CN111302643A - Glass optical fiber for neutron detection, scintillation material and preparation method thereof - Google Patents
Glass optical fiber for neutron detection, scintillation material and preparation method thereof Download PDFInfo
- Publication number
- CN111302643A CN111302643A CN202010150514.0A CN202010150514A CN111302643A CN 111302643 A CN111302643 A CN 111302643A CN 202010150514 A CN202010150514 A CN 202010150514A CN 111302643 A CN111302643 A CN 111302643A
- Authority
- CN
- China
- Prior art keywords
- glass
- powder
- optical fiber
- fiber core
- parts
- 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
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
- C03C13/00—Fibre or filament compositions
- C03C13/04—Fibre optics, e.g. core and clad fibre compositions
- C03C13/045—Silica-containing oxide glass compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
- C03B37/025—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from reheated softened tubes, rods, fibres or filaments, e.g. drawing fibres from preforms
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T3/00—Measuring neutron radiation
- G01T3/06—Measuring neutron radiation with scintillation detectors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- High Energy & Nuclear Physics (AREA)
- Molecular Biology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a glass fiber for neutron detection, which comprises a fiber core and a cladding pipe coated on the outer layer of the fiber core; the fiber core is made of a scintillating material and is used as a scintillator of the neutron detector; the cladding tube is made of high-purity quartz material and is used as a scintillator shell of the neutron detector. The scintillation material is prepared into the glass optical fiber, so that the scintillation luminescence of the activator ions can be realized and totally reflected in the fiber core; when the glass fiber is used for neutron and gamma ray detection, the position resolution of thermal neutron detection can be greatly improved, and the glass fiber is easy to be designed and processed into various detector structures. The invention also provides a preparation method for preparing the glass optical fiber.
Description
Technical Field
The invention relates to the technical field of neutron detection, in particular to a glass fiber and a scintillation material for neutron detection and a preparation method thereof.
Background
The scintillation detector utilizes the flash light generated by ionizing radiation in some substances to detect, and is one of the most widely used ionizing radiation detectors at present, and the core component of the scintillation detector is a scintillator, which is a luminescent material capable of converting the ionizing energy of X-rays, gamma rays or high-energy particles into ultraviolet/visible light, as early as 1903, william klukes invented a scintillation mirror made of zinc sulfide fluorescent material and used to observe radiation emitted by radium decay, rutherford also used a zinc sulfide phosphor screen to observe α particles in its famous rutherford scattering experiment, however, since the conventional fluorescent material is inconvenient to use, the scintillation detector has not been greatly developed, in 1947, Coltman and Marshall successfully utilized a photomultiplier tube to measure weak fluorescent photons generated by radiation in the scintillator, which marks the origin of the scintillator detector.
Due to Ce3+The emission of (1) belongs to 5d-4f transition, the decay time is short, the energy level difference between 5d-4f is minimum in La ions, the energy transfer is very favorable, and the rare earth ions Ce3+Doped with a compound containing6Li lithium silicate scintillating materials are well suited for neutron detection, thus attracting a large number of researchers. Currently, rare earth ion Ce for thermal neutron detection3+Doped with a compound containing6Li-lithium silicate scintillation glass has been widely used in the fields of neutron flight time experiments, oil well logging, nondestructive testing, neutron photography and the like. The modern scintillation detector mainly comprises a scintillator (and a shell thereof) and a photomultiplier, has a relatively simple structure, low detection efficiency and relatively low spatial resolution, is limited by the shape and the size of the scintillator, and has great limitation on application occasions and application fields, so that how to improve the detection efficiency and the spatial resolution of the scintillation detector is how to improve the detection efficiency and the spatial resolution of the scintillation detector, and the application occasions and the application fields thereof are radiation detection imaging technologyThe focus of the study is on the art.
Disclosure of Invention
Aiming at the existing problems, the invention provides the glass optical fiber for neutron detection, the scintillation material is prepared into the glass optical fiber, the scintillation luminescence of the activator ions can be realized to be totally reflected in the fiber core, when the glass optical fiber is used for neutron and gamma ray detection, the position resolution of thermal neutron detection can be greatly improved, the position resolution can reach one hundred micrometers or more and even tens of micrometers, and the glass optical fiber is easy to be designed and processed into various detector structures and has wider applicability.
The invention adopts the following technical scheme:
a glass optical fiber for neutron detection, characterized by: comprises a fiber core and a cladding tube coated on the outer layer; the fiber core is made of a scintillating material and is used as a scintillator of the neutron detector; the cladding tube is made of any one of quartz glass, high silica glass and aluminosilicate glass, preferably high-purity quartz glass and is used as a scintillator shell of the neutron detector.
In the invention, the scintillating material is made into the glass optical fiber, the fiber core is made of the scintillating material, the cladding tube is made of the material with the refractive index lower than that of the fiber core, or a layer of resin material is coated outside, so that the total reflection of the ion luminescence of the activator in the fiber core can be realized. The glass fiber can be applied to the fields of neutron flight time experiments, nuclear material monitoring, neutron irradiation field detection and the like. The glass fiber has the following advantages in the application aspects of neutron and gamma ray detection and the like: firstly, the position resolution of the thermal neutron detector can be greatly improved, and the position resolution can reach one hundred microns or more and even tens of microns; and secondly, the glass optical fiber is easy to be designed and processed into various detector structures, so that the application occasion and the range of the neutron detector can be effectively expanded, for example, the glass optical fiber can be applied to the detection of Pu lung, and the optical fiber panel can increase the detection efficiency and the detection precision.
The preparation method of the glass optical fiber comprises the following steps:
step 1: manufacturing a fiber core thin rod with a preset size by adopting a scintillating material;
step 2: according to the size of the core slim rod, a cladding tube is made of any one of quartz glass, high silica glass and aluminosilicate glass, and the inner diameter of the cladding tube is slightly larger than the outer diameter of the core slim rod;
and step 3: cleaning the fiber core slim rod and the cladding tube, and performing vacuum drying treatment after cleaning;
and 4, step 4: placing the fiber core slim rod in the cladding pipe, sealing one end of the cladding pipe, vacuumizing the interior of the cladding pipe, and sealing the other end of the cladding pipe to obtain an optical fiber preform;
and 5: and carrying out wire drawing operation on the optical fiber preform to obtain the glass optical fiber.
Further, in the step 1, the scintillating material is made into the fiber core slim rod through cutting and polishing operations;
further, in the step 2, the inner diameter of the cladding pipe is 1mm to 2mm larger than the outer diameter of the core slim rod;
further, in the step 3, the fiber core slim rod and the cladding tube are ultrasonically cleaned by taking acetone as a medium, and then vacuum drying treatment is carried out by using a vacuum drying oven at the temperature of 110-150 ℃;
further, in the step 4, after the core pin and the cladding pipe are cooled to normal temperature, the core pin is placed in the cladding pipe;
further, in the step 5, the optical fiber preform is drawn at a softening temperature of the material for making the cladding pipe according to a preset drawing speed and a preset size of the obtained optical fiber.
Further, in the step 1, the grinding and polishing operation includes rough grinding, rough polishing and finish polishing;
further, in the step 4, the inside of the cladding pipe is evacuated for 1 to 3 hours.
In order to meet the manufacturing requirements of glass optical fibers for neutron detection, the scintillating material needs to have the characteristics of high luminous efficiency, high melting point, high thermal stability, strong chemical stability and the like, and the scintillating material should haveHas the characteristics of relatively low phonon energy and easy drawing into fibers. Therefore, the invention also provides a scintillating material for manufacturing the glass optical fiber, which is characterized in that: the scintillation material is Ce3+Ion doping of6Li-Al-silicate glass or Ce3+Ion doping of6Li lithium magnesium aluminosilicate glass.
Further, the scintillation material is Ce3+Ion doping of6The Li lithium aluminosilicate glass comprises the following oxide components in parts by weight: 13 to 21 parts of Li2O, 15-25 parts of Al2O345.5 to 72 parts of SiO2And 0.50 to 1.25 parts of Ce2O3(ii) a Or, the scintillating material is Ce3+Ion doping of6The Li lithium magnesium aluminosilicate glass comprises the following oxide components in parts by weight: 13 to 21 parts of Li2O, 15-25 parts of Al2O345.5 to 72 parts of SiO20.50 to 1.25 parts of Ce2O3And not more than 8.5 parts of MgO.
The preparation method of the scintillation material comprises the following steps:
step 01: taking the appropriate amount6Hydrolyzing LiH powder to obtain6Li2O powder; at least respectively weighing the right amount6Li2O powder and SiO2、Al2O3And CeO2Powder, or a suitable amount of6Li2O powder and SiO2、Al2O3MgO and CeO2Powder is mixed by high-energy ball milling to obtain mixed oxide powder;
step 02: the mixed oxide powder is melted, cast and annealed to obtain Ce3+Ion doping of6Li-Al-silicate glass or Ce3+Ion doping of6Li-Al-Mg silicate glass is the scintillating material.
Further, in the step 01,
weighing appropriate amount of the product with purity of more than 90%6LiH powder, which is produced by hydrolysis reaction in multiple portions6LiOH; wherein, the first part is prepared6After the LiH powder completely reacts with water to obtain clear transparent liquid, the later parts of the LiH powder are sequentially added into the clear transparent liquid6LiH powder and deionized water to finally obtain6Transparent LiH powder completely reacted with deionized water6An aqueous solution of LiOH;
will obtain6The LiOH aqueous solution is dried at the temperature of 120-150 ℃ to obtain dried LiOH6LiOH powder.
Will obtain6Placing the LiOH powder into a silicon-molybdenum rod resistance furnace at the temperature of 500-700 ℃, and keeping the LiOH powder at constant temperature for 3-5 h, preferably 2-4 h to obtain6Decomposition products of LiOH6Li2And (4) O powder.
Further, in the step 01, ZrO is adopted for the high-energy ball milling2Ceramic pot with absolute ethyl alcohol, ZrO2The ball is used as a grinding medium, the ball milling speed is 400 r/min-600 r/min, and the ball milling time is 24 h-36 h.
Further, in the step 02, the melting temperature is 1400-1650 ℃, the melting time is 2-4 h, activated carbon powder is used as a reducing agent in the melting process, and CeO in the raw materials is used as the reducing agent2Reduction to Ce2O3(ii) a The casting temperature is 350-550 ℃; the annealing temperature is 450-650 ℃, the annealing heat preservation time is 2-4 h, and the cooling time is not less than 10 h.
The above preparation method uses Ce3+As activator ions and doped in6Li-Al-silicate glasses or glass containing6The scintillation material prepared from the Li-Mg-aluminosilicate glass has ultrahigh rare earth ion doping concentration, the highest doping concentration reaches 1.25%, the scintillation material has high luminous efficiency, and the light integral intensity reaches about 4.6 times of that of bismuth germanate crystals under the excitation of cathode rays. The scintillating material has the characteristics of easily adjustable components, good tissue uniformity, relatively easy preparation, capability of being cast into various shapes, easy realization of large-batch and/or large-size production and easy drawing. In addition, the scintillation material also has high thermal neutron excitation luminous efficiency and excellent thermophysical properties, for example, when the cladding tube is high-purity quartz, the melting point, the thermal expansion coefficient, the refractive index and the like of the scintillation material and the high purityThe matching degree between quartz materials is high.
Drawings
The invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a schematic view showing the structure of a glass optical fiber in examples 1 to 3;
FIG. 2 is a graph showing a white light transmittance curve of a glass optical fiber in a wavelength range of 220nm to 1000nm in examples 1 to 3;
FIG. 3 is an emission spectrum of the glass optical fiber under excitation of laser light at 351nm in examples 1 to 3;
FIG. 4 is a view showing the glass optical fiber in examples 1 to 3252And (3) pulse waveforms under the excitation of Cf spontaneous fission neutrons.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention discloses a glass fiber for neutron detection, which comprises a fiber core 1 and a cladding tube 2 coated on the outer layer of the fiber core 1, wherein the fiber core 1 is used as a scintillator of a neutron detector, and the cladding tube 2 is used as a scintillator shell. Wherein the fiber core 1 is doped with rare earth6Li silicate glass material, in particular Ce3+Doping with6Li-Al-Si-silicate materials or compositions containing6Li-Mg-aluminosilicate material; the cladding pipe 2 is made of quartz glass, high silica glass and aluminum siliconAny one of the materials of the acid salt glass, preferably a high-purity quartz material. In the core material of the glass optical fiber6The Li nuclide has a high thermal neutron capture cross section, and releases high nuclear reaction energy after reacting with neutrons, as shown in the following formula:
n+6Li(7.5％)→4He(2.05MeV)+3H(2.75MeV)σ＝520b(λ～1.5mm)
produced by reaction4He、3The H particles deposit most of nuclear reaction energy in the glass matrix to excite the Ce doped in the glass matrix3+Ions, causing energy level transition, Ce3+When the ion energy level returns to the ground state from the excited state, scintillation fluorescence with a certain wavelength is emitted, the scintillation fluorescence can realize total reflection transmission in a glass optical fiber designed by adopting a proper structure and material parameters, and the neutron signal can be detected by adopting a photoelectric conversion element to receive a photon signal.
The glass fiber designed by the invention has high fluorescence emission efficiency and high luminous band transmittance, and can effectively improve the properties of neutron detection efficiency, energy resolution and the like. The glass optical fiber comprises the following main components:6Li2O、Al2O3、SiO2、Ce2O3(ii) a In addition, an appropriate amount of MgO may be added to promote the formability and fluorescence emission efficiency of the glass. In the invention, the content and the main functions of each component are as follows:
6Li2o: on the one hand, the method comprises the following steps of,6Li+the ions are used as capture ions of neutron reaction, react with neutrons to provide nuclear reaction energy, and excite the doped rare earth ions to emit light; on the other hand, the invention has small radius and large electric field intensity, has the functions of high-temperature fluxing and reducing the high-temperature viscosity of the glass, and can improve the forming capability and the chemical stability of the glass6Li2The designed content of O is 13-21 parts (by weight);6Li2the content of O is too low, the neutron detection efficiency of the glass fiber is low,6Li2too high an amount of O will introduce a significant amount of non-bridging oxygen into the glass matrix, resulting in fluorescence quenching.
Al2O3：Al3+Can be used as network forming ions and network modifying ions. Its substitution for Si can form AlO4、AlO5、AlO6The structure of the ligand is equal, the structural form of the glass optical fiber network can be greatly enriched, and the Al of the invention2O3The design content is 15-25 parts (by weight).
SiO2：SiO2The silicate glass has the characteristics of high melting point, high thermal stability, chemical stability and the like, the relatively low phonon energy is favorable for emitting photons in the fiber core, and the silicate glass also has the characteristic of being easy to draw into fibers; SiO of the invention2The design content is 45.5-72 parts (by weight);
Ce2O3：Ce3+the material has a very unique valence layer electronic structure, the 4f-5d energy level transition of the material is allowed by parity, the emission efficiency is high, the luminous intensity is high, and the material is widely used for preparing luminescent materials and scintillating materials; in the invention, nested corundum crucibles are adopted, a proper amount of activated carbon powder is added at the bottom of a large crucible, C powder is not completely combusted in the high-temperature melting process, and the provided CO atmosphere can be mixed with CeO in a molten reactant2Reaction to form Ce2O3(ii) a By adopting a reducing atmosphere melting method, most of Ce ions can be ensured to be in a trivalent state to be used as luminescence center ions; in addition, the high-efficiency ball milling method is adopted to lead Ce in the glass matrix to be in3+Ions are uniformly doped, so that the high-efficiency fluorescence emission efficiency of the optical fiber core material is ensured, and Ce is mixed according to different components of the glass optical fiber core matrix2O3The design content of (b) is 0.50 to 1.25 parts by weight.
MgO: as network modified ions, the material has the functions of fluxing and balancing local charges; exists in the glass matrix in the form of MgO, can provide ionic bonds and occupy the interstitial positions of a network structure; the field intensity is high, the introduction of the field intensity into the glass matrix can increase the phase separation degree of glass, and the high-efficiency luminous efficiency of the glass fiber core material is improved; the MgO design content of the present invention is not more than 8.5 parts by weight.
The invention designs a glass optical fiber, and the preparation method thereof can comprise the following steps:
weighing in fume hood to obtain product with purity of over 90%6LiH powder is divided into a plurality of parts to react with a proper amount of deionized water, and each part is less than or equal to 1.5 g; concretely, one part is firstly taken6LiH powder is added into a plastic beaker with the volume of 500-2000 ml, and then deionized water is carefully and slowly added into the plastic beaker by a plastic dropper, wherein the deionized water and the deionized water are mixed6LiH powder reacts violently to form6LiOH, discharging a large amount of gas, adding deionized water, and stirring with an organic glass rod until6The reaction of LiH with water was complete to give a clear transparent liquid, and then one portion was added again in sequence to the plastic beaker6LiH powder and deionized water are stirred until the reaction is complete, and finally a certain amount of the LiH powder and the deionized water are obtained6Transparent LiH powder completely reacted with deionized water6A LiOH solution;
will obtain6Pouring the LiOH aqueous solution into a clean beaker, and drying at the temperature of 120-150 ℃ by using a vacuum oven to obtain dried LiOH aqueous solution6LiOH powder;
will obtain6Transferring LiOH powder into a clean corundum crucible, placing the corundum crucible into a silicon-molybdenum rod resistance furnace at the temperature of 500-700 ℃, and keeping the constant temperature for 3-5 hours to obtain the LiOH powder6Decomposition products of LiOH6Li2O powder;
respectively weighing oxide powder according to preset components6Li2O、SiO2、Al2O3、MgO、CeO2Powder; with ZrO2The ceramic pot is a grinding container and is made of absolute ethyl alcohol and ZrO2The small balls are used as grinding media and are mixed by high-energy ball milling; the ball milling rotation speed is 400 r/min-600 r/min, the ball milling time is 20 h-36 h, and the mixed oxide powder is obtained after the ball milling and the mixing are uniform.
The obtained mixed oxide powder is subjected to processes of melting, casting, annealing and the like to prepare Ce3+Ion doped with6A Li silicate glass; the melting temperature is 1400 ℃ to 1650 ℃, the melting time is 2h to 4h, and active carbon powder is used as a reducing agent in the melting processCeO (B) of2Reduction to Ce2O3(ii) a The casting temperature is 350-550 ℃; the annealing temperature is 450-650 ℃, the annealing heat preservation time is 2-4 h, and the cooling time is not less than 10 h;
by using Ce3+Ion doped with6Cutting, grinding and polishing the Li silicate glass to prepare a fiber core slim rod with a preset size;
according to the size of the prepared fiber core slim rod, pure quartz glass is adopted to prepare a cladding tube, and the inner diameter of the cladding tube is 1-2 mm larger than the outer diameter of the fiber core slim rod;
using acetone as a medium, ultrasonically cleaning a fiber core slim rod and a cladding tube, and performing vacuum drying treatment at 110-150 ℃ by using a vacuum drying oven after cleaning;
after the fiber core slim rod and the cladding pipe are cooled to normal temperature, the fiber core slim rod is placed in the cladding pipe, one end of the cladding pipe is sealed, vacuumizing treatment is carried out on the interior of the cladding pipe, the vacuum degree is 10Pa, the vacuumizing time is 3 hours, and then the other end of the cladding pipe is sealed, so that an optical fiber preform is prepared;
and (3) carrying out wire drawing operation on the optical fiber preform at the softening temperature of the manufacturing material of the cladding pipe according to the preset wire drawing speed and the preset size of the obtained glass optical fiber to obtain the glass optical fiber.
The invention further designs the Ce in detail3+Ion doping of6Li-Al-Si-salt or Ce3+Ion doping of6Specific examples, preparation steps and performance test results of the preparation method of the Li-Mg-aluminosilicate glass optical fiber are shown in the following examples.
Example 1 specifically includes the following steps:
weighing in a fume hood to obtain a product with purity of over 90.5%6LiH powder, divided into a plurality of portions, and a proper amount of deionized water, wherein each portion is 1.5 g; concretely, one part is firstly taken6LiH powder was added to a 2000ml capacity plastic beaker and then deionized water was carefully added slowly to the plastic beaker with a plastic dropper6LiH powder reacts violently to form6LiOH, discharging a large amount of gas, adding deionized water, and stirring with an organic glass rod until6The reaction of LiH with water was complete to give a clear transparent liquid, and then one portion was added again in sequence to the plastic beaker6LiH powder and deionized water are stirred until the reaction is complete, and finally a certain amount of the LiH powder and the deionized water are obtained6Transparent LiH powder completely reacted with deionized water6A LiOH solution;
will obtain6Pouring the LiOH aqueous solution into a clean beaker, and drying at 150 ℃ by using a vacuum oven to obtain dried LiOH aqueous solution6LiOH powder;
will obtain6Transferring LiOH powder into a clean corundum crucible, placing the corundum crucible into a silicon-molybdenum rod resistance furnace at the temperature of 650 ℃, and keeping the constant temperature for 3 hours to obtain the LiOH powder6Decomposition products of LiOH6Li2O powder;
respectively weighing 12 parts of oxide powder according to preset components6Li2O, 62 parts of SiO226 parts of Al2O30.81 part of Ce2O3Powder; with ZrO2The ceramic pot is a grinding container and is made of absolute ethyl alcohol and ZrO2The small balls are used as grinding media and are mixed by high-energy ball milling; the ball milling rotation speed is 400r/min, the ball milling time is 20h, and the mixed oxide powder is obtained after the ball milling and the mixing are uniform.
The obtained mixed oxide powder is subjected to processes of melting, casting, annealing and the like to prepare Ce3+Ion doped with6A Li silicate glass; the melting temperature is 1620 ℃, the melting time is 3 hours, and active carbon powder is adopted as a reducing agent in the melting process, and CeO in the raw materials2Reduction to Ce2O3(ii) a The casting temperature is 350 ℃; the annealing temperature is 450 ℃, the annealing heat preservation time is 4 hours, and the cooling time is 18 hours;
by using Ce3+Ion doped with6Cutting, coarse grinding, coarse polishing and fine polishing are sequentially carried out on the Li silicate glass to prepare a fiber core thin rod with the size of phi 6mm multiplied by 20 mm;
the method comprises the following steps of (1) preparing a cladding tube from high-purity quartz glass, wherein the size of the cladding tube is phi 20mm multiplied by phi 6.5mm multiplied by 550mm and is matched with a glass fiber core slim rod, and the inner diameter of the cladding tube is slightly larger than the outer diameter of the fiber core slim rod;
soaking the fiber core slim rod and the cladding tube with acetone and ultrasonically cleaning, and then preserving heat for 3h at 120 ℃ by using a vacuum drying oven and drying;
sleeving a cladding tube on the outer layer of the fiber core slim rod, sealing one end of the cladding tube, vacuumizing the interior of the sleeve for 3 hours with the vacuum degree of 10Pa, and sealing the other end of the cladding tube to obtain an optical fiber preform;
fixing the optical fiber perform on the upper part of a drawing tower, adjusting the fixing position and the height of the optical fiber perform according to the heating height range of a heating furnace of the drawing tower and the length of the optical fiber perform, and setting the temperature of the heating furnace of the drawing tower at 2200 ℃, namely drawing the optical fiber perform under the condition of ensuring the softening temperature of a high-purity quartz glass material; wherein, the speed of the wire drawing rotating wheel is controlled to be 10r/min, the descending speed of the optical fiber preform is 1mm/min by controlling the descending speed of the feeder on the wire drawing tower, and the optical fiber with the diameter of 280 microns is drawn. The drawing tower and its auxiliary equipment are prior art and will not be described herein.
For the glass optical fiber obtained in the embodiment, a transmittance curve of the glass optical fiber is detected by adopting white light with a wavelength range of 220nm to 1000nm, an emission spectrum of the glass optical fiber is detected by adopting 351nm laser, and the glass optical fiber is obtained by adopting252The Cf spontaneous fission neutron source detects the pulse waveform thereof under the excitation of spontaneous fission neutrons, and the detection results are respectively shown as a curve 11 in FIG. 2, a curve 12 in FIG. 3 and a curve 13 in FIG. 4.
Example 2 is different from example 1 in that Li is increased as appropriate2The component ratio of O is reduced, and Al is reduced2O3、SiO2The component ratio of (A) is increased2O3The method specifically comprises the following steps:
weighing in a fume hood to obtain a product with purity of over 90.5%6LiH powder which is divided into a plurality of portions and reacts with a proper amount of deionized water, and each portion is 1.0 g; concretely, one part is firstly taken6LiH powder was added to a 1000ml capacity plastic beaker and then deionized water was carefully added slowly to the plastic beaker with a plastic dropper6LiH powder reacts violently to form6LiOH, discharging a large amount of gas, adding deionized water and adopting organic glassStirring with a rod until6The reaction of LiH with water was complete to give a clear transparent liquid, and then one portion was added again in sequence to the plastic beaker6LiH powder and deionized water are stirred until the reaction is complete, and finally a certain amount of the LiH powder and the deionized water are obtained6Transparent LiH powder completely reacted with deionized water6A LiOH solution;
will obtain6Pouring the LiOH aqueous solution into a clean beaker, and drying at 135 ℃ by using a vacuum oven to obtain dried LiOH aqueous solution6LiOH powder;
will obtain6Transferring LiOH powder into a clean corundum crucible, placing the corundum crucible into a silicon-molybdenum rod resistance furnace at the temperature of 650 ℃, and keeping the constant temperature for 3 hours to obtain the LiOH powder6Decomposition products of LiOH6Li2O powder;
respectively weighing 21 parts of oxide powder according to preset components6Li2O, 59 parts of SiO220 parts of Al2O31.12 parts of Ce2O3Powder; with ZrO2The ceramic pot is a grinding container and is made of absolute ethyl alcohol and ZrO2The small balls are used as grinding media and are mixed by high-energy ball milling; the ball milling rotation speed is 400r/min, the ball milling time is 20h, and the mixed oxide powder is obtained after the ball milling and the mixing are uniform.
The obtained mixed oxide powder is subjected to processes of melting, casting, annealing and the like to prepare Ce3+Ion doped with6A Li silicate glass; the melting temperature is 1530 ℃, the melting time is 3 hours, and active carbon powder is adopted as a reducing agent in the melting process, CeO in the raw materials2Reduction to Ce2O3(ii) a The casting temperature is 450 ℃; the annealing temperature is 550 ℃, the annealing heat preservation time is 3 hours, and the cooling time is 15 hours;
by using Ce3+Ion doped with6Cutting, coarse grinding, coarse polishing and fine polishing are sequentially carried out on the Li silicate glass to prepare a fiber core thin rod with the size of phi 6mm multiplied by 20 mm;
the method comprises the following steps of (1) preparing a cladding tube from high-purity quartz glass, wherein the size of the cladding tube is phi 20mm multiplied by phi 6.5mm multiplied by 550mm and is matched with a glass fiber core slim rod, and the inner diameter of the cladding tube is slightly larger than the outer diameter of the fiber core slim rod;
soaking the fiber core slim rod and the cladding tube with acetone and ultrasonically cleaning, and then preserving heat for 3h at 120 ℃ by using a vacuum drying oven and drying;
sleeving a cladding tube on the outer layer of the fiber core slim rod, sealing one end of the cladding tube, vacuumizing the interior of the sleeve for 3 hours with the vacuum degree of 10Pa, and sealing the other end of the cladding tube to obtain an optical fiber preform;
fixing the optical fiber perform on the upper part of a drawing tower, adjusting the fixing position and the height of the optical fiber perform according to the heating height range of a heating furnace of the drawing tower and the length of the optical fiber perform, and setting the temperature of the heating furnace of the drawing tower at 2000 ℃, namely drawing the optical fiber perform at the softening temperature of a high-purity quartz glass material; wherein, the speed of the wire drawing rotating wheel is controlled to be 20r/min, the descending speed of the optical fiber preform is controlled to be 3mm/min by controlling the descending speed of the feeder on the wire drawing tower, and the optical fiber with the diameter of 180 microns is drawn.
For the glass optical fiber obtained in the embodiment, a transmittance curve of the glass optical fiber is detected by adopting white light with a wavelength range of 220nm to 1000nm, an emission spectrum of the glass optical fiber is detected by adopting 351nm laser, and the glass optical fiber is obtained by adopting252The Cf spontaneous fission neutron source detects the pulse waveform thereof under the excitation of spontaneous fission neutrons, and the detection results are respectively shown as a curve 21 in FIG. 2, a curve 22 in FIG. 3 and a curve 23 in FIG. 4.
Compared with the embodiment 1, the melting temperature of the glass is obviously reduced, and the glass has stronger glass forming capability; the white light transmittance of the material in the wave band of 220 nm-1000 nm is obviously improved, the fluorescence emission efficiency under the excitation of 351nm laser is also obviously improved, and correspondingly, the pulse waveform amplitude under the excitation of spontaneous fission neutrons is also improved to a certain extent.
Example 3 based on example 2, MgO with a certain ratio of components was introduced and Al was maintained2O3、SiO2The content is not changed, and Li is properly reduced2O、Ce2O3The method specifically comprises the following steps:
weighing in a fume hood to obtain a product with purity of over 90.5%6LiH powder, divided into a plurality of portions, and a proper amount of deionized water, wherein each portion is 1.5 g; concretely, one part is firstly taken6LiH powder was added to a 500ml capacity plastic beaker and then deionized water was carefully added slowly to the plastic beaker with a plastic dropper6LiH powder reacts violently to form6LiOH, discharging a large amount of gas, adding deionized water, and stirring with an organic glass rod until6The reaction of LiH with water was complete to give a clear transparent liquid, and then one portion was added again in sequence to the plastic beaker6LiH powder and deionized water are stirred until the reaction is complete, and finally a certain amount of the LiH powder and the deionized water are obtained6Transparent LiH powder completely reacted with deionized water6A LiOH solution;
will obtain6Pouring the LiOH aqueous solution into a clean beaker, and drying at 120 ℃ by using a vacuum oven to obtain dried LiOH aqueous solution6LiOH powder;
will obtain6Transferring LiOH powder into a clean corundum crucible, placing the corundum crucible into a silicon-molybdenum rod resistance furnace at the temperature of 650 ℃, and keeping the constant temperature for 3 hours to obtain the LiOH powder6Decomposition products of LiOH6Li2O powder;
respectively weighing 17 parts of oxide powder according to preset components6Li2O, 59 parts of SiO220 parts of Al2O34 parts of MgO and 0.95 part of Ce2O3Powder; with ZrO2The ceramic pot is a grinding container and is made of absolute ethyl alcohol and ZrO2The small balls are used as grinding media and are mixed by high-energy ball milling; the ball milling rotation speed is 400r/min, the ball milling time is 20h, and the mixed oxide powder is obtained after the ball milling and the mixing are uniform.
The obtained mixed oxide powder is subjected to processes of melting, casting, annealing and the like to prepare Ce3+Ion doped with6A Li silicate glass; the melting temperature is 1535 ℃, the melting time is 3h, and active carbon powder is adopted as a reducing agent in the melting process, CeO in the raw materials2Reduction to Ce2O3(ii) a The casting temperature is 550 ℃; the annealing temperature is 650 ℃, the annealing heat preservation time is 2 hours, and the cooling time is 10 hours;
by using Ce3+Ion doped with6The Li silicate glass is cut, coarsely ground and coarsely polished in sequenceFine polishing to obtain fiber core thin rod with the size of phi 6mm multiplied by 20 mm;
the method comprises the following steps of (1) preparing a cladding tube from high-purity quartz glass, wherein the size of the cladding tube is phi 20mm multiplied by phi 6.5mm multiplied by 550mm and is matched with a glass fiber core slim rod, and the inner diameter of the cladding tube is slightly larger than the outer diameter of the fiber core slim rod;
soaking the fiber core slim rod and the cladding tube with acetone and ultrasonically cleaning, and then preserving heat for 3h at 120 ℃ by using a vacuum drying oven and drying;
sleeving a cladding tube on the outer layer of the fiber core slim rod, sealing one end of the cladding tube, vacuumizing the interior of the sleeve for 3 hours with the vacuum degree of 10Pa, and sealing the other end of the cladding tube to obtain an optical fiber preform;
fixing the optical fiber perform on the upper part of a drawing tower, adjusting the fixing position and the height of the optical fiber perform according to the heating height range of a heating furnace of the drawing tower and the length of the optical fiber perform, and setting the temperature of the heating furnace of the drawing tower at 1800 ℃, namely drawing the optical fiber perform at the softening temperature of a high-purity quartz glass material; wherein the drawing speed is controlled to be 30r/min, the descending speed of the optical fiber preform is controlled to be 5mm/min by controlling the descending speed of the feeder on the drawing tower, and the optical fiber with the diameter of 120 microns is drawn.
For the glass optical fiber obtained in the embodiment, a transmittance curve of the glass optical fiber is detected by adopting white light with a wavelength range of 220nm to 1000nm, an emission spectrum of the glass optical fiber is detected by adopting 351nm laser, and the glass optical fiber is obtained by adopting252The Cf spontaneous fission neutron source detects the pulse waveform thereof under the excitation of spontaneous fission neutrons, and the detection results are respectively shown as a curve 31 in fig. 2, a curve 32 in fig. 3 and a curve 33 in fig. 4. .
Compared with the embodiment 2, the white light transmittance of the material in the 220 nm-1000 nm wave band is further improved, the fluorescence emission efficiency under the excitation of 351nm laser is greatly improved, and correspondingly, the pulse waveform amplitude under the excitation of spontaneous fission neutrons is also obviously improved.
Analysis shows that the proper amount of MgO is introduced into the core matrix of the glass optical fiber to reduce Li2O can promote the glass forming ability, reduce the content of non-bridging oxygen in the glass matrix and reduce Ce in a proper amount2O3The content of Ce in the matrix can be reduced3+The ions form cluster proportion, and the oxidation of the ions to generate Ce is reduced4+The ratio of (a) to (b) further improves the fluorescence efficiency of the glass fiber core material. Proper amount of MgO is introduced into the glass matrix, although Li is reduced2The content of O and the melting temperature of the glass are not obviously increased, so that the forming capability and the optical performance of the glass are further improved.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (10)
1. A glass optical fiber for neutron detection, characterized by:
comprises a fiber core and a cladding tube coated on the outer layer; the fiber core is made of a scintillating material and is used as a scintillator of the neutron detector; the cladding tube is made of any one of quartz glass, high silica glass and aluminosilicate glass and is used as a scintillator shell of the neutron detector.
2. A preparation method of a glass optical fiber for neutron detection is characterized by comprising the following steps:
step 1: manufacturing a fiber core thin rod with a preset size by adopting a scintillating material;
step 2: according to the size of the core slim rod, a cladding tube is made of any one of quartz glass, high silica glass and aluminosilicate glass, and the inner diameter of the cladding tube is slightly larger than the outer diameter of the core slim rod;
and step 3: cleaning the fiber core slim rod and the cladding tube, and performing vacuum drying treatment after cleaning;
and 4, step 4: placing the fiber core slim rod in the cladding pipe, sealing one end of the cladding pipe, vacuumizing the interior of the cladding pipe, and sealing the other end of the cladding pipe to obtain an optical fiber preform;
and 5: and carrying out wire drawing operation on the optical fiber preform to obtain the glass optical fiber.
3. The method of claim 2, wherein:
in the step 1, the scintillating material is cut and polished to prepare the fiber core slim rod;
in the step 2, the inner diameter of the cladding pipe is 1 mm-2 mm larger than the outer diameter of the fiber core slim rod;
in the step 3, the fiber core slim rod and the cladding tube are ultrasonically cleaned by taking acetone as a medium, and then vacuum drying treatment is carried out by using a vacuum drying oven at the temperature of 110-150 ℃;
in the step 4, after the fiber core slim rod and the cladding pipe are cooled to normal temperature, the fiber core slim rod is placed in the cladding pipe;
in the step 5, the optical fiber preform is drawn at the softening temperature of the material for manufacturing the cladding pipe according to a preset drawing speed and a preset obtained optical fiber size.
4. The production method according to claim 3, characterized in that:
in the step 1, the grinding and polishing operation comprises coarse grinding, coarse polishing and fine polishing;
in the step 4, the interior of the cladding pipe is vacuumized for 1 to 3 hours.
5. A scintillating material for producing glass optical fibers, characterized in that:
the glass optical fiber is used for neutron detection;
the scintillation material is Ce3+Ion doping of6Li-Al-silicate glass or Ce3+Ion doping of6Li lithium magnesium aluminosilicate glass.
6. The scintillating material of claim 5, wherein:
the scintillation material is Ce3+Ion doping of6Li-aluminosilicate glass having an oxidation in parts by weight13 to 21 parts of Li2O, 15-25 parts of Al2O345.5 to 72 parts of SiO2And 0.50 to 1.25 parts of Ce2O3；
Or, the scintillating material is Ce3+Ion doping of6The Li-Mg-aluminosilicate glass comprises, by weight, 13-21 parts of Li2O, 15-25 parts of Al2O345.5 to 72 parts of SiO20.50 to 1.25 parts of Ce2O3And not more than 8.5 parts of MgO.
7. A method for preparing a scintillating material according to claim 5 or 6, characterized in that it comprises the following steps:
step 01: at least respectively weighing appropriate amount6Li2O、SiO2、Al2O3And CeO2The powder is obtained by weighing at least appropriate amount of the above materials6Li2O、SiO2、Al2O3、CeO2Mixing the MgO powder and the MgO powder by high-energy ball milling to obtain mixed oxide powder;
step 02: the mixed oxide powder is melted, cast and annealed to obtain Ce3+Ion doping of6Li-Al-silicate glass or Ce3+Ion doping of6Li-Al-Mg silicate glass is the scintillating material.
8. The method according to claim 7, wherein the step 01 is a step of preparing the resin composition6Li2The O powder is prepared by the following preparation method:
step 001: weighing appropriate amount of the product with purity of more than 90%6LiH powder, which is produced by hydrolysis reaction in multiple portions6LiOH; wherein, the first part is prepared6After the LiH powder completely reacts with water to obtain clear transparent liquid, the later parts of the LiH powder are sequentially added into the clear transparent liquid6LiH powder and deionized water to finally obtain6Transparent LiH powder completely reacted with deionized water6An aqueous solution of LiOH;
step 002: will obtain6The LiOH aqueous solution is dried at the temperature of 120-150 ℃ to obtain dried LiOH6LiOH powder;
step 003: will obtain6Putting LiOH powder into a silicon-molybdenum rod resistance furnace at the temperature of 500-700 ℃, and keeping the constant temperature for 3-5 h to obtain6Decomposition products of LiOH6Li2And (4) O powder.
9. The production method according to claim 7 or 8, characterized in that:
in the step 01, ZrO is adopted for the high-energy ball milling2Ceramic pot with absolute ethyl alcohol, ZrO2The ball is used as a grinding medium, the ball milling speed is 400 r/min-600 r/min, and the ball milling time is 24 h-36 h.
10. The production method according to claim 7 or 8, characterized in that:
in the step 02, the melting temperature is 1400-1650 ℃, the melting time is 2-4 h, and active carbon powder is used as a reducing agent in the melting process, and CeO in the raw materials is used as a reducing agent2Reduction to Ce2O3(ii) a The casting temperature is 350-550 ℃; the annealing temperature is 450-650 ℃, the annealing heat preservation time is 2-4 h, and the cooling time is not less than 10 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010150514.0A CN111302643A (en) | 2020-03-06 | 2020-03-06 | Glass optical fiber for neutron detection, scintillation material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010150514.0A CN111302643A (en) | 2020-03-06 | 2020-03-06 | Glass optical fiber for neutron detection, scintillation material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111302643A true CN111302643A (en) | 2020-06-19 |
Family
ID=71153561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010150514.0A Pending CN111302643A (en) | 2020-03-06 | 2020-03-06 | Glass optical fiber for neutron detection, scintillation material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111302643A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112684485A (en) * | 2021-03-22 | 2021-04-20 | 武汉光谷航天三江激光产业技术研究院有限公司 | Optical fiber irradiation monitoring device and method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030020044A1 (en) * | 2001-07-30 | 2003-01-30 | General Electric Company | Scintillator compositions of alkali and rare-earth tungstates |
| CN1903763A (en) * | 2006-08-09 | 2007-01-31 | 中国建筑材料科学研究总院 | Glass scintillator for thermal neutron detection and its preparation method |
| CN104556671A (en) * | 2015-01-19 | 2015-04-29 | 华南理工大学 | Preparation method of transition metal ion doped microcrystalline glass fibers |
| CN105676345A (en) * | 2016-04-06 | 2016-06-15 | 中国科学院上海光学精密机械研究所 | Glass wrapping layer scintillating fiber and preparation method thereof |
| CN106698925A (en) * | 2017-02-22 | 2017-05-24 | 吉林师范大学 | Terbium ion-activated scintillating optical fiber panel and preparation method thereof |
-
2020
- 2020-03-06 CN CN202010150514.0A patent/CN111302643A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030020044A1 (en) * | 2001-07-30 | 2003-01-30 | General Electric Company | Scintillator compositions of alkali and rare-earth tungstates |
| CN1903763A (en) * | 2006-08-09 | 2007-01-31 | 中国建筑材料科学研究总院 | Glass scintillator for thermal neutron detection and its preparation method |
| CN104556671A (en) * | 2015-01-19 | 2015-04-29 | 华南理工大学 | Preparation method of transition metal ion doped microcrystalline glass fibers |
| CN105676345A (en) * | 2016-04-06 | 2016-06-15 | 中国科学院上海光学精密机械研究所 | Glass wrapping layer scintillating fiber and preparation method thereof |
| CN106698925A (en) * | 2017-02-22 | 2017-05-24 | 吉林师范大学 | Terbium ion-activated scintillating optical fiber panel and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| MICHAEL MOORE等: "A multicore compound glass optical fiber for neutron imaging", 《IEEE》 * |
| 李景镇等: "《光学手册》", 31 July 2010, 陕西科学出版社 * |
| 陈艳平: "热中子探测用稀土离子掺杂锂硅酸盐玻璃的制备与荧光性质研究", 《中国优秀博士论文全文数据库•工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112684485A (en) * | 2021-03-22 | 2021-04-20 | 武汉光谷航天三江激光产业技术研究院有限公司 | Optical fiber irradiation monitoring device and method |
| CN112684485B (en) * | 2021-03-22 | 2021-06-18 | 武汉光谷航天三江激光产业技术研究院有限公司 | Optical fiber irradiation monitoring device and method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101538194B1 (en) | Scintillator for neutron detection and neutron detector | |
| US9279891B2 (en) | Transparent glass scintillators, methods of making same and devices using same | |
| Xu et al. | Perovskite nanocrystal doped all-inorganic glass for X-ray scintillators | |
| JP3870418B2 (en) | Phosphor and phosphor composition containing the same | |
| Shan et al. | Luminescent properties of Tb3+ doped high density borogermanate scintillating glasses | |
| CN111499204A (en) | Ce3+Silicate-doped scintillation glass and preparation method and application thereof | |
| CN105293905A (en) | Flashing optical fiber panel and preparation method | |
| JP2010285596A (en) | Oxide crystal for neutron scintillator and neutron scintillator using the same | |
| CN113293435B (en) | Halide perovskite nanocrystalline material based on cerium-doped glass matrix and preparation method thereof | |
| CN114634312A (en) | Doped Al3+CsPbBr of3Quantum dot glass ceramic and preparation method thereof | |
| CN111302643A (en) | Glass optical fiber for neutron detection, scintillation material and preparation method thereof | |
| CN113213766B (en) | Perovskite quantum dot scintillation glass-ceramic and preparation method thereof | |
| CN110451798B (en) | Divalent europium activated lithium borate scintillation glass and preparation method thereof | |
| CN106892564B (en) | Preparation method of high silica scintillation glass | |
| CN112684492A (en) | Halogenated perovskite quantum dot composite material for neutron detection and preparation method thereof | |
| JP4640176B2 (en) | Glass scintillator | |
| CN113860747B (en) | Chloride crystal and glass composite transparent optical functional material and preparation method and application thereof | |
| JP5994149B2 (en) | X-ray scintillator materials | |
| CN114085664A (en) | Perovskite-scintillator monocrystal-based composite scintillator and preparation method thereof | |
| CN110451795A (en) | A kind of high density tellurate scintillation glass and preparation method thereof | |
| CN114133137B (en) | Neutron detection glass scintillator and preparation method and application thereof | |
| CN112723749B (en) | High-transparency microcrystalline glass containing scintillation nanocrystals and preparation method thereof | |
| RU2467354C1 (en) | Barium fluoride-based high-speed scintillation material and method for production thereof (versions) | |
| CN117071070B (en) | Transition metal doped sodium-based halogen scintillation crystal and preparation method and application thereof | |
| JP5842292B2 (en) | Oxide crystal for neutron scintillator and neutron scintillator using the same |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200619 |