take out product, and grind in agate mortar, until obtain even-grained powder, i.e. the second mixture.
(4) nested large and small two the high-purity corundum crucibles of energy are prepared, second mixture is loaded in the little corundum crucible of φ 70mm × 80mm, then little corundum crucible is inserted in the large corundum crucible of φ 90mm × 110mm, proper amount of nano carbon dust is placed in advance bottom large corundum crucible, corundum ceramic piece is added a cover on large corundum crucible surface, obtains nested crucible.Then, nested crucible is proceeded in silicon molybdenum rod furnace, be warming up to 1550 DEG C with the temperature rise rate of 5 ~ 10 DEG C/min, at 1550 DEG C of insulation 3h, obtain glass metal.
(5) fully melt until glass metal, evenly after, by the oven door opening of silicon molybdenum rod furnace, with long handle crucible tongs, large corundum crucible is taken out, immediately glass metal in little corundum crucible is cast in preheated stainless steel mould, then the sample obtained is proceeded to rapidly in the electrical heater of preheated accurate temperature controlling, anneal is carried out, to eliminate the internal stress formed in glass casting cycle at 600 DEG C of constant temperature 2 ~ 3h; Then, slow cooling, to room temperature, obtains glass sample.
(6) adopt diamond metal composite saw blade to be cut by glass sample obtained in the previous step, obtain being of a size of φ 20mm × 2mm chip sample, through 500 #, 800 #, 1000 #, 1200 #abrasive paper for metallograph is polished step by step, and then employing granularity is the diamond paste polishing of 5 μm, obtains being of a size of the glass scintillator that can be used for optical property and detect.
Jobin Yvon company FLUOROLOG-3-TAU steady-state fluorescence spectrograph is adopted to detect different concns Tb 3+ion doping scintillation glass Li 6mgAlSi 6o 17.5: yTb(y=0.04,0.08,0.12,0.16) ultraviolet light induced emmission spectrum.Test time, setting excitation wavelength is 273nm, excite slit, transmitting slit be respectively 8nm, 10nm, obtain typical Tb 3+the emission spectrum characteristics of ion doping Lithium silicate glass, relatively with the fluorescent emission intensity of group sample under identical ultraviolet light source effect, obtains Tb best in this oxide compound composition glass matrix 3+ion doping concentration.
Li when Fig. 2 gives doping y different value 6mgAlSi 6o 17.5: the XRD figure spectrum of yTb scintillation glass.
Embodiment 3
Ce 3+, Tb 3+codoped scintillation glass Li 6mgAlSi 6o 17.5: xce ytb(x=0.06, y=0.04,0.08,0.12) preparation
(1) according to scintillation glass Li 6mgAlSi 6o 17.5: xce ytb(x=0.06, y=0.04,0.08,0.12) chemical formula, according to its mole of metering ratio, takes Li 2cO 3, MgO, Al 2o 3, SiO 2, CeO 2, Tb 4o 7powder also tentatively mixes.
(2) powder step 1 be mixed to get adopts dehydrated alcohol, agate ball, agate tank as grinding medium, adopt that rotating speed is 300 revs/min, Ball-milling Time 30 minutes, the mode of 12 minutes intermittent times, planetary ball mill 24 hours, obtains uniform color, dense thick mixture.The dense fused mixture obtained is placed in air atmosphere together with ball grinder, dries at 120 DEG C of constant temperature 5h, obtain dry mixture powder, be i.e. the first mixture.
(3) the first mixture step 2 prepared is placed in and is of a size of in the high-purity corundum crucible of φ 70mm × 80mm, and high-purity corundum crucible is put into retort furnace, in retort furnace, 1000 DEG C of constant temperature 4h calcine, after cooling, take out product, and grind in agate mortar, until obtain even-grained powder, i.e. the second mixture.
(4) nested large and small two the high-purity corundum crucibles of energy are prepared, second mixture is loaded in the little corundum crucible of φ 70mm × 80mm, then little corundum crucible is inserted in the large corundum crucible of φ 90mm × 110mm, proper amount of nano carbon dust is placed in advance bottom large corundum crucible, corundum ceramic piece is added a cover on large corundum crucible surface, obtains nested crucible.Then, nested crucible is proceeded in silicon molybdenum rod furnace, be warming up to 1550 DEG C with the temperature rise rate of 5 ~ 10 DEG C/min, at 1550 DEG C of insulation 3h, obtain glass metal.
(5) fully melt until glass metal, evenly after, by the oven door opening of silicon molybdenum rod furnace, with long handle crucible tongs, large corundum crucible is taken out, immediately glass metal in little corundum crucible is cast in preheated stainless steel mould, then the sample obtained is proceeded to rapidly in the electrical heater of preheated accurate temperature controlling, anneal is carried out, to eliminate the internal stress formed in glass casting cycle at 600 DEG C of constant temperature 2 ~ 3h; Then, slow cooling, to room temperature, obtains glass sample.
(6) diamond metal composite saw blade is adopted to be cut by glass sample obtained in the previous step, obtain being of a size of φ 20mm × 2mm chip sample, polish step by step through 500#, 800#, 1000#, 1200# abrasive paper for metallograph, then employing granularity is the diamond paste polishing of 5 μm, obtains being of a size of the glass scintillator that can be used for optical property and detect.
(2) experimental data
(1) by Li that embodiment 1, embodiment 2, embodiment 3 obtain 6mgAlSi 6o 17.5: 0.06Ce sample, Li 6mgAlSi 6o 17.5: 0.08Tb sample, Li 6mgAlSi 6o 17.5: 0.06Ce ,0.08Tb sample broke, grinding obtain the uniform powder being of a size of 150-200 μm, Dutch PANalytical company X ' Pert PRO type Multi-functional X ray diffractometer is adopted to carry out material phase analysis, obtain XRD figure spectrum as shown in Figure 3, result shows: be typical amorphous state feature, and the envelope peak at diffraction angle about 22.5 ° place corresponds to SiO 2crystalline phase.
(2) Jobin Yvon company FLUOROLOG-3-TAU steady-state fluorescence spectrograph is adopted to detect different concentration of Ce 3+, Tb 3+ion co-doped scintillation glass Li 6mgAlSi 6o 17.5: xCe, yTb(x=0.06, y=0.04,0.08,0.12) ultraviolet light induced emmission spectrum.When testing, setting excitation wavelength is 273nm, excites slit, launches slit and be respectively 8nm, 10nm, relatively with the group fluorescent emission intensity of sample under identical ultraviolet light source effect, obtain the Ce of the best in this oxide compound composition glass matrix 3+, Tb 3+ion doping concentration.The Li obtained 6mgAlSi 6o 17.5: 0.06Ce sample, Li 6mgAlSi 6o 17.5: 0.08Tb sample, Li 6mgAlSi 6o 17.5: the emmission spectrum of 0.06Ce, 0.08Tb sample under ultraviolet excites is as shown in Figure 4.
Wherein, Bi 4ge 3o 12crystal is bought from Shanghai silicate institute, lower same.In Fig. 4, X-coordinate is emission wavelength, and ordinate zou is luminous intensity.Fig. 5 is that ultraviolet excites lower fluorescent glass sample figure, is followed successively by Li from left to right 6mgAlSi 6o 17.5: 0.06Ce sample, Li 6mgAlSi 6o 17.5: 0.08Tb sample, Li 6mgAlSi 6o 17.5: 0.06Ce, 0.08Tb sample, Bi 4ge 3o 12crystal.
(3) the MonoCL3+ cathode-luminescence spectrograph of Quanta 400 FEG Flied emission environmental scanning electronic microscope configuration is adopted to detect Li 6mgAlSi 6o 17.5: 0.06Ce sample, Li 6mgAlSi 6o 17.5: 0.08Tb sample, Li 6mgAlSi 6o 17.5: 0.06Ce, 0.08Tb sample, Bi 4ge 3o 12the cathodoluminescence spectrum of crystal, as shown in Figure 6.Integration is made to the negative ray spectral radiation curves obtained, the Li prepared by contrast 6mgAlSi 6o 17.5: 0.06Ce sample, Li 6mgAlSi 6o 17.5: 0.08Tb sample, Li 6mgAlSi 6o 17.5: 0.06Ce, 0.08Tb sample and Bi 4ge 3o 12the size of crystal fluorescent emission efficiency under negative ray effect.
In Fig. 6, X-coordinate is emission wavelength, and ordinate zou is luminous intensity, and embedded form is emitting fluorescence integrated intensity (relative percentage).In Fig. 6, Li 6mgAlSi 6o 17.5: the integrated intensity of 0.06Ce sample is 60.47%, Li 6mgAlSi 6o 17.5: the integrated intensity of 0.08Tb sample is 23.42%, Li 6mgAlSi 6o 17.5: 0.06Ce, 0.08Tb sample integrated intensity be 100%, Bi 4ge 3o 12the integrated intensity of crystal is 21.59%.
(4) excitation of X-rays spectrophotofluorometer is adopted to detect Li 6mgAlSi 6o 17.5: 0.06Ce sample, Li 6mgAlSi 6o 17.5: 0.08Tb sample, Li 6mgAlSi 6o 17.5: 0.06Ce, 0.08Tb sample, Bi 4ge 3o 12emmission spectrum under the excitation of X-rays of crystal, as shown in Figure 7.The operating voltage of X-ray tube is 80kV, and electric current is 4mA, and measurement wavelength region is 220nm ~ 700nm.In Fig. 7, X-coordinate is emission wavelength, and ordinate zou is luminous intensity, and embedded form is emitting fluorescence integrated intensity (relative percentage).
Integration is made to the spectral radiation curves under the excitation of X-rays obtained, the Li prepared by contrast 6mgAlSi 6o 17.5: 0.06Ce sample, Li 6mgAlSi 6o 17.5: 0.08Tb sample, Li 6mgAlSi 6o 17.5: 0.06Ce, 0.08Tb sample and Bi 4ge 3o 12the size of crystal fluorescent emission efficiency under X-ray effect.In Fig. 7, Li 6mgAlSi 6o 17.5: the integrated intensity of 0.06Ce sample is 16.0%, Li 6mgAlSi 6o 17.5: the integrated intensity of 0.08Tb sample is 10.8%, Li 6mgAlSi 6o 17.5: 0.06Ce, 0.08Tb sample integrated intensity be 33.6%, Bi 4ge 3o 12the integrated intensity of crystal is 100%.
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature of disclosing in this manual or any combination newly, and the step of the arbitrary new method disclosed or process or any combination newly.

Claims (10)

1. an elements doped lithium silicate scintillation glass, is characterized in that, its chemical molecular formula is A 6mgAlD 6o 17.5: xce or A 6mgAlD 6o 17.5: ytb or A 6mgAlD 6o 17.5: xce ytb, in this chemical molecular formula, A is one or more in Li, Na, K, and D is one or more of Si, B, P, 0 < x≤1.024,0 < y≤0.16.
2. elements doped lithium silicate scintillation glass according to claim 1, it is characterized in that, x is 0.001 ~ 1.024, y is 0.001 ~ 0.16.
3. elements doped lithium silicate scintillation glass according to claim 1 or 2, is characterized in that, 0.0025≤x≤1.024,0.04≤y≤0.16.
4. elements doped lithium silicate scintillation glass according to any one of claim 1-3, it is characterized in that, described A is 6li or D is 10b.
5. the preparation method of elements doped lithium silicate scintillation glass according to any one of claim 1-4, is characterized in that, comprise the steps:
(1) pre-treatment
Get raw material by chemical molecular formula atomic molar score another name, raw material is mixed through ball milling, after drying, obtain the first mixture;
(2) presintering
The first mixture obtained is placed in crucible, and by crucible at 900 ~ 1200 DEG C of calcining 3 ~ 6h, after cooling, presintering product is ground to powdery, obtains the second mixture;
(3) melting
Prepare large corundum crucible, little corundum crucible that energy is nested, little corundum crucible is placed in large corundum crucible, and places nano-carbon powder between little corundum crucible and large corundum crucible, then large corundum crucible is heated to 1200 ~ 1600 DEG C, constant temperature 1 ~ 5h, obtains glass metal;
(4) cast, anneal
After step 3 completes, the glass metal obtained is cast in mould, then the foliated glass cycle annealing 1 ~ 4h at 400 ~ 620 DEG C will obtained in mould, be then cooled to room temperature, obtain glass sample.
6. preparation method according to claim 5, it is characterized in that, in described step 1, A is Li, Na, one or more in K, D is Si, B, one or more of P, 0 < x≤1.024, 0 < y≤0.16, A raw material is the oxide compound of A or its carbonate or its nitrate, Mg raw material is the oxide compound of Mg or its carbonate or its nitrate, Al raw material is oxide compound or its nitrate of Al, D raw material is the oxide compound of D or sour or ammonium salt, Ce raw material is oxide compound or the nitrate of Ce, Tb raw material is oxide compound or the nitrate of Tb.
7. preparation method according to claim 6, is characterized in that, A raw material adopts Li 2o, Na 2o, K 2o, Li 2cO 3, Na 2cO 3, K 2cO 3, LiNO 3, NaNO 3, KNO 3in one or more, Mg raw material adopt MgO, 4MgCO 3mg (OH) 25H 2one or more in O, Al raw material adopts Al 2o 3or Al(NO 3) 39H 2o, D adopt SiO 2or B 2o 3or H 3bO 3or P 2o 5or (NH 4) 2hPO 4or (NH 4) H 2pO 4in one or more, Ce raw material adopt CeO 2or Ce (NO 3) 36H 2o, Tb raw material adopts Tb 4o 7or Tb (NO 3) 35H 2o.
8. preparation method according to claim 5, it is characterized in that, in described step 2, the first mixture obtained is placed in high-purity corundum crucible, and crucible is put into the inherent 1000 DEG C of calcining at constant temperature 4h of retort furnace, after cooling, presintering product agate mortar is ground to powdery, obtains the second mixture.
9. preparation method according to any one of claim 5-8, it is characterized in that, in described step 3, little corundum crucible is placed in large corundum crucible, and nano-carbon powder is placed between little corundum crucible and large corundum crucible, after then large corundum crucible being added a cover corundum ceramic piece, put into silicon molybdenum rod furnace and be heated to 1550 ~ 1600 DEG C, constant temperature 2 ~ 3h, obtains glass metal.
10. preparation method according to any one of claim 5-9, is characterized in that, also comprise the steps:
(5) aftertreatment
Step 4 is obtained glass sample and is cut to desired size, through abrasive paper for metallograph polishing, after diamond paste polishing, obtain the glass scintillator detected for optical property.
CN201510370304.1A 2015-06-30 2015-06-30 Lithium silicate doped scintillating glass and preparation method thereof Pending CN104926122A (en)

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