CN107236540A - Europkium-activated orthosilicate flash luminous material of one class divalence and preparation method thereof and the application in X-ray detection - Google Patents
Europkium-activated orthosilicate flash luminous material of one class divalence and preparation method thereof and the application in X-ray detection Download PDFInfo
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- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
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Abstract
The invention discloses europkium-activated orthosilicate flash luminous material of a class divalence and preparation method thereof and the application in X-ray detection.Chemical composition expression formula is：Ba2‑x‑ySrxEuySiO4, x in formula, y is respectively Doped ions Sr2+, Eu2+Replace barium ions Ba in matrix2+Amount, span：0≤x≤1.9,0<y≤0.01.Such flash luminous material, matrix is a series of orthosilicate Ba of isomorphisms2‑xSrxSiO4, the centre of luminescence is bivalent rare earth europium ion Eu2+.Flash luminous material in the present invention is synthesized using high temperature solid-state method, and preparation technology is simple, and safe operation, condition is easily controlled.In view of such flash luminous material radiation light output is high, and the characteristic that chemical stability is good and fluorescence decay is fast, it is expected to be used to detect X-ray radiation as new flash luminous material.
Description
Technical field
The invention belongs to flash luminous material and sigmatron field of detecting.Swash more particularly, to a class divalent europium
Orthosilicate Ba living2-x-ySrxEuySiO4Flash luminous material preparation and its in the application of X-ray detection.
Background technology
Flash luminous material refers to：One class is by high energy particle (including uncharged particle such as X-ray, gamma-rays and powered
Particle such as α particles, β particles and) radiation after, these particles can be converted to the material of optical signal.People are to flashing material
Existing more than 100 years of material research, its be widely used in high-energy physics, safety inspection, geological exploration, environmental monitoring and nuclear medicine into
As etc. field, be one of core material in numerous technical fields.Flash luminous material requirement has radiation light output height, lights and decline
Subtract that fast, self-absorption is few, easily fabricated and performance is stable.Conventional flash luminous material mainly has BaF2, Bi4Ge3O12(BGO),
CdWO4, Lu2SiO5:Ce(LSO), Lu3Al5O12:Ce(LuAG), LuAlO3:Ce(LuAP), Lu2Si2O7:Ce(LPS),
LaCl3:Ce, SrI2:Eu and CsI:Tl etc., their radiation light output is between 8000-80000 (photons/MeV).But this
A little materials are there is also more or less weak point, such as (1) BaF2, BGO and CdWO4Radiate light output relatively low；(2) Lu sills
Due to its radiativity176Lu isotopes, and the longer twilight sunset of generally existing；(3) although LaCl3:Ce, SrI2:Eu, CsI:Tl
There is very high radiation light output Deng halide, but they the easily moisture absorption because that can not be exposed in air.Therefore study
New have a strong radiation light output, excellent stability and has the flash luminous material of very fast fluorescence decay concurrently for core thing
Reason and medical imaging, the development in the field such as port security inspection and industrial nondestructive testing are most important.
Alkaline earth orthosilicate (Ba, Sr)2SiO4With excellent chemical stability, it is not easy to the moisture absorption, when in atmosphere can be long
Between it is stable.When it is rare earth ion doped arrive its alkaline-earth metal case when, excellent luminescent properties can be obtained.Bivalent rare earth Eu2+Just
It is one of them, its luminous 5d-4f transition for being related to parity permission lights strong, quantum yield is high, and is widely studied and applies
In white light LEDs.(CN102899037 B;US7642708 B2) however, its radioluminescence property is but little affected by concern.It is general
For, Eu2+Radiation light output often compare Ce3+It is higher, and relative to CdWO4And CsI:Tl etc. has glimmering faster
Optical attenuation (usual hundreds of nanosecond).
Therefore, the present invention have developed the europkium-activated orthosilicate Ba of a class divalence2-x-ySrxEuySiO4Flash luminous material,
It is high that they have radiation light output concurrently, and stability is good and the features such as fast fluorescence decay.It has been inquired into the potential of X-ray detection simultaneously
Using.It is worth noting that, by regulating and controlling suitable Ba/Sr ratios, the light output of such flash luminous material can be significantly increased
Intensity, while its emission peak positions of controllable.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art to have radiation light output height there is provided a class, and stability is good, glimmering
The fast flash luminous material of optical attenuation.
Another object of the present invention is to provide the preparation method of above-mentioned flash luminous material.
The further object of the present invention is to provide the application that above-mentioned flash luminous material is detected in X-ray radiation.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：
The europkium-activated orthosilicate flash luminous material of one class divalence, its chemical composition expression formula is：Ba2-x-ySrxEuySiO4,
X in formula, y are respectively Doped ions Sr2+, Eu2+Replace matrix barium ions Ba2+Amount, span：0≤x≤1.9,0<y≤
0.01。
By regulating and controlling Ba/Sr ratio, the light output intensity of above-mentioned flash luminous material can be significantly increased, while controllable
Its emission peak positions.The flash luminous material, matrix is a series of orthosilicate Ba of isomorphisms2-xSrxSiO4, the centre of luminescence is two
Valency rare-earth europium ion Eu2+.Under excitation of X-rays, the radioluminescence wave-length coverage of sample is in 450-750 nm.By regulating and controlling Ba/
Sr ratio, glow color of the sample under X-ray radiation can be from green glow regulation and control to gold-tinted：I.e. as x=0,0.5,1.0,
When 1.5,1.9, its emission peak positions corresponds respectively to ~ 509,520,526,561 and 573 nm.Their light output intensity
Respectively commodity Lu3Al5O12:Ce3+The 0.68 of scintillator, 1.50,1.67,1.14,1.22 times, wherein
Ba0.9995SrEu0.0005SiO4Light output highest, reach ~ 30000 photons/MeV.In view of such flash luminous material light
Output is high, the good and relatively short fluorescence decay characteristic of chemical stability, and it is expected to be used to detect X as new scintillation material
Ray is radiated.
Above-mentioned flash luminous material is synthesized using high temperature solid-state method, and preparation technology is simple, and safe operation, condition is easily controlled
System.Comprise the following steps：
S1. according to the chemical composition embodied in chemical composition expression formula described in claim 1, raw material is accurately weighed, is fully ground
It is well mixed, obtain mixture；
S2. it is placed in after mixture is transferred in corundum crucible in horizontal pipe furnace, and after the roasting of reducing atmosphere high temperature, from
So it is cooled to room temperature；
S3. grind uniform after step S2 products therefroms take out, that is, obtain the flash luminous material of pistac.
Wherein, raw material described in step S1 is barium carbonate, strontium carbonate, silica and europium oxide.
Preferably, raw material described in step S1 is ground uniformly in alcohol solvent.
Furthermore it is preferred that being fully ground described in step S1 is fully ground in agate mortar or ball mill.
Preferably, roasting in reducing atmosphere is placed in described in step S2 and refers to the 10%H for being passed through mixing2/90%N2In reducing atmosphere
Roasting.
Furthermore it is preferred that calcination procedure described in step S2 is：With the times of 5 hours from room temperature to 1400 DEG C, and protect
Temperature 5 hours, then naturally cools to room temperature.
The application of above-mentioned flash luminous material also should be within protection scope of the present invention.Specifically refer in X-ray radiation
The application of field of detecting.
The invention has the advantages that：
（1）The flash luminous material of the present invention, by regulating and controlling suitable Ba/Sr ratios, can significantly increase its light output intensity,
And it is substantially better than commodity Lu3Al5O12:Ce3+Scintillator；
（2）The flash luminous material of the present invention, by regulating and controlling Ba/Sr ratio, its radioluminescence peak value can be in 509-573
Regulate and control in the range of nm；
（3）The flash luminous material of the present invention, with good chemical stability, is difficult deliquescence；
（4）The flash luminous material of the present invention, with comparatively faster fluorescence decay；
（5）Flash luminous material of the present invention, its process of preparing is simple, it is easy to accomplish, and cost is relatively low, extensive work
Industry has a extensive future.
Brief description of the drawings
Fig. 1 is Ba2-xSrxEu0.0005SiO4(x=0,0.5,1.0,1.5,1.9) 5 samples are in excitation of X-rays
Under radioluminescence spectrum, in addition commodity Lu3Al5O12:Ce3+Monocrystalline (LuAG:Ce SG) and powder (LuAG:Ce powder)
It is also depicted in as reference in Fig. 1.These spectrum are all to measure under the same conditions, and wherein X-ray is by equipped with tungsten anode
X-ray tube produce, operating voltage and electric current are respectively 90 kV and 5 mA.
Embodiment
The present invention is further illustrated below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention
Limit in any form.Unless stated otherwise, the reagent of the invention used, method and apparatus routinely try for the art
Agent, method and apparatus.
Unless stated otherwise, following examples agents useful for same and material are purchased in market.
Embodiment 1
Weigh barium carbonate (BaCO3) 1.1837 g, silica (SiO2) 0.1802 g, europium oxide (Eu2O3) 0.0003 g
Be placed in agate mortar grind 20 min it is well mixed after be fitted into corundum crucible, by corundum crucible load level tube furnace simultaneously
In 10%H2/90%N2Reducing atmosphere high temperature calcination, specific heating schedule is as follows：With the times of 5 hours from room temperature to
1400 DEG C, 5 hours are incubated, room temperature is then naturally cooled to.Sample taking-up grinding is obtained into product, its chemical composition expression formula
For：Ba1.9995Eu0.0005SiO4。
Embodiment 2
Weigh barium carbonate (BaCO3) 0.8877 g, strontium carbonate (SrCO3) 0.2214 g, silica (SiO2) 0.1802 g,
Europium oxide (Eu2O3) 0.0003 g be placed in agate mortar grind 20 min it is well mixed after be fitted into corundum crucible, by corundum
In crucible load level tube furnace and in 10%H2/90%N2Reducing atmosphere high temperature calcination, specific heating schedule is as follows：With 5
The time of hour, from room temperature to 1400 DEG C, is incubated 5 hours, then naturally cools to room temperature.Sample taking-up grinding is obtained
Product, its chemical composition expression formula is：Ba1.4995Sr0.5Eu0.0005SiO4。
Embodiment 3
Weigh barium carbonate (BaCO3) 0.5917 g, strontium carbonate (SrCO3) 0.4429 g, silica (SiO2) 0.1802 g,
Europium oxide (Eu2O3) 0.0003 g be placed in agate mortar grind 20 min it is well mixed after be fitted into corundum crucible, by corundum
In crucible load level tube furnace and in 10%H2/90%N2Reducing atmosphere high temperature calcination, specific heating schedule is as follows：With 5
The time of hour, from room temperature to 1400 DEG C, is incubated 5 hours, then naturally cools to room temperature.Sample taking-up grinding is obtained
Product, its chemical composition expression formula is：Ba0.9995SrEu0.0005SiO4。
Embodiment 4
Weigh barium carbonate (BaCO3) 0.2957 g, strontium carbonate (SrCO3) 0.6643 g, silica (SiO2) 0.1802 g,
Europium oxide (Eu2O3) 0.0003 g be placed in agate mortar grind 20 min it is well mixed after be fitted into corundum crucible, by corundum
In crucible load level tube furnace and in 10%H2/90%N2Reducing atmosphere high temperature calcination, specific heating schedule is as follows：With 5
The time of hour, from room temperature to 1400 DEG C, is incubated 5 hours, then naturally cools to room temperature.Sample taking-up grinding is obtained
Product, its chemical composition expression formula is：Ba0.4995Sr1.5Eu0.0005SiO4。
Embodiment 5
Weigh barium carbonate (BaCO3) 0.0589 g, strontium carbonate (SrCO3) 0.8415 g, silica (SiO2) 0.1802 g,
Europium oxide (Eu2O3) 0.0003 g be placed in agate mortar grind 20 min it is well mixed after be fitted into corundum crucible, by corundum
In crucible load level tube furnace and in 10%H2/90%N2Reducing atmosphere high temperature calcination, specific heating schedule is as follows：With 5
The time of hour, from room temperature to 1400 DEG C, is incubated 5 hours, then naturally cools to room temperature.Sample taking-up grinding is obtained
Product, its chemical composition expression formula is：Ba0.0995Sr1.9Eu0.0005SiO4。
In the present invention, the flash luminous material obtained by embodiment 1-5 measures emission spectrum under excitation of X-rays,
And shown in Figure 1, the wherein Lu of commodity3Al5O12:Ce3+Monocrystalline (LuAG:Ce SG) and powder (LuAG:Ce powder) conduct
Reference.Under excitation of X-rays, the fluorescent wavelength ranges of electromagnetic radiation in 450-750 nm, most strong emission peak respectively be located at ~
509,520,526,561 and 573 nm, their light output intensity is respectively commodity Lu3Al5O12:Ce3+Scintillator
0.68,1.50,1.67,1.14,1.22 times, wherein Ba0.9995SrEu0.0005SiO4Light output highest, reach ~ 30000
photons/MeV。
Claims (6)
1. the europkium-activated orthosilicate flash luminous material of a class divalence, it is characterised in that its chemical constitution formula is：Ba2-x- ySrxEuySiO4, x in formula, y is respectively Doped ions Sr2+, Eu2+Replace barium ions Ba in matrix2+Amount, span：0≤x
≤ 1.9,0<y≤0.01；
The preparation method of flash luminous material described in claim 1, it is characterised in that comprise the following steps：
S1. according to the chemical composition embodied in chemical composition expression formula described in claim 1, raw material is accurately weighed, is fully ground
It is well mixed, obtain mixture；
S2. it is placed in after mixture is transferred in corundum crucible in horizontal pipe furnace, and after the roasting of reducing atmosphere high temperature, from
So it is cooled to room temperature；
S3. grind uniform after step S2 products therefroms take out, that is, obtain the flash luminous material of pistac.
2. preparation method as claimed in claim 2, it is characterised in that raw material described in step S1 is barium carbonate, strontium carbonate, dioxy
SiClx and europium oxide.
3. preparation method as claimed in claim 2, it is characterised in that raw material described in step S1 is ground in alcohol solvent
It is even；Described be fully ground is fully ground in agate mortar or ball mill.
4. preparation method as claimed in claim 2, it is characterised in that roasting in reducing atmosphere is placed in described in step S2 and refers to lead to
Enter the 10%H of mixing2/90%N2It is calcined in reducing atmosphere.
5. preparation method as claimed in claim 2, it is characterised in that calcination procedure described in step S2 is：With the time of 5 hours
From room temperature to 1400 DEG C, and 5 hours are incubated, then naturally cool to room temperature.
6. application of the flash luminous material described in claim 1 in detection X-ray radiation.
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| CN201710411174.0A CN107236540A (en) | 2017-06-05 | 2017-06-05 | Europkium-activated orthosilicate flash luminous material of one class divalence and preparation method thereof and the application in X-ray detection |
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| CN201710411174.0A CN107236540A (en) | 2017-06-05 | 2017-06-05 | Europkium-activated orthosilicate flash luminous material of one class divalence and preparation method thereof and the application in X-ray detection |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114774128A (en) * | 2022-03-09 | 2022-07-22 | 苏州大学 | Near-infrared scintillator of bivalent europium sulfide and preparation method thereof |
| CN116837461A (en) * | 2023-07-05 | 2023-10-03 | 国瑞科创稀土功能材料(赣州)有限公司 | Divalent europium ion activated aluminate scintillation crystal and preparation method thereof |
-
2017
- 2017-06-05 CN CN201710411174.0A patent/CN107236540A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| KRISTIN A. DENAULT: "Consequences of optimal bond valence on structural rigidity and improved luminescence properties in SrxBa2-xSiO4:Eu2+ orthosilicate phosphors", 《CHEMISTRY OF MATERIALS》 * |
| YETTA EAGLEMAN: "Investigation of Eu2+ doped barium silicates as scintillators", 《IEEE TRANSACTIONS ON NUCLEAR SCIENCE》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114774128A (en) * | 2022-03-09 | 2022-07-22 | 苏州大学 | Near-infrared scintillator of bivalent europium sulfide and preparation method thereof |
| CN114774128B (en) * | 2022-03-09 | 2023-06-27 | 苏州大学 | Divalent europium sulfide near infrared scintillator and preparation method thereof |
| CN116837461A (en) * | 2023-07-05 | 2023-10-03 | 国瑞科创稀土功能材料(赣州)有限公司 | Divalent europium ion activated aluminate scintillation crystal and preparation method thereof |
| CN116837461B (en) * | 2023-07-05 | 2024-02-06 | 国瑞科创稀土功能材料(赣州)有限公司 | Divalent europium ion activated aluminate scintillation crystal and preparation method thereof |
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