CN118084307A - Batch preparation method of infrared chalcogenide glass beads - Google Patents
Batch preparation method of infrared chalcogenide glass beads Download PDFInfo
- Publication number
- CN118084307A CN118084307A CN202410234878.5A CN202410234878A CN118084307A CN 118084307 A CN118084307 A CN 118084307A CN 202410234878 A CN202410234878 A CN 202410234878A CN 118084307 A CN118084307 A CN 118084307A
- Authority
- CN
- China
- Prior art keywords
- glass beads
- chalcogenide glass
- optical fiber
- core optical
- infrared
- 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
- 239000011324 bead Substances 0.000 title claims abstract description 101
- 239000005387 chalcogenide glass Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000011521 glass Substances 0.000 claims abstract description 79
- 239000013307 optical fiber Substances 0.000 claims abstract description 79
- 238000010438 heat treatment Methods 0.000 claims abstract description 51
- 239000000835 fiber Substances 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 22
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 238000007873 sieving Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000003365 glass fiber Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 33
- 239000004697 Polyetherimide Substances 0.000 claims description 16
- 229920001601 polyetherimide Polymers 0.000 claims description 16
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000005253 cladding Methods 0.000 abstract description 5
- 239000004005 microsphere Substances 0.000 abstract description 4
- 239000011325 microbead Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/10—Forming beads
- C03B19/1005—Forming solid beads
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a batch preparation method of infrared chalcogenide glass beads. Firstly, preparing a multi-core optical fiber with a fiber core of chalcogenide glass and a cladding of thermoplastic polymer; then tightly stacking a plurality of multi-core optical fibers into a metal mold, and placing the metal mold into a vacuum furnace for heat treatment, so that glass fiber cores in the multi-core optical fibers are broken to form glass beads; and finally, putting the thermally treated multi-core optical fiber into an organic solvent to dissolve out the thermoplastic polymer, and then washing, sieving and drying the thermoplastic polymer by using absolute ethyl alcohol to obtain the glass beads with uniform size. The preparation method can obviously reduce the consumption of the polymer and the organic solvent; the number of the chalcogenide glass beads prepared at a time can reach more than million; the prepared chalcogenide glass microsphere has smaller eccentricity and higher quality factor, and can be applied to the fields of infrared regression reflection, microcavity sensing, infrared laser generation, nonlinear optics and the like.
Description
Technical Field
The invention relates to a preparation method of glass beads, in particular to a batch preparation method of infrared chalcogenide glass beads.
Background
Glass beads are a high-performance reflective material (also known as retroreflective material or retro-reflective material) and have been widely used in the fields of road safety, architectural decoration, aerospace, etc. The glass microsphere is also an optical resonant cavity with excellent performance, has the characteristics of high quality factor, small mode volume, narrow resonant mode line width, high intra-cavity energy density and the like, and has great application potential in the fields of high-sensitivity sensors, narrow-band filters, low-threshold lasers, nonlinear optics and the like. In recent years, with the progress of infrared technology, there has been an increasing demand for infrared glass beads operating in high-transparency windows of 3 to 5 μm and 8 to 12 μm in atmosphere, for example, aerospace equipment requiring a large number of glass beads having diameters of 50 to 300 μm as infrared reflecting materials.
Chalcogenide glass (amorphous material formed based on chalcogenides S, se, te) is the only glass material that can cover the light transmission range of 3 to 5 μm and 8 to 12 μm wavelength bands, and has a high refractive index, excellent chemical stability and thermal stability, so that chalcogenide glass beads are considered as excellent infrared reflecting materials. At present, three main methods for preparing chalcogenide glass beads are available. The first method is a "high temperature melting powder method", i.e. pouring chalcogenide glass powder into a tube furnace with a protective atmosphere, and the powder is heated to form balls by surface tension during the falling process in the furnace chamber. When the method is used for preparing the microbeads, the chalcogenide glass powder is seriously volatilized by heating, the balling rate is low, and the material utilization rate is generally less than 10 percent from glass crushing and sieving to final balling. The second method is the "fiber ball-melt method", i.e., a laser or ring heater is used to heat the tiny end of the fiber to obtain the microbeads. The quality factor of the microbeads prepared by the method is extremely high, but only a few microbeads can be prepared at one time, and the preparation efficiency is extremely low. The third method is the "fiber-optic core melting method" (ZL 201310593026.7), i.e., heating the chalcogenide glass/polymer composite fiber to about the glass softening temperature, and breaking the chalcogenide glass filaments inside the polymer to form microbeads. By adopting the method, a large amount of microbeads can be prepared at one time, the material utilization rate is usually more than 30%, the quality factor of the microbeads is high, but the microbeads are formed by using optical fibers with thick polymer cladding to realize better binding of fiber cores at high temperature, so that a large amount of expensive polymers and organic solvents for dissolving the polymers are consumed, and the low-cost mass preparation of the chalcogenide glass microbeads is difficult to realize.
Disclosure of Invention
Aiming at the problems of low preparation efficiency and difficulty in realizing low-cost large-batch preparation of chalcogenide glass beads in the prior art, the invention provides a batch preparation method of infrared chalcogenide glass beads by accumulating multi-core optical fibers with thinner polymer cladding and performing heat treatment to greatly improve the preparation efficiency of the glass beads and reduce the preparation cost.
In order to solve the problems in the prior art, the invention adopts the following technical scheme:
the batch preparation method of the infrared chalcogenide glass beads comprises the following steps:
(1) Preparation of multicore optical fibers
Preparing a chalcogenide glass rod with the diameter of d 1 in a vacuum quartz tube by adopting a melting-quenching method, and inserting the chalcogenide glass rod into a thermoplastic polymer sleeve with the inner diameter and the outer diameter of d 1 and d 2 respectively to form a first optical fiber preform, wherein d 2/d1 = 1.4-2.0; drawing the first optical fiber preform into a thin rod with a diameter d 3; tightly stacking a plurality of thin rods into a hollow cuboid metal mold, and then performing heat treatment on the tightly stacked thin rods to adhere thermoplastic polymers on the surfaces of the thin rods together to form a second optical fiber preform; drawing the second optical fiber preform into a multi-core optical fiber with a diagonal length d 4;
(2) Preparation of chalcogenide glass beads by heat treatment of multi-core optical fiber
Tightly stacking a plurality of multi-core optical fibers prepared in the step (1) into a hollow cuboid metal mold, plugging two ports of the mold, placing the mold into a vacuum furnace, vacuumizing to enable the vacuum degree in the furnace to be less than 1kPa, and then raising the furnace temperature to 300-360 ℃ for heat treatment for 10-30 minutes to enable glass fiber cores in the multi-core optical fibers to be broken to form glass beads;
(3) Cleaning the polymer and sieving to obtain uniform-size chalcogenide glass beads
Taking the multicore fiber after the heat treatment in the step (2) out of the metal mold, putting the multicore fiber into a beaker containing an organic solvent and a magnet, putting the beaker on a heating platform of a magnetic stirrer, and setting the temperature of the heating platform to enable the thermoplastic polymer to be rapidly dissolved into the organic solvent along with stirring and heating; changing the organic solvent once every 30-60 minutes, and continuously changing for 3-5 times to completely dissolve the thermoplastic polymer; washing the glass beads in the beaker with absolute ethyl alcohol for 3-5 times, and sieving the glass beads and the absolute ethyl alcohol together to obtain the glass beads with uniform size; and finally, drying the glass beads.
Preferably, the glass transition temperature of the chalcogenide glass rod in the step (1) is 160 to 200 ℃.
Preferably, the material of the thermoplastic polymer sleeve in step (1) is Polyetherimide (PEI), polyethersulfone (PES) or Polysulfone (PSU).
Preferably, the diameter d 3＝1.5～3mm;d4 >800 μm in step (1).
Preferably, the glass beads in step (2) have a diameter of 60 to 300. Mu.m.
Preferably, in the step (3), the organic solvent is dimethylacetamide, and the temperature set by the heating platform is 50-60 ℃.
The beneficial effects are that:
compared with the prior art, the batch preparation method of the infrared chalcogenide glass beads has the following advantages:
(1) The invention prepares the chalcogenide glass beads through the way of preparing the multi-core optical fibers, closely stacking a plurality of multi-core optical fibers and performing heat treatment, and can greatly improve the preparation efficiency by increasing the number of cores in the multi-core optical fibers and the number of stacked multi-core optical fibers, and the number of beads prepared at a time can reach more than million.
(2) The close packing of the multi-core optical fibers in the preparation method promotes the mutual binding between the optical fibers, and even if a thinner thermoplastic polymer cladding layer is used, the sufficient binding can be realized to ensure the formation of microbeads in the heat treatment process. Compared with the existing method for preparing microbeads by heat-treating optical fibers, the method reduces the ratio of the cladding diameter of the thermoplastic polymer to the core diameter of the thermoplastic polymer (= d 2/d1) from more than or equal to 3 to 1.4-2.0, reduces the polymer consumption by more than half, reduces the organic solvent consumption for dissolving the polymer by more than half, and can obviously reduce the cost.
(3) The invention can be used for preparing chalcogenide glass beads with the diameter of 60-300 mu m, the eccentricity of less than 2 percent and the microcavity quality factor Q of more than or equal to 2x10 5, and has great application prospect in the fields of infrared retro-reflection, microcavity sensing, infrared laser generation, nonlinear optics and the like.
Drawings
FIG. 1 is a schematic view of the first optical fiber preform preparation (left), the second optical fiber preform preparation (middle) and the multicore optical fiber close-packing (right) in example 1;
FIG. 2 is an optical photograph of the chalcogenide glass beads prepared in example 1;
FIG. 3 is an optical photograph of the chalcogenide glass beads prepared in comparative example 1;
FIG. 4 is an optical photograph of the chalcogenide glass beads prepared in comparative example 2.
Detailed Description
The following examples further illustrate the invention but are not to be construed as limiting the invention. Modifications and substitutions to the method, steps or conditions of the invention without departing from the spirit and nature of the invention are intended to be within the scope of the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated.
Example 1
The chemical formula of the sulfur-based glass beads prepared in the embodiment is Ge 10As30Se40Te20, and the glass transition temperature of the glass is 170 ℃. The preparation method comprises the following steps: preparing a Ge 10As30Se40Te20 chalcogenide glass rod (weight about 130 g) with the diameter of 15mm and the length of 150mm in a vacuum quartz tube by using simple substances of Ge, as, se and Te with the purity of more than or equal to 99.999% As raw materials through a melting-quenching method, and inserting the Ge 10As30Se40Te20 chalcogenide glass rod into a Polyetherimide (PEI) sleeve with the inner diameter and the outer diameter of 15mm and 24mm respectively to form a first optical fiber preform, wherein the first optical fiber preform is shown in a left diagram in FIG. 1; drawing the first optical fiber preform into a thin rod with a diameter of 2 mm; closely stacking 60 thin rods with the length of about 280mm into a hollow cuboid metal mold, and then performing heat treatment on the closely stacked thin rods to adhere PEI (polyethylene terephthalate) on the surfaces of the closely stacked thin rods together to form a second optical fiber preform with the size of about 16mm x 14.1mm x 280mm, as shown in the middle diagram in fig. 1; drawing the second optical fiber preform into a multicore fiber having a diagonal length of about 850 μm, wherein the corresponding multicore fiber has a single core diameter of about 50 μm; 900 multicore fibers with the length of about 175mm are closely piled up in a hollow cuboid metal mold, as shown in the right diagram in fig. 1, and then two ports of the mold are plugged; placing a die provided with the multi-core optical fiber into a vacuum furnace, vacuumizing to enable the vacuum degree in the furnace to be less than 1kPa, and then heating the furnace to 340 ℃ for 20 minutes to enable the glass fiber cores in the multi-core optical fiber to be broken to form glass beads; taking the heat-treated multi-core optical fiber out of a metal mold, putting the multi-core optical fiber into a beaker containing dimethylacetamide and a magnet, then putting the beaker on a heating platform of a magnetic stirrer, setting the temperature of the heating platform to be 50 ℃, and enabling PEI to be dissolved into an organic solvent rapidly along with stirring and heating; changing the organic solvent once every 60 minutes, and continuously changing for 3 times to completely dissolve PEI; washing the glass beads in the beaker with absolute ethyl alcohol for 5 times, and then sieving the glass beads and the absolute ethyl alcohol together through a 80-mesh sieve and a 100-mesh sieve to obtain the glass beads with uniform size; and finally, drying the glass beads.
The size and the eccentricity of the glass beads are measured by an optical microscope with size calibration, the weight of the glass beads is weighed by an electronic balance with the precision of 0.01g, and the microcavity quality factor Q is measured by a tapered optical fiber coupling measurement system.
The detection result shows that: more than 80% of the obtained glass beads have a diameter of 160-180 μm, and the eccentricity of the glass beads is less than 2%, as shown in figure 2; the glass beads have a weight of about 51.48g and about 3.7x10 6 glass beads; microcavity quality factor q=4x 5 (@ 8.3 μm).
Example 2
The chemical formula of the sulfur-based glass beads prepared in the embodiment is As 40S60, and the glass transition temperature of the glass is 200 ℃. The preparation method comprises the following steps: as and S simple substances with purity more than or equal to 99.999% are used As raw materials, an As 40S60 chalcogenide glass rod (weight about 84.6 g) with diameter of 15mm and length of 150mm is prepared in a vacuum quartz tube by adopting a melting-quenching method, and is inserted into a polyether sulfone (PES) sleeve with inner and outer diameters of 15mm and 30mm respectively to form a first optical fiber preform; drawing the first optical fiber preform into a thin rod with a diameter of 1.5 mm; tightly stacking 189 thin rods with the length of about 250mm into a hollow cuboid metal mold, and then performing heat treatment on the tightly stacked thin rods to adhere PES on the surfaces of the thin rods together to form a second optical fiber preform with the size of about 21mm x 18.4mm x 250mm; drawing the second optical fiber preform into a multicore fiber having a diagonal length of about 930 μm, wherein the corresponding multicore fiber has a single core diameter of about 25 μm; tightly stacking 900 multicore fibers with the length of about 225mm into a hollow cuboid metal mold, and then plugging two ports of the mold; placing a die provided with the multi-core optical fiber into a vacuum furnace, vacuumizing to enable the vacuum degree in the furnace to be less than 1kPa, and then raising the furnace temperature to 360 ℃ for heat treatment for 30 minutes to enable the glass fiber cores in the multi-core optical fiber to be broken to form glass beads; taking out the heat-treated multicore fiber from the metal mold, putting the multicore fiber into a beaker containing dimethylacetamide and a magnet, then putting the beaker on a heating platform of a magnetic stirrer, setting the temperature of the heating platform to be 60 ℃, and enabling PES to be dissolved into an organic solvent rapidly along with stirring and heating; changing the organic solvent every 30 minutes, and continuously changing for 5 times to completely dissolve PES; washing the glass beads in the beaker with absolute ethyl alcohol for 3 times, and then sieving the glass beads and the absolute ethyl alcohol together through a 200-mesh sieve and a 230-mesh sieve to obtain the glass beads with uniform size; and finally, drying the glass beads.
The size and the eccentricity of the glass beads are measured by an optical microscope with size calibration, the weight of the glass beads is weighed by an electronic balance with the precision of 0.01g, and the microcavity quality factor Q is measured by a tapered optical fiber coupling measurement system.
The detection result shows that: more than 80% of the obtained glass beads have diameters of 60-70 mu m, and the eccentricity of the glass beads is less than 2%; the weight of the glass beads is about 32.32g, and the glass beads contain 7.0x10 7 glass beads; microcavity quality factor q=2x 5 (@ 4.6 μm).
Example 3
The chemical formula of the sulfur-based glass beads prepared in the embodiment is As 37Se63, and the glass transition temperature of the glass is 160 ℃. The preparation method comprises the following steps: as and Se simple substances with purity more than or equal to 99.999% are used As raw materials, an As 37Se63 chalcogenide glass rod (weight about 122 g) with diameter of 15mm and length of 150mm is prepared in a vacuum quartz tube by adopting a melting-quenching method, and is inserted into a Polysulfone (PSU) sleeve with inner and outer diameters of 15mm and 21mm respectively to form a first optical fiber preform; drawing the first optical fiber preform into a thin rod with a diameter of 3 mm; tightly stacking 39 thin rods with the length of about 150mm into a hollow cuboid metal mold, and then performing heat treatment on the tightly stacked thin rods to adhere PSU on the surfaces of the thin rods together to form a second optical fiber preform with the size of about 18mm x 18.6mm x 150mm; drawing the second optical fiber preform into a multicore fiber having a diagonal length of about 1200 μm, wherein the corresponding multicore fiber has a single core diameter of about 100 μm; tightly stacking 440 multicore fibers with the length of about 140mm into a hollow cuboid metal mold, and then plugging two ports of the mold; placing a die provided with the multi-core optical fiber into a vacuum furnace, vacuumizing to enable the vacuum degree in the furnace to be less than 1kPa, and then heating the furnace to 300 ℃ for 10 minutes to enable the glass fiber cores in the multi-core optical fiber to be broken to form glass beads; taking the heat-treated multi-core optical fiber out of the metal mold, putting the multi-core optical fiber into a beaker containing dimethylacetamide and a magnet, then putting the beaker on a heating platform of a magnetic stirrer, setting the temperature of the heating platform to be 55 ℃, and enabling PSU to be dissolved into an organic solvent quickly along with stirring and heating; changing the organic solvent once every 45 minutes, and continuously changing for 4 times to completely dissolve PSU; washing the glass beads in the beaker with absolute ethyl alcohol for 4 times, and then sieving the glass beads and the absolute ethyl alcohol together by a 50-mesh sieve and a 60-mesh sieve to obtain the glass beads with uniform size; and finally, drying the glass beads.
The size and the eccentricity of the glass beads are measured by an optical microscope with size calibration, the weight of the glass beads is weighed by an electronic balance with the precision of 0.01g, and the microcavity quality factor Q is measured by a tapered optical fiber coupling measurement system.
The detection result shows that: more than 80% of the obtained glass beads have diameters of 270-300 mu m, and the eccentricity of the glass beads is less than 2%; the glass beads have a weight of about 50.95g and about 1.1x10 6 glass beads; microcavity quality factor q=6x 5 (@ 4.6 μm).
Comparative example 1
The chemical formula of the chalcogenide glass bead prepared in the comparative example is Ge 10As30Se40Te20, the glass transition temperature of the glass is 170 ℃, and the preparation method is mainly different from that of example 1 in that d 2/d1 is less than 1.4, and the specific preparation method is as follows: preparing a Ge 10As30Se40Te20 chalcogenide glass rod (weight about 130 g) with the diameter of 15mm and the length of 150mm in a vacuum quartz tube by using simple substances of Ge, as, se and Te with the purity of more than or equal to 99.999% As raw materials through a melting-quenching method, and inserting the Ge 10As30Se40Te20 chalcogenide glass rod into a PEI sleeve with the inner diameter and the outer diameter of 15mm and 19.5mm respectively to form a first optical fiber preform; drawing the first optical fiber preform into a thin rod with a diameter of 1.63 mm; tightly stacking 60 thin rods with the length of about 280mm into a hollow cuboid metal mold, and then performing heat treatment on the tightly stacked thin rods to adhere PEI (polyethylene terephthalate) on the surfaces of the thin rods together to form a second optical fiber preform with the size of about 13mm x 11.5mm x 280mm; drawing the second optical fiber preform into a multicore fiber having a diagonal length of about 700 μm, wherein the corresponding multicore fiber has a single core diameter of about 50 μm; tightly stacking 900 multicore fibers with the length of about 175mm into a hollow cuboid metal mold, and then plugging two ports of the mold; placing a die provided with the multi-core optical fiber into a vacuum furnace, vacuumizing to enable the vacuum degree in the furnace to be less than 1kPa, and then heating the furnace to 340 ℃ for 20 minutes to enable the glass fiber cores in the multi-core optical fiber to be broken to form glass beads; taking the heat-treated multi-core optical fiber out of a metal mold, putting the multi-core optical fiber into a beaker containing dimethylacetamide and a magnet, then putting the beaker on a heating platform of a magnetic stirrer, setting the temperature of the heating platform to be 50 ℃, and enabling PEI to be dissolved into an organic solvent rapidly along with stirring and heating; changing the organic solvent once every 60 minutes, and continuously changing for 3 times to completely dissolve PEI; washing glass beads in a beaker with absolute ethyl alcohol for 5 times, and then sieving the glass beads and the absolute ethyl alcohol together through a sieve of 80 meshes and a sieve of 100 meshes; and finally, drying the glass microspheres.
Glass beads were observed using a size-calibrated optical microscope, and it was found that a large number of glass cores of the multicore fibers failed to form beads after breakage, and the balling rate was very low, as shown in fig. 3.
As can be seen from the results of comparative example 1, comparative example 1 is difficult to form microbeads, and has a very low balling rate, which is associated with an excessively thin polymer coating, and the thinner polymer does not sufficiently bind the fracture deformed core to form microbeads upon heat treatment.
Comparative example 2
The chemical formula of the chalcogenide glass beads prepared in the comparative example is Ge 10As30Se40Te20, the glass transition temperature of the glass is 170 ℃, and the preparation method is mainly different from that of the embodiment 1 in that the multi-core optical fibers are not closely packed, but a plurality of multi-core optical fibers are randomly placed in a vacuum furnace for heat treatment. The preparation method comprises the following steps: preparing a Ge 10As30Se40Te20 chalcogenide glass rod (weight about 130 g) with the diameter of 15mm and the length of 150mm in a vacuum quartz tube by using simple substances of Ge, as, se and Te with the purity of more than or equal to 99.999% As raw materials through a melting-quenching method, and inserting the Ge 10As30Se40Te20 chalcogenide glass rod into a PEI sleeve with the inner diameter and the outer diameter of 15mm and 24mm respectively to form a first optical fiber preform; drawing the first optical fiber preform into a thin rod with a diameter of 2 mm; tightly stacking 60 thin rods with the length of about 280mm into a hollow cuboid metal mold, and then performing heat treatment on the tightly stacked thin rods to adhere PEI (polyethylene terephthalate) on the surfaces of the thin rods together to form a second optical fiber preform with the size of about 16mm x 14.1mm x 280mm; drawing the second optical fiber preform into a multicore fiber having a diagonal length of about 850 μm, wherein the corresponding multicore fiber has a single core diameter of about 50 μm; randomly placing 900 multicore fibers with the length of about 175mm into a metal tray; placing the metal tray into a vacuum furnace, and vacuumizing to enable the vacuum degree in the furnace to be less than 1kPa; then the furnace temperature is increased to 340 ℃ for heat treatment for 20 minutes, so that glass fiber cores in the multi-core optical fiber are broken to form glass beads; taking out the heat-treated multicore fiber from the metal tray, putting the multicore fiber into a beaker containing dimethylacetamide and a magneton, then putting the beaker on a heating platform of a magnetic stirrer, setting the temperature of the heating platform to be 50 ℃, and enabling PEI to be dissolved into an organic solvent rapidly along with stirring and heating; changing the organic solvent once every 60 minutes, and continuously changing for 3 times to completely dissolve PEI; and washing the glass beads in the beaker with absolute ethyl alcohol for 5 times, and finally drying the glass beads.
The glass beads were observed using a size-calibrated optical microscope, and it was found that the obtained glass beads were very non-uniform in size (150 to 500 μm) and that a large number of the beads were oval-shaped, as shown in fig. 4.
As can be seen from the results of comparative example 2, the glass beads were not uniform in size and a large number of beads were oval, all of which were related to the binding state of the polymer to the glass cores during the heat treatment, and when the multicore fibers were arranged in a disordered manner, no uniform binding could be formed between neighboring multicore fibers, so that the glass beads were formed in size very non-uniformly.
In summary, the chalcogenide glass beads are prepared by the method of preparing the multi-core optical fibers, closely stacking a plurality of multi-core optical fibers and performing heat treatment, and the preparation efficiency can be greatly improved by increasing the number of cores in the multi-core optical fibers and the number of stacked multi-core optical fibers, and the number of beads prepared at a time can reach more than million. The prepared chalcogenide glass microsphere has the diameter of 60-300 mu m, the eccentricity of less than 2 percent, the microcavity quality factor Q is more than or equal to 2x10 5, and has great application prospect in the fields of infrared regression reflection, microcavity sensing, infrared laser generation, nonlinear optics and the like.
The invention and its embodiments have been described above by way of illustration and not limitation, and the invention is illustrated in the accompanying drawings and described in the drawings in which the actual structure is not limited thereto. Therefore, if one of ordinary skill in the art is informed by this disclosure, the structural mode and the embodiments similar to the technical scheme are not creatively designed without departing from the gist of the present invention.
Claims (6)
1. The batch preparation method of the infrared chalcogenide glass beads is characterized by comprising the following steps of:
(1) Preparation of multicore optical fibers
Preparing a chalcogenide glass rod with the diameter of d 1 in a vacuum quartz tube by adopting a melting-quenching method, and inserting the chalcogenide glass rod into a thermoplastic polymer sleeve with the inner diameter and the outer diameter of d 1 and d 2 respectively to form a first optical fiber preform, wherein d 2/d1 = 1.4-2.0; drawing the first optical fiber preform into a thin rod with a diameter d 3; tightly stacking a plurality of thin rods into a hollow cuboid metal mold, and then performing heat treatment on the tightly stacked thin rods to adhere thermoplastic polymers on the surfaces of the thin rods together to form a second optical fiber preform; drawing the second optical fiber preform into a multi-core optical fiber with a diagonal length d 4;
(2) Preparation of chalcogenide glass beads by heat treatment of multi-core optical fiber
Tightly stacking a plurality of multi-core optical fibers prepared in the step (1) into a hollow cuboid metal mold, plugging two ports of the mold, placing the mold into a vacuum furnace, vacuumizing to enable the vacuum degree in the furnace to be less than 1kPa, and then raising the furnace temperature to 300-360 o ℃ for heat treatment for 10-30 minutes to enable glass fiber cores in the multi-core optical fibers to be broken to form glass beads;
(3) Cleaning the polymer and sieving to obtain uniform-size chalcogenide glass beads
Taking the multicore fiber after the heat treatment in the step (2) out of the metal mold, putting the multicore fiber into a beaker containing an organic solvent and a magnet, putting the beaker on a heating platform of a magnetic stirrer, and setting the temperature of the heating platform to enable the thermoplastic polymer to be rapidly dissolved into the organic solvent along with stirring and heating; changing the organic solvent once every 30-60 minutes, and continuously changing for 3-5 times to completely dissolve the thermoplastic polymer; washing the glass beads in the beaker with absolute ethyl alcohol for 3-5 times, and sieving the glass beads and the absolute ethyl alcohol together to obtain the glass beads with uniform size; and finally, drying the glass beads.
2. The method for batch preparation of the infrared chalcogenide glass beads according to claim 1, wherein the method comprises the following steps: the glass transition temperature of the chalcogenide glass rod in the step (1) is 160 oC~200 o C.
3. The method for batch preparation of the infrared chalcogenide glass beads according to claim 1, wherein the method comprises the following steps: the thermoplastic polymer sleeve in the step (1) is made of polyetherimide, polyethersulfone or polysulfone.
4. The method for batch preparation of the infrared chalcogenide glass beads according to claim 1, wherein the method comprises the following steps: the diameter d 3=1.5~3 mm;d4 in step (1) is >800 μm.
5. The method for batch preparation of the infrared chalcogenide glass beads according to claim 1, wherein the method comprises the following steps: and (3) the diameter of the glass beads in the step (2) is 60-300 mu m.
6. The method for batch preparation of the infrared chalcogenide glass beads according to claim 1, wherein the method comprises the following steps: the organic solvent in the step (3) is dimethylacetamide; the temperature set by the heating platform is 50 oC~60 o C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410234878.5A CN118084307A (en) | 2024-03-01 | 2024-03-01 | Batch preparation method of infrared chalcogenide glass beads |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410234878.5A CN118084307A (en) | 2024-03-01 | 2024-03-01 | Batch preparation method of infrared chalcogenide glass beads |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118084307A true CN118084307A (en) | 2024-05-28 |
Family
ID=91163017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410234878.5A Pending CN118084307A (en) | 2024-03-01 | 2024-03-01 | Batch preparation method of infrared chalcogenide glass beads |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118084307A (en) |
-
2024
- 2024-03-01 CN CN202410234878.5A patent/CN118084307A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Luo et al. | Toward optical fibre fabrication using 3D printing technology | |
| US7286739B2 (en) | Porous optical fiber and method for manufacturing the same | |
| US6968107B2 (en) | Holey optical fibres | |
| US20100104869A1 (en) | Photonic Crystal Fibers and Methods for Manufacturing the Same | |
| CN104181636B (en) | The flexible infrared chalcogenide glass fiber coherent fiber bundle of high-resolution and preparation method | |
| GB2365992A (en) | Compound glass holey fibre | |
| JP4466813B2 (en) | Glass preform and method for producing the same | |
| US20050147366A1 (en) | Constructing preforms from capillaries and canes | |
| JP2002529357A (en) | Method and apparatus for manufacturing optical fiber | |
| Luo et al. | 3D printing specialty multi-function twin core Bi/Er co-doped silica optical fibres for ultra-broadband polarized near infrared emission and sensing applications | |
| CN118084307A (en) | Batch preparation method of infrared chalcogenide glass beads | |
| JP2004020836A (en) | Optical fiber and its manufacturing method | |
| WO2003058309A1 (en) | A method and apparatus relating to microstructured optical fibres | |
| WO2003093884A2 (en) | A method and apparatus relating to optical fibres | |
| JP5539594B2 (en) | Fiber and fiber manufacturing method | |
| CN103613276B (en) | A kind of preparation method of high-performance chalcogenide glass microballoon | |
| WO2003100488A1 (en) | Optical waveguide, method of its production, and its use | |
| US20050172674A1 (en) | Method for fabricating preform for holey fiber | |
| EP1309890B1 (en) | Holey optical fibres, preforms and manufacturing methods | |
| EP1571131A2 (en) | Method of fabricating a preform for holey optical fibre | |
| Yu et al. | A new generation of plastic optical fibers and its functional exploiting | |
| JPH0791087B2 (en) | Ge-As-S glass fiber having core-clad structure | |
| CN117192680A (en) | Special optical fiber with super structure and preparation method and application thereof | |
| CN113126199A (en) | Hollow inner suspension core optical fiber and manufacturing method thereof | |
| Shaukat et al. | A COMPARISON OF THE TRANSMISSION LOSSES OF DIFFERENT OPTICAL FIBER MATERIALS |
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 |