CN116814252A - X-ray storage luminescent material, preparation method and application - Google Patents
X-ray storage luminescent material, preparation method and application Download PDFInfo
- Publication number
- CN116814252A CN116814252A CN202311083712.XA CN202311083712A CN116814252A CN 116814252 A CN116814252 A CN 116814252A CN 202311083712 A CN202311083712 A CN 202311083712A CN 116814252 A CN116814252 A CN 116814252A
- Authority
- CN
- China
- Prior art keywords
- luminescent material
- ray storage
- storage luminescent
- barium
- iodide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000003384 imaging method Methods 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 20
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 18
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940107816 ammonium iodide Drugs 0.000 claims abstract description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 11
- 230000005855 radiation Effects 0.000 claims abstract description 8
- 239000011575 calcium Substances 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 25
- 238000005245 sintering Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 16
- MSQCWIHWHAEZLC-UHFFFAOYSA-N [Ba].BrF Chemical class [Ba].BrF MSQCWIHWHAEZLC-UHFFFAOYSA-N 0.000 claims description 12
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000002189 fluorescence spectrum Methods 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 6
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 claims description 5
- 229940075444 barium iodide Drugs 0.000 claims description 5
- 229910001638 barium iodide Inorganic materials 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 claims description 4
- 229910001620 barium bromide Inorganic materials 0.000 claims description 4
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 4
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 4
- 229910001940 europium oxide Inorganic materials 0.000 claims description 4
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- IRFHBCVRLKISOO-UHFFFAOYSA-N P.I.I.I Chemical compound P.I.I.I IRFHBCVRLKISOO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 22
- 230000005284 excitation Effects 0.000 abstract description 15
- IRFOGHALURZKLH-UHFFFAOYSA-N BrI.[Ba] Chemical compound BrI.[Ba] IRFOGHALURZKLH-UHFFFAOYSA-N 0.000 abstract description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 9
- 230000035945 sensitivity Effects 0.000 abstract description 7
- VGWVQHQITFLBJF-UHFFFAOYSA-K [I-].[Ba+2].[Br+].[F].[I-].[I-] Chemical compound [I-].[Ba+2].[Br+].[F].[I-].[I-] VGWVQHQITFLBJF-UHFFFAOYSA-K 0.000 abstract description 6
- -1 europium activated fluorine bromine barium iodide Chemical class 0.000 abstract description 4
- 230000001502 supplementing effect Effects 0.000 abstract description 4
- 208000012868 Overgrowth Diseases 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 241001289141 Babr Species 0.000 description 6
- 229910052788 barium Inorganic materials 0.000 description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 6
- 239000011232 storage material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910017855 NH 4 F Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PYSGNAVVCAQNNL-UHFFFAOYSA-N [Ba].[I].[Br].[F] Chemical compound [Ba].[I].[Br].[F] PYSGNAVVCAQNNL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- 238000010893 electron trap Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012856 weighed raw material Substances 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
- Conversion Of X-Rays Into Visible Images (AREA)
Abstract
The invention provides an X-ray storage luminescent material, a preparation method and application thereof, wherein the material is rare earth element europium activated fluorine bromine barium iodide fluorescent powder, and the chemical structure is Ba 1‑x‑y Ca y F（Br 1‑ z I z ）：xEu 2+ （0＜x≤0.1，0<y≤0.2，0<z.ltoreq.1). The invention successfully introduces Ca into the conventional barium bromoiodide fluoride 2+ So that the light excitation luminous intensity is higher than that of the conventional material (Ca is not introduced 2+ ) The enhancement is obvious. The material is used in the imaging plate for radiation imaging, and can greatly improve the sensitivity and the spatial resolution of the imaging plate. In addition, the invention successfully enters the crystal lattice of the fluorine bromine barium iodide crystal by the way of secondary roasting and supplementing gaseous ammonium iodide, thereby avoiding the overgrowth of crystal grains of the fluorine bromine barium iodide in the secondary roasting, preparing the fluorine bromine barium iodide with the grain size of 2-10 mu m, and further avoiding the application of the material in the field ofWhen the image plate is used, the spatial resolution of the image is low, the normalized signal to noise ratio is low, and the national standard requirement cannot be met.
Description
Technical Field
The invention relates to the technical field of optical storage luminescent materials, in particular to an X-ray storage luminescent material, a preparation method and application.
Background
At present, with the development of the information age, the optical storage luminescent material becomes a hot spot subject in the technical field of information storage, and is widely applied to industries such as medical treatment, industrial flaw detection, national defense field and the like. Wherein, the electron-trapping optical storage material which is widely used commercially is BaFBr: eu 2+ The imaging plate can be used in an imaging plate of a computer radiation imaging (CR), and has the advantages of high detection efficiency, low cost, repeated use, environmental protection, simple operation and the like compared with the traditional film imaging.
However, the main problem of the existing image plate is that the sensitivity and the spatial resolution are not high. This is mainly due to the electron-trapping optical storage material BaFBr: eu 2+ The light excitation luminous intensity of (2) is obviously insufficient.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an X-ray storage luminescent material, a preparation method and application thereof, wherein the storage luminescent material is rare earth element europium activated barium fluorobromide iodide fluorescent powder Ba 1-x-y Ca y F（Br 1-z I z ）：xEu 2+ （0＜x≤0.1，0<y≤0.2，0<z is less than or equal to 1), is fluorescent powder with high pulse laser (high density excitation) light excitation luminescence (PSL) intensity, and can greatly improve the space sensitivity and resolution of the image plate.
The specific invention comprises the following steps:
in a first aspect, the present invention provides an X-ray storageThe X-ray storage luminescent material is rare earth element europium activated barium fluorobromide iodide fluorescent powder, and the chemical structure of the fluorescent powder is Ba 1-x-y Ca y F（Br 1-z I z ）：xEu 2+ （0＜x≤0.1，0<y≤0.2，0<z≤1）。
Optionally, the rare earth element europium activated fluorine bromine barium iodide fluorescent powder has a chemical formula of Ba 0.95 Ca 0.05 F(Br 0.85 I 0.15 ):0.005Eu 2+ Or Ba (Ba) 0.9 Ca 0.1 F(Br 0.85 I 0.15 ):0.02Eu 2+ 。
Optionally, the broadband of the light-induced fluorescence emission spectrum of the X-ray storage luminescent material is 350-450nm;
the X-ray storage luminescent material has a pulse intensity of 2500-3000 a. U under the conditions that the exposure voltage is 50-70kV, the exposure current is 0.1mA, and the exposure time is 1-20 s.
Optionally, the particle diameter of the X-ray storage luminescent material is 2-10 micrometers.
In a second aspect, the present invention provides a method for preparing the X-ray storage luminescent material according to the first aspect, the method comprising the steps of:
s1, determining chemical structure Ba 1-x-y Ca y F(Br 1-z I z ):xEu 2+ The numerical values of x, y and z in the formula I are determined;
s2, determining the mass of raw materials of barium fluoride, calcium chloride, ammonium fluoride, barium bromide, barium iodide and europium oxide required by the reaction according to the determined chemical structural formula, weighing the raw materials, and grinding and uniformly mixing to obtain a mixed grinding body;
s3, transferring the mixed grinding body to an alumina crucible, and performing primary sintering to obtain a first sintered body;
s4, grinding the first sintered body into powder, adding ammonium iodide, grinding and mixing uniformly, transferring to an alumina crucible, and performing secondary sintering to obtain a second sintered body;
and S5, grinding the cooled second sintered body into powder to obtain the X-ray storage luminescent material.
Optionally, in step S3, the primary sintering is performed in a reducing atmosphere;
the temperature of the primary sintering is 600-900 ℃ and the time is 1-10 h.
Optionally, in step S4, the amount of ammonium iodide added is not more than 10% of the mass of the first sintered body.
Optionally, in step S4, the secondary sintering is performed in a reducing atmosphere;
the temperature of the secondary sintering is 600-900 ℃ and the time is 1-10 h.
In a third aspect, the present invention provides a use of the X-ray storage luminescent material of the first aspect described above in an imaging plate for radiation imaging.
Optionally, the X-ray storage luminescent material is subjected to particle size grading screening to obtain the X-ray storage luminescent material with the particle size of 5+/-2 mu m for coating the image plate.
Compared with the prior art, the invention has the following advantages:
the invention provides an X-ray storage luminescent material which is rare earth element europium activated fluorine bromine barium iodide fluorescent powder, and has a chemical structure of Ba 1-x-y Ca y F（Br 1-z I z ）：xEu 2+ （0＜x≤0.1，0<y≤0.2，0<z.ltoreq.1). The invention successfully introduces Ca into the conventional barium bromoiodide fluoride 2+ So that the light excitation luminous intensity is higher than that of the conventional material (Ca is not introduced 2+ ) The enhancement is obvious. The material is used in the imaging plate for radiation imaging, and can greatly improve the spatial sensitivity and resolution of the imaging plate.
The invention also provides a preparation method of the X-ray storage luminescent material, which ensures that the required calculated amount of iodine successfully enters the crystal lattice of the barium fluobromide-iodide crystal by means of secondary roasting and supplementing gaseous ammonium iodide, thereby avoiding the overlarge grain growth of the barium fluobromide-iodide in the secondary roasting, and preparing the barium fluobromide-iodide with the grain size of 2-10 mu m, and further avoiding the problems that the material has low image resolution and low normalized signal-to-noise ratio and cannot meet the national standard requirement when being applied to an image plate.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a flow chart of a preparation method of an X-ray storage luminescent material provided by an embodiment of the invention;
FIG. 2 shows a photo-induced fluorescence emission spectrum of an X-ray storage luminescent material provided by an embodiment of the invention;
fig. 3 shows a laser light excitation fluorescence pulse spectrum of an X-ray storage luminescent material provided by an embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. Any product that is the same as or similar to the present invention, which anyone in the light of the present invention or combines the present invention with other prior art features, falls within the scope of the present invention based on the embodiments of the present invention. And all other embodiments that may be made by those of ordinary skill in the art without undue burden and without departing from the scope of the invention.
Specific experimental steps or conditions are not noted in the examples and may be performed in accordance with the operation or conditions of conventional experimental steps described in the prior art in the field. The reagents used, as well as other instruments, are conventional reagent products available commercially, without the manufacturer's knowledge. Furthermore, the drawings are merely schematic illustrations of embodiments of the invention and are not necessarily drawn to scale. The same reference numerals in the drawings denote the same or similar parts, and thus a repetitive description thereof will be omitted. Some of the block diagrams shown in the figures are functional entities and do not necessarily correspond to physically or logically separate entities.
Techniques, methods, and apparatus known to one of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate.
In the description of the present invention, it should be understood that the terms "first," "second," and the like are used for defining the components, and are merely for convenience in distinguishing the corresponding components, and the terms are not meant to have any special meaning unless otherwise indicated, so that the scope of the present invention is not to be construed as being limited.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Before describing in detail an X-ray storage luminescent material, a preparation method and an application provided by the present invention, the following description is necessary for the related art:
the rare earth europium activated barium fluorobromide iodide crystal not only has common fluorescence emission, but also has light excitation luminescence property, and can be used for an X-ray storage luminescent material only because of the property. The working principle is that when the crystal is irradiated by rays with certain energy, a large number of electron/hole pairs are generated, so that a certain amount of photons are stored in the crystal in a metastable state, and when the crystal is subjected to light excitation with little energy, the stored photons are released in a light emitting form, and the phenomenon is called light excitation light emission (PSL for short).
Existing europium-activated barium bromoiodide fluoride BaF (BrI): eu 2+ As an optical storage material, there is still a problem that sensitivity and spatial resolution are not high for use in an image plate, which is caused by that the light-excitation light-emission starting luminance (light-excitation light-emission intensity) of the optical storage material is not high. Based onThe present invention is directed to the existing europium-activated barium bromoiodide fluoride BaF (BrI): eu 2+ Introduction of Ca into the Material 2+ Obtaining the chemical formula Ba 1-x-y Ca y F（Br 1-z I z ）：xEu 2+ （0＜x≤0.1，0<y≤0.2，0<z is less than or equal to 1). The material has the advantage of high light excitation luminous intensity, is used in an imaging plate for radiation imaging, and can greatly improve the sensitivity and the spatial resolution of the imaging plate. The specific implementation content is as follows:
in a first aspect, the invention provides an X-ray storage luminescent material, which is rare earth element europium activated barium fluorobromide iodide fluorescent powder, and has a chemical structure of Ba 1-x-y Ca y F（Br 1-z I z ）：xEu 2+ （0＜x≤0.1，0<y≤0.2，0<z≤1）。
In particular, the invention is based on the existing europium-activated barium bromoiodide fluoride BaF (BrI): eu 2+ The material has insufficient light-excitation luminous intensity, and is expected to be improved by introducing calcium ions (Ca 2+ ) To influence the crystal structure of barium fluorobromide iodide. Thus obtaining the fluorescent powder material of the barium bromoiodide fluoride with higher light excitation luminous intensity.
In practice, the ionic radius of calcium ions is about 1.00 a and the ionic radius of barium ions is about 1.35 a, which results in distortion of the crystal lattice (change in crystal structure) of the crystal, tending to form smaller crystal lattices, as calcium has a smaller ionic radius than barium, which results in the formation of a crystal of barium fluorobromide iodide. The particle diameter of the formed fluorine bromine iodine barium material is 2-10 mu m. The fluorescent property of the barium bromoiodide material provided by the invention is also changed under the influence of lattice distortion, and the broadband of the photoinduced fluorescence emission spectrum of the barium bromoiodide material is 350-450nm; the pulse intensity of the laser pulse spectrum is obviously improved.
In some embodiments, the rare earth element europium activated barium fluorobromide iodide phosphor may specifically have the chemical formula Ba 0.95 Ca 0.05 F(Br 0.85 I 0.15 ):0.005Eu 2+ Or Ba (Ba) 0.9 Ca 0.1 F(Br 0.85 I 0.15 ):0.02Eu 2+ 。
The invention successfully introduces Ca into the conventional barium bromoiodide fluoride 2+ So that the light excitation luminous intensity is higher than that of the conventional material (Ca is not introduced 2+ ) The enhancement is obvious. The material is used in the imaging plate for radiation imaging, and can greatly improve the sensitivity and the spatial resolution of the imaging plate.
In a second aspect, the present invention provides a method for preparing an X-ray storage luminescent material according to the first aspect, fig. 1 shows a flowchart of a method for preparing an X-ray storage luminescent material according to an embodiment of the present invention, and as shown in fig. 1, the method for preparing an X-ray storage luminescent material includes the following steps:
s1, determining chemical structure Ba 1-x-y Ca y F(Br 1-z I z ):xEu 2+ The numerical values of x, y and z in the formula I are determined;
s2, determining the mass of raw materials of barium fluoride, calcium chloride, ammonium fluoride, barium bromide, barium iodide and europium oxide required by the reaction according to the determined chemical structural formula, weighing the raw materials, and grinding and uniformly mixing to obtain a mixed grinding body;
s3, transferring the mixed grinding body to an alumina crucible, and performing primary sintering to obtain a first sintered body;
s4, grinding the first sintered body into powder, adding ammonium iodide, grinding and mixing uniformly, transferring to an alumina crucible, and performing secondary sintering to obtain a second sintered body;
and S5, grinding the cooled second sintered body into powder to obtain the X-ray storage luminescent material.
In specific implementation, the existing europium-activated barium bromoiodide fluoride BaF (BrI): eu 2+ The material is a typical inorganic material and is sensitive to moisture and oxygen in the air, which results in the existing europium activated barium bromoiodide fluoride BaF (BrI): eu 2+ During the preparation process, the obtained BaF (BrI) Eu is absorbed by moisture and oxygen 2+ The chemical stability and the thermal stability of the material are poor. The calcium doping (in the form of calcium chloride) plays a role in drying to a certain extent, and the interaction of the calcium chloride and the surrounding environment discharges the water in the reaction environment. And under sintering conditionsThe reaction products of the calcium chloride are formed by CaO and HCI, which provide acidic conditions for the reaction, thereby removing oxygen in the reaction environment and having the function of deoxidizing.
Further, since the ionic radius of calcium is smaller than that of barium, this causes the doping of calcium during sintering to change the lattice structure of the original barium fluorobromoiodide, the crystal lattice is distorted, resulting in the formation of lattice defects, and tends to be smaller. The particle diameter of the formed fluorine bromine iodine barium material is 2-10 mu m. The fluorescence performance of the barium bromoiodide material prepared by the invention is also changed under the influence of lattice distortion, and the broadband of the photoinduced fluorescence emission spectrum of the barium bromoiodide material is 350-450nm; the exposure parameters are exposure voltage: 50-70kV and exposure current: 0.1mA, exposure time: after exposure under the condition of 1-20s, the pulse intensity of the laser pulse spectrum of the fluorine bromine barium iodide material prepared by the invention is 2500-3000 a.u, and the light excitation luminous intensity is obviously improved.
In specific implementation, the invention firstly determines the specific chemical structural formula of the rare earth element europium activated fluorine bromine barium iodide fluorescent powder, namely, determines Ba 1-x-y Ca y F（Br 1-z I z ) The values of x, y and z in the formula (I) are calculated by the determined values of x, y and z, and barium fluoride, calcium chloride, ammonium fluoride, barium bromide, barium iodide and europium oxide are used as reaction raw materials to prepare Ba 1-x-y Ca y F（Br 1-z I z ) The amount and mass of each raw material are calculated according to the mole ratio.
Weighing the raw materials with calculated mass, grinding and mixing uniformly, transferring the mixed grinding body to an alumina crucible, and performing primary sintering at 600-900 ℃ for 1-10 h. The reaction raw materials form barium fluorobromide iodide crystals under the roasting condition, and in order to prevent oxidation reaction of the crystal surfaces in the process, the growth of the crystals needs to be carried out in a reducing atmosphere, and the reducing atmosphere can be provided by nitrogen/hydrogen or carbon monoxide gas so as to prevent oxidation of the crystal surfaces.
The invention is to test and try to get the first sintered body after roasting once, make it become powder, add ammonium iodide not more than 10% of the first sintered body mass into it, carry on secondary sintering, in order to realize the supplement of iodine. In consideration of overlarge crystal growth of the barium fluorobromide iodide caused by continuously supplementing solid barium iodide, the invention selects gaseous ammonium iodide as an iodine supplementing source so as to ensure that the grain size of the barium fluorobromide iodide formed after secondary roasting meets the use requirement of an image plate.
In particular, the secondary calcination also needs to be performed in a reducing atmosphere, which may be provided by nitrogen/hydrogen or carbon monoxide gas, to prevent oxidation of the crystal surface. The temperature of the secondary sintering is 600-900 ℃ and the time is 1-10 h.
In a third aspect, the present invention provides a use of the X-ray storage luminescent material of the first aspect described above in an imaging plate for radiation imaging.
In some embodiments, the X-ray storage luminescent material is subjected to particle size classification screening to obtain an X-ray storage luminescent material with a particle size of 5±2 μm for coating of the imaging plate.
The X-ray storage luminescent material prepared by the invention can be coated into high-quality image plates, and is used in the industries of medical treatment, industrial flaw detection, national defense field and the like, thereby realizing domestic substitution.
In order to make the present invention more clearly understood by those skilled in the art, the X-ray storage luminescent material, the preparation method and the application according to the present invention will now be described in detail by the following examples.
Example 1
First purchased BaBr 2 •2H 2 Baking the O raw material in an oven at 100-110 ℃ for 3 hours to obtain BaBr 2 •H 2 O，BaI 2 •2H 2 Baking the O raw material in a vacuum drying oven at 100-110 ℃ for 3 hours to obtain BaI 2 •H 2 O。
The chemical structure of the fluorine bromine barium iodide fluorescent powder is determined to be Ba 0.95 Ca 0.05 F(Br 0.85 I 0.15 ):0.005Eu 2+ According to the metering ratio of each element shown in the chemical formula, accurately weighing corresponding mol of BaF by using an electronic balance 2 、BaBr 2 •H 2 O、BaI 2 •H 2 O，Eu 2 O 3 And NH 4 F and a small amount of CaCl 2 Powder raw materials are put into an agate mortar, fully ground and uniformly mixed, put into an alumina crucible, baked for 5 hours in a high temperature of 840 ℃ in a CO reducing atmosphere in a furnace, and then naturally cooled to room temperature. And grinding the sintered body into powder, adding 1wet percent of ammonium iodide, grinding and mixing uniformly, placing into an alumina crucible, and roasting in a CO reducing atmosphere at 700 ℃ for 3 hours in a furnace to finally obtain the X-ray storage luminescent material. FIG. 2 shows a photo-induced fluorescence emission spectrum of an X-ray storage luminescent material provided by an embodiment of the invention; as shown in FIG. 2, the photo-induced fluorescence emission spectrum shows Eu 2+ Ion electron from 4f 7 Ground state direction 4f 6 5d 1 The energy level is transited, and the broadband of the light-induced fluorescence emission spectrum is 350-450nm.
Fig. 3 shows a laser light excitation fluorescence pulse spectrum of the X-ray storage luminescent material provided by the embodiment of the invention, as shown in fig. 3. Under the exposure condition that the exposure voltage of the X-ray is 70kV, the exposure current is 0.1mA and the exposure time is 6s, the X-ray storage luminescent material Ba provided by the invention 0.95 Ca 0.05 F(Br 0.85 I 0.15 ):0.005Eu 2+ (incorporation of CaCl) 2 ) With conventional optical storage materials BaF (Br) 0.85 I 0.15 ):0.005Eu 2+ (without CaCl incorporation) 2 ) There is a significant energy difference in the PSL (laser) pulse profile. Not incorporating CaCl 2 In this case, the pulse intensity of the PSL (laser) pulse spectrum is about 1800a.u; to incorporate CaCl 2 In this case, the pulse intensity of the PSL (laser) pulse spectrum is around 2900a.u; as can be seen, when BaF (BrI): eu 2+ Incorporating CaCl therein 2 After that, the light excitation luminous intensity of the sample is obviously enhanced, and the intensity is improved by about 1.6 times.
Example 2
First purchased BaBr 2 •2H 2 Baking the O raw material in an oven at 100-110 ℃ for 3 hours to obtain BaBr 2 •H 2 O，BaI 2 •2H 2 Baking the O raw material in a vacuum drying oven at 100-110 ℃ for 3 hours to obtain BaI 2 •H 2 O。
The chemical structure of the fluorine bromine barium iodide fluorescent powder is determined to be Ba 0.9 Ca 0.1 F(Br 0.85 I 0.15 ):0.02Eu 2+ According to the metering ratio of each element shown in the chemical formula, accurately weighing corresponding mol of BaF by using an electronic balance 2 、BaBr 2 •H 2 O、BaI 2 •H 2 O，Eu 2 O 3 And NH 4 F and a small amount of CaCl 2 Powder raw materials, putting the weighed raw materials into an agate mortar, fully grinding and uniformly mixing, putting into an alumina crucible, and putting into a furnace in N 2 /H 2 Roasting at 750 ℃ in a reducing atmosphere for 3 hours, and then naturally cooling to room temperature. Grinding the sintered body into powder, adding 5 wt% ammonium iodide, grinding, mixing, placing into aluminum oxide crucible, and adding into N in furnace 2 /H 2 Roasting for 3 hours at 600 ℃ in a reducing atmosphere to finally obtain the X-ray storage luminescent material.
The results of the photoluminescence emission spectrum and the laser photoluminescence pulse spectrum characterization of the X-ray storage luminescent material obtained in this example are substantially identical to those provided in example 1 and fig. 2 and 3, and are not repeated in this example.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, one skilled in the art can combine and combine the different embodiments or examples described in this specification.
For the purposes of simplicity of explanation, the methodologies are shown as a series of acts, but one of ordinary skill in the art will recognize that the present invention is not limited by the order of acts described, as some acts may, in accordance with the present invention, occur in other orders and concurrently. Further, those skilled in the art will recognize that the embodiments described in the specification are all of the preferred embodiments, and that the acts and components referred to are not necessarily required by the present invention.
The above description of the X-ray storage luminescent material, the preparation method and the application provided by the invention has been presented in detail, and specific examples are applied herein to illustrate the principles and embodiments of the invention, and the above examples are only used to help understand the method and core idea of the invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (10)
1. An X-ray storage luminescent material is characterized in that the X-ray storage luminescent material is rare earth element europium activated barium fluorobromide iodide fluorescent powder, and the chemical structure is Ba 1-x-y Ca y F（Br 1-z I z ）：xEu 2+ （0＜x≤0.1，0<y≤0.2，0<z≤1）。
2. The X-ray storage phosphor of claim 1, wherein said rare earth europium activated barium fluorobromide iodide phosphor has the formula Ba 0.95 Ca 0.05 F(Br 0.85 I 0.15 ):0.005Eu 2+ Or Ba (Ba) 0.9 Ca 0.1 F(Br 0.85 I 0.15 ):0.02Eu 2+ 。
3. The X-ray storage luminescent material according to claim 1, wherein the broadband of the photo-induced fluorescence emission spectrum of the X-ray storage luminescent material is 350-450nm;
the X-ray storage luminescent material has the pulse intensity of 2500-3000 a. U under the conditions that the exposure voltage is 50-70kV, the exposure current is 0.1mA and the exposure time is 1-20 s.
4. The X-ray storage luminescent material according to claim 1, wherein the particle diameter of the X-ray storage luminescent material is 2-10 μm.
5. A method for preparing an X-ray storage luminescent material as claimed in any one of the preceding claims 1-4, characterized in that the method comprises the steps of:
s1, determining chemical structure Ba 1-x-y Ca y F(Br 1-z I z ):xEu 2+ The numerical values of x, y and z in the formula I are determined;
s2, determining the mass of raw materials of barium fluoride, calcium chloride, ammonium fluoride, barium bromide, barium iodide and europium oxide required by the reaction according to the determined chemical structural formula, weighing the raw materials, and grinding and uniformly mixing to obtain a mixed grinding body;
s3, transferring the mixed grinding body to an alumina crucible, and performing primary sintering to obtain a first sintered body;
s4, grinding the first sintered body into powder, adding ammonium iodide, grinding and mixing uniformly, transferring to an alumina crucible, and performing secondary sintering to obtain a second sintered body;
and S5, grinding the cooled second sintered body into powder to obtain the X-ray storage luminescent material.
6. The X-ray storage luminescent material according to claim 5, wherein in step S3, the primary sintering is performed in a reducing atmosphere;
the temperature of the primary sintering is 600-900 ℃ and the time is 1-10 h.
7. The X-ray storage luminescent material according to claim 5, wherein in step S4, the addition amount of ammonium iodide is not more than 10% by mass of the first sintered body.
8. The X-ray storage luminescent material according to claim 5, wherein in step S4, the secondary sintering is performed in a reducing atmosphere;
the temperature of the secondary sintering is 600-900 ℃ and the time is 1-10 h.
9. Use of an X-ray storage luminescent material as claimed in any of the preceding claims 1-4, characterized in that the X-ray storage luminescent material is used in an imaging plate for radiation imaging.
10. The use according to claim 9, characterized in that the X-ray storage luminescent material is subjected to particle size classification screening to obtain an X-ray storage luminescent material with a particle size of 5±2 μm for coating of the image plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311083712.XA CN116814252A (en) | 2023-08-28 | 2023-08-28 | X-ray storage luminescent material, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311083712.XA CN116814252A (en) | 2023-08-28 | 2023-08-28 | X-ray storage luminescent material, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116814252A true CN116814252A (en) | 2023-09-29 |
Family
ID=88120566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311083712.XA Pending CN116814252A (en) | 2023-08-28 | 2023-08-28 | X-ray storage luminescent material, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116814252A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239968A (en) * | 1978-07-12 | 1980-12-16 | Fuji Photo Film Co., Ltd. | Method and apparatus for recording and reproducing a radiation image |
| EP0148507A2 (en) * | 1983-12-28 | 1985-07-17 | Fuji Photo Film Co., Ltd. | Phosphor and radiation image storage panel employing the same |
| JP2002265941A (en) * | 2001-03-12 | 2002-09-18 | Fuji Photo Film Co Ltd | Production method for photostimulable phosphor |
| JP2004238512A (en) * | 2003-02-06 | 2004-08-26 | Konica Minolta Holdings Inc | Photostimulable phosphor, liquid-phase preparation method thereof and radiological image conversion panel |
| CN101434841A (en) * | 2008-12-18 | 2009-05-20 | 北京交通大学 | Functional material for X ray image storage and preparation thereof |
| CN114316985A (en) * | 2021-12-30 | 2022-04-12 | 马兰 | Ray storage luminescent material and preparation method and application thereof |
-
2023
- 2023-08-28 CN CN202311083712.XA patent/CN116814252A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239968A (en) * | 1978-07-12 | 1980-12-16 | Fuji Photo Film Co., Ltd. | Method and apparatus for recording and reproducing a radiation image |
| EP0148507A2 (en) * | 1983-12-28 | 1985-07-17 | Fuji Photo Film Co., Ltd. | Phosphor and radiation image storage panel employing the same |
| JP2002265941A (en) * | 2001-03-12 | 2002-09-18 | Fuji Photo Film Co Ltd | Production method for photostimulable phosphor |
| JP2004238512A (en) * | 2003-02-06 | 2004-08-26 | Konica Minolta Holdings Inc | Photostimulable phosphor, liquid-phase preparation method thereof and radiological image conversion panel |
| CN101434841A (en) * | 2008-12-18 | 2009-05-20 | 北京交通大学 | Functional material for X ray image storage and preparation thereof |
| CN114316985A (en) * | 2021-12-30 | 2022-04-12 | 马兰 | Ray storage luminescent material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHENG ZHEN ET AL.: "Electron Traps in Si4+ doped BaFBr : Eu2+ X-ray storage", JOURNAL OF OPTOELECTRONICS LASER, vol. 15, no. 1, pages 116 - 119 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4507560A (en) | Terbium-activated gadolinium oxysulfide X-ray phosphor | |
| EP1013741B1 (en) | Phosphor preparation method | |
| Sahu et al. | Luminescent properties of R+ doped Sr 2 MgSi 2 O 7: Eu 3+(R+= Li+, Na+ and K+) orange–red emitting phosphors | |
| Secu et al. | Preparation and optical properties of BaFCl: Eu2+ X-ray storage phosphor | |
| JP2001172623A (en) | Fluorescent substance and fluorescent lamp using the same | |
| US4608190A (en) | X-ray image storage panel comprising anion-deficient BaFCl:Eu/BaFBr:Eu phosphors | |
| CN116814252A (en) | X-ray storage luminescent material, preparation method and application | |
| JP2002212550A (en) | Method for producing rare earth-activated alkaline earth metal fluoride halide-based phosphorescent particle, and rare earth-activated alkaline earth metal fluoride halide-based phosphorescent particle | |
| JPH08170077A (en) | Fluorescent substance, its production, luminescent screen and cathode ray tube using the fluophor | |
| JP4205936B2 (en) | Aluminate phosphor, method for producing the same, phosphor paste composition, and vacuum ultraviolet light-emitting device | |
| EP0159014A2 (en) | Phosphor | |
| JP2007314709A (en) | Metal oxide phosphor, its manufacturing method, and scintillator plate for radiation obtained using the same | |
| JP3268761B2 (en) | High brightness and long afterglow aluminate phosphor with excellent heat and weather resistance | |
| US4871474A (en) | Phosphor | |
| JP2002080847A (en) | Rare earth silicate phosphor and luminescent screen using the same | |
| US6623661B2 (en) | Method for producing photostimulable phosphor | |
| JPH11106749A (en) | Phosphor for active light-emitting liquid display element | |
| JPH0514751B2 (en) | ||
| US6361714B1 (en) | Method of preparing barium fluorohalide phosphor | |
| JP2000290649A (en) | Fluorescent substance, its production, and color cathode ray tube | |
| JP2010215717A (en) | Illuminant and method for producing the illuminant | |
| JP2004091641A (en) | Precursor of rare earth-activated fluorinated barium halide-based fluorophor, method for producing the same and fluorophor | |
| JPS6312687A (en) | Europium activated barium/strontium/magnesium fluorobromide light inductive phosphor having ba1-x-y-zsrxmgyeuzfbr composition | |
| JP2008115275A (en) | Rare earth oxide phosphor and light-emitting device using the same | |
| JPS60190489A (en) | Fluorescent substance of bivalent metal fluorohalide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |