CN113860747A - Chloride crystal and glass composite transparent optical functional material and preparation method and application thereof - Google Patents
Chloride crystal and glass composite transparent optical functional material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 105
- 239000013078 crystal Substances 0.000 title claims abstract description 81
- 239000011521 glass Substances 0.000 title claims abstract description 68
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 58
- 230000003287 optical effect Effects 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 11
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims abstract description 26
- 229910001631 strontium chloride Inorganic materials 0.000 claims abstract description 24
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- 150000002500 ions Chemical class 0.000 claims abstract description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims abstract description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 10
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011780 sodium chloride Substances 0.000 claims abstract description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 7
- 239000001110 calcium chloride Substances 0.000 claims abstract description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 7
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims abstract description 6
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 38
- 238000001514 detection method Methods 0.000 claims description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 150000002910 rare earth metals Chemical class 0.000 claims description 10
- 229910016644 EuCl3 Inorganic materials 0.000 claims description 8
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical group [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 8
- -1 rare earth ions Chemical class 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003628 erosive effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 16
- 229910052593 corundum Inorganic materials 0.000 description 9
- 239000010431 corundum Substances 0.000 description 9
- 238000004020 luminiscence type Methods 0.000 description 9
- 229940102127 rubidium chloride Drugs 0.000 description 9
- 238000000411 transmission spectrum Methods 0.000 description 8
- 230000005284 excitation Effects 0.000 description 6
- 238000001748 luminescence spectrum Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000005385 borate glass Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002059 diagnostic imaging Methods 0.000 description 1
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/16—Halogen containing crystalline phase
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/615—Halogenides
- C09K11/616—Halogenides with alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7704—Halogenides
- C09K11/7705—Halogenides with alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7732—Halogenides
- C09K11/7733—Halogenides with alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/779—Halogenides
- C09K11/7791—Halogenides with alkali or alkaline earth metals
Abstract
The invention belongs to the technical field of scintillator materials, and discloses a chloride crystal and glass composite transparent optical functional material, and a preparation method and application thereof. The transparent optical functional material comprises the following components: 50-99 mol% of chloride crystal phase and 1-50 mol% of glass phase, wherein the chloride crystal phase is formed by more than one of alkali metal chloride or alkaline earth metal chloride; the glass phase is formed by boron oxide or phosphorus pentoxide; the alkaline earth metal chloride is CaCl2、SrCl2More than one of the above; the alkali metal chloride is more than one of LiCl, NaCl, KCl, RbCl and CsCl. The invention also discloses a preparation method of the material. The material of the invention has high transparency, high crystal content, continuously adjustable crystal content and strong water erosion resistance, and is dopedThe luminescent ion has good luminescent performance. The material of the invention is used for preparing scintillator materials and/or laser materials.
Description
Technical Field
The invention relates to a transparent composite light function material, in particular to a transparent composite material containing chloride crystals and glass, a preparation method and application thereof.
Background
The composite material is a material with wide application, and the transparent composite material has important application in the fields of high-energy ray detection, laser, infrared luminescence and the like. In the field of high-energy ray detection, a scintillator material is a luminescent material which can effectively convert various invisible high-energy rays (such as X rays, alpha rays, beta rays, gamma rays, high-energy particles of protons, neutrons and the like) into visible light or ultraviolet light, and is widely applied to the fields of high-energy physics, medical imaging, astronomical physics, atomic energy, homeland security and the like.
At present, the composite material has a very important role in the scintillator, such as will6LiF and ZnS: the scintillation screen prepared by Ag through the organic adhesive can be used for large-area neutron detection experiments. While6Li6Gd(BO3)3: ce crystal and Y2SiO5: composites of Ce crystals can also be used for the discrimination of neutrons from gamma rays. However, these composite materials often have problems such as refractive index mismatch, which causes scattering and absorption of self-luminescence signals, and thus cannot be applied to quantitative analysis of pulse height spectra, and limits the application range thereof.
In the laser field, laser materials play an important role in the current social development and scientific research, are widely applied to the fields of communication, medical treatment, aerospace, processing and manufacturing, exploration and the like, and have irreplaceable effects. At present, the laser material mainly adopts a crystal material, such as Y3Al5O12Or a glass material. The research on the laser material of the chloride crystal is less, on one hand, the preparation of the chloride crystal is complex and the cost is high, and the chloride is easy to absorb moisture, and the performance of the chloride crystal in the aspect of laser needs to be improved. How to further solve the application of chloride crystal in laserThe problem is a very important issue.
In addition, infrared lasers also play a significant role in communication and detection.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a transparent optical functional material compounded by chloride crystals and glass and a preparation method thereof. The material of the invention has high transparency, high crystal content, continuously adjustable crystal content, strong water erosion resistance and easy preparation of block materials. The transparent optical functional material of the invention has better luminous performance by doping luminous ions.
The invention also aims to provide application of the composite transparent optical functional material. The composite transparent optical functional material is used for preparing a laser material and/or a scintillator material.
The purpose of the invention is realized by the following technical scheme:
a transparent optical functional material compounded by chloride crystals and glass comprises the following components:
50-99 mol% of chloride crystal phase
1 to 50 mol% of glass phase
The above percentages are mole percentages calculated on the basis of the amounts of the raw materials of the chloride crystal phase and the raw materials of the glass phase.
The mole percentage of the chloride crystals is preferably 85 to 95%, and more preferably 87 to 95%.
The chloride crystal phase is formed by more than one of alkali metal chloride or alkaline earth metal chloride;
the glass phase is boron oxide (B)2O3) Or phosphorus pentoxide (P)2O5) The glass phase formed.
The alkaline earth metal chloride is CaCl2、SrCl2One or more of (1);
the alkali metal chloride is more than one of LiCl, NaCl, KCl, RbCl and CsCl.
When the glass phase is boron oxide (B)2O3) When the glass phase is formed, the crystal phase of the chloride is CaCl2、SrCl2More than one of the above; when the glass phase is phosphorus pentoxide (P)2Os) When the glass phase is formed, the crystal phase of the chloride is CaCl2、SrCl2More than one of LiCl, NaCl, KCl, RbCl and CsCl.
Preferably, when the glass phase is boron oxide (B)2O3) When the glass phase is formed, the chloride crystal phase is SrCl2(ii) a When the glass phase is phosphorus pentoxide (P)2O5) When the glass phase is formed, the chloride crystal phase is more than one of KCl and RbCl. Under this condition, the optically functional material has high transparency.
The preparation method of the transparent optical functional material compounded by the chloride crystal and the glass comprises the following steps:
and (3) uniformly mixing the chloride crystal phase raw material and the glass phase raw material, melting at high temperature, and quenching to obtain the transparent optical functional material.
The high-temperature melting condition is melting at 1100-1200 ℃, and keeping the temperature for 5-20 min. The melting is carried out in an air atmosphere.
The quenching refers to placing the high-temperature molten melt in a mold and naturally cooling.
The mold was not preheated, cold mold.
The transparent optical functional material is used for preparing a scintillator material and/or a laser material.
The scintillator material comprises the transparent optical functional material and doped rare earth ions; the doping amount of the rare earth ions is 0.1-5 mol% of the amount of the transparent optical functional material (the total amount of the chloride crystal raw material and the glass phase raw material).
Doped with rare-earth luminescent ions mainly Eu2+And/or Ce3+。
The melting point of the chloride is within or below the glass phase melting temperature range, and the glass phase melting temperature range is generally 600-1200 ℃.
The rare earth luminescent ion is EuCl3Or CeCl3As doping material.
The scintillator material is EuCl3Or CeCl3As a doping raw material, the doping raw material is uniformly mixed with a chloride crystal raw material and a glass phase raw material in the transparent optical functional material, and the mixture is melted at a high temperature.
The scintillator material is applied to the fields of radiation detection (such as ray detection), neutron detection and laser detection, and is used for preparing a ray detection device, a neutron detection device and a laser detection device.
When neutron detection is carried out, the glass phase is 95% abundance10B2O3As the glassy phase.
The laser material comprises the transparent optical functional material and doped rare earth ions; the doping amount of the rare earth ions is 0.1-5 mol% of the amount of the transparent optical functional material (the total amount of the chloride crystal raw material and the glass phase raw material).
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the transparent optical functional material compounded by the chloride crystal and the glass has good optical transparency, and is more beneficial to transmitting a luminescent signal from the interior of the material and the collection effect of the luminescent signal of the material compared with the common semitransparent or opaque composite material.
(2) The transparent optical functional material compounded by the chloride crystal and the glass has the characteristic of continuously adjusting the volume fraction of the crystal (the volume percentage of the crystal phase and the glass phase in the composite material is changed by adjusting the mole percentage of the raw material of the chloride crystal phase and the raw material of the glass phase), the content of the crystal can be continuously adjusted between 0 and 95 percent according to the use requirement, and the transparency of the material is kept at the same time (the material has the best comprehensive performance on the transparency and the luminescence performance when the mole percentage of the raw material of the chloride crystal is 90 percent).
(3) The transparent optical functional material compounded by the chloride crystal and the glass can obtain high chloride crystal content after being doped with luminescent ions, and compared with oxide glass, the chloride crystal often has higher luminescent intensity, thereby being beneficial to the application of the material in the aspects of ray detection (radiation detection material), infrared luminescence and the like.
(4) After the transparent optical functional material compounded by the chloride crystal and the glass is doped with luminescent ions, the sizes of the chloride crystal and the glass are respectively 2-10 um and 0.5-5 um, and 95% abundance can be used10B2O3As the glass phase, use is made of10B reacts with thermal neutrons to produce alpha and7and Li secondary particles, the range of which can effectively penetrate through the glass phase to reach the chloride crystal phase, and the excited crystal phase obtains high luminescence performance, and the secondary particles have higher light output in neutron detection than commercial GS 20.
(5) The microstructure of the transparent optical functional material compounded by the chloride crystals and the glass is that the glass phase wraps the chloride crystal phase, the crystal phase is distributed in a discrete island shape, the chloride is very easy to dissolve in water, and the contact between the crystals and the water can be effectively isolated by forming the closed glass phase among the chloride crystals, so that the water erosion resistance of the composite material is effectively improved.
Drawings
FIG. 1 is an XRD pattern of the composite transparent optically functional material of example 1;
FIG. 2 is a transmission spectrum of the composite transparent optically functional material in example 1;
FIG. 3 is an XRD spectrum of the composite transparent optically functional material doped with rare earth luminescent ions in example 2;
FIG. 4 is a scanning electron microscope photograph of the glass phase of the composite transparent optically functional material doped with rare earth luminescent ions of example 2 after the crystal phase is removed;
FIG. 5 is an X-ray excited luminescence spectrum of the composite transparent optically functional material doped with rare earth luminescent ions of example 2;
FIG. 6 is a transmission spectrum of the composite transparent optically functional material doped with rare earth luminescent ions of example 2;
FIG. 7 is an XRD pattern of the composite material of comparative example 1;
FIG. 8 is a graph of the transmission spectrum of the composite material in comparative example 1;
FIG. 9 is an X-ray excitation luminescence spectrum of the composite material in comparative example 1;
FIG. 10 is an XRD pattern of the composite material of comparative example 2;
FIG. 11 is a transmission spectrum of the composite material in comparative example 2;
fig. 12 is an X-ray excitation luminescence spectrum of the composite material in comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Rubidium chloride (RbCl) crystal and phosphorus pentoxide (P) of the present example2O5) The preparation method of the glass composite transparent optical functional material comprises the following steps:
(1) selecting high-purity anhydrous RbCl crystal powder and high-purity P2O5The powder is used as raw material, RbCl: P2O5The molar ratio of (1) is 95: 5;
(2) weighing 20g of raw materials in the glove box, grinding the raw materials in an agate mortar for 40 minutes, then putting the raw materials into a corundum crucible, covering the corundum crucible, and putting the corundum crucible into a sealing box, taking out the glove box and storing the corundum crucible; and (3) putting the corundum crucible into a 1150 ℃ smelting furnace, preserving the temperature for 10 minutes (the smelting furnace is directly communicated with the atmosphere, and the internal atmosphere is air atmosphere), pouring the smelted high-temperature melt on a copper plate, and naturally cooling to obtain the transparent optical functional material compounded by the transparent RbCl crystal and the phosphate glass.
Fig. 1 is an XRD spectrum of the composite transparent optically functional material prepared in this example. As can be seen from fig. 1, the material mainly contains an RbCl crystal phase.
Fig. 2 is a transmission spectrum of the composite transparent optical functional material prepared in this example. As can be seen from fig. 2, the material has good visible light transmittance. Wherein the transmittance of the visible light wave band of 500nm is about 40 percent.
Example 2
Strontium chloride (SrCl) doped with luminescent ion of the present example2) Crystals and boron oxide (B)2O3) The preparation method of the glass composite transparent optical functional material comprises the following steps:
(1) selecting high-purity anhydrous SrCl2Crystalline powder, high purity B2O3Powder, high purity anhydrous EuCl3Crystal powder is used as raw material, and the mol ratio of the raw materials is SrCl2∶B2O3∶EuCl3＝90∶10∶1；
(2) Weighing 20g of raw materials in a glove box, grinding in an agate mortar for 40 minutes, then putting the raw materials into a corundum crucible, covering the corundum crucible, and putting the corundum crucible into a sealed box, taking out the glove box and storing the raw materials; putting the corundum crucible into a 1150 ℃ smelting furnace, preserving the heat for 15 minutes, pouring the smelted high-temperature melt on a copper plate, and naturally cooling to obtain transparent SrCl2Crystal and borate glass compounded transparent optical functional material.
Fig. 3 is an XRD spectrum of the composite transparent optically functional material doped with rare earth luminescent ions prepared in this example. As can be seen from the figure, the material mainly contains SrCl2A crystalline phase.
Fig. 4 is a scanning electron microscope photograph of the composite transparent optical functional material doped with rare earth luminescent ions prepared in this example. The samples were polished and solution rinsed to remove the crystalline phase (EuCl)3With SrCl2Crystalline phase) fraction (in the composite sample, EuCl in the crystalline phase3With SrCl2The crystal phases are fused together and can be regarded as a whole, so SrCl2When the crystalline phase is removed, the corresponding EuCl3Also jointly removed), the remaining borate glass framework can be seen, and SrCl can be determined2The crystal phase is distributed in discrete islands, the size is several micrometers, the borate glass phase is distributed continuously, and the thickness is about 1 micrometer.
In the material of this example, after melting at high temperature, a small amount of SrCl was partially present2The raw materials will react with B2O3The raw materials are mixed to form a glass phase of the boundary. Not pure B in the boundary glass phase2O3But at the same time contains a small amount of SrCl2And EuCl3Just like salt NaCl dissolved in water (B)2O3Can dissolve into a certain amount of SrCl just like water2). After quenching, the boundary glass phase of the composite material is actualBelong to SrCl2-EuCl3-B2O3The glass having such a structure is also called a borate glass because the main component thereof is boron.
Fig. 5 is an X-ray excitation luminescence spectrum of the composite transparent optical functional material prepared in this example. As can be seen from FIG. 5, the material has excellent radiation excited luminescence property, and the luminescence peak height is about Bi under the excitation of 40keV X-ray4Ge3O128.6 times of the crystal.
Fig. 6 is a transmission spectrum of the composite transparent optically functional material prepared in this example. As can be seen from FIG. 6, the transmittance of the material sample at 500nm in the visible band is about 62%, and the transmittance at 1900nm in the near infrared band is about 88%.
Comparative example 1
The crystal phase raw material is NaCl, the glass phase raw material is P2O5The other conditions were the same as in example 1. The result was a white opaque bulk sample.
Fig. 7 is an XRD pattern of the composite material prepared in the present comparative example. As can be seen from FIG. 7, the material mainly contains NaCl crystal phase.
FIG. 8 is a transmission spectrum of a composite material prepared in this comparative example. As can be seen from fig. 8, the material is a white opaque bulk material, and therefore is substantially opaque to visible and infrared wavelengths.
Fig. 9 is an X-ray excitation luminescence spectrum of the composite material prepared in this comparative example. As can be seen from fig. 9, the luminescence intensity of the sample prepared in this comparative example is only about 1% of that of the composite transparent optically functional material in example 2.
Comparative example 2
The crystal phase raw material is SrCl2The glass phase raw material is P2O5The other conditions were the same as in example 2. The result was a white opaque bulk sample.
Fig. 10 is an XRD pattern of the composite material prepared in the present comparative example. As is clear from FIG. 10, the material mainly contains SrCl2A crystalline phase.
FIG. 11 is a transmission spectrum of a composite material prepared in this comparative example. As can be seen from fig. 11, the material is a white opaque bulk material, and therefore is substantially opaque to visible and infrared wavelengths.
Fig. 12 is an X-ray excitation luminescence spectrum of the composite material prepared in this comparative example. As can be seen from fig. 12, the luminescence intensity of the sample prepared in this comparative example is only about 3% of that of the composite transparent optically functional material in example 2.
Claims (10)
1. A transparent optical functional material compounded by chloride crystals and glass is characterized in that: comprises the following components:
50-99 mol% of chloride crystal phase
1 to 50 mol% of glass phase
The percentage is mole percentage, which is calculated by the amount of the raw material of the chloride crystal phase and the raw material of the glass phase;
the chloride crystal phase is formed by more than one of alkali metal chloride or alkaline earth metal chloride;
the glass phase is formed by boron oxide or phosphorus pentoxide;
the alkaline earth metal chloride is CaCl2、SrCl2One or more of (1);
the alkali metal chloride is more than one of LiCl, NaCl, KCl, RbCl and CsCl.
2. The transparent optical functional material compounded of chloride crystal and glass according to claim 1, characterized in that: when the glass phase is formed by boron oxide, the chloride crystal phase is CaCl2、SrCl2More than one of the above; when the glass phase is formed by phosphorus pentoxide, the chloride crystal phase is CaCl2、SrCl2More than one of LiCl, NaCl, KCl, RbCl and CsCl.
3. The transparent optical functional material compounded of chloride crystal and glass according to claim 2, characterized in that: when the glass phase is a glass phase formed of boron oxideThe chloride crystal phase is SrCl2(ii) a When the glass phase is formed by phosphorus pentoxide, the chloride crystal phase is more than one of KCl and RbCl.
4. The transparent optical functional material compounded of chloride crystal and glass according to claim 1, characterized in that: the mol percent of the chloride crystal phase is 85-95%, and the mol percent of the glass phase is 15-5%.
5. The method for preparing the transparent optical functional material compounded by the chloride crystal and the glass according to any one of claims 1 to 4, which is characterized in that: the method comprises the following steps:
and (3) uniformly mixing the chloride crystal phase raw material and the glass phase raw material, melting at high temperature, and quenching to obtain the transparent optical functional material.
6. The method for preparing the transparent optical functional material compounded of the chloride crystal and the glass according to claim 5, is characterized in that: the high-temperature melting condition is melting at 1100-1200 ℃, and keeping the temperature for 5-20 min;
the quenching refers to placing the high-temperature molten melt in a mold and naturally cooling.
7. The use of the transparent optical functional material compounded of chloride crystal and glass according to any one of claims 1 to 4, characterized in that: the transparent optical functional material is used for preparing a scintillator material and/or a laser material.
8. A scintillator material, characterized in that: comprises transparent optical functional material and doped rare earth ions; the transparent optically functional material is as defined in any one of claims 1 to 4; the doping amount of the rare earth ions is 0.1-5 mol% of the dosage of the transparent optical functional material.
9. The scintillator material of claim 8, wherein: the rare earth doped luminescent ion is mainly Eu2+And/or Ce3+；
The rare earth luminescent ion is EuCl3And/or CeCl3As a doping raw material;
the scintillator material is EuCl3Or CeCl3The doped material is used as a doping raw material, and is uniformly mixed with a chloride crystal raw material and a glass phase raw material in the transparent optical functional material, and then the mixture is melted at high temperature to obtain the transparent optical functional material.
10. Use of a scintillator material according to one of the claims 8 to 9, characterized in that: the scintillator material is used in the fields of radiation detection, neutron detection and laser detection.
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