CN115594388B - Preparation method of intermediate infrared band low-absorption As-Se chalcogenide glass - Google Patents
Preparation method of intermediate infrared band low-absorption As-Se chalcogenide glass Download PDFInfo
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- CN115594388B CN115594388B CN202211340598.XA CN202211340598A CN115594388B CN 115594388 B CN115594388 B CN 115594388B CN 202211340598 A CN202211340598 A CN 202211340598A CN 115594388 B CN115594388 B CN 115594388B
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- 239000005387 chalcogenide glass Substances 0.000 title claims abstract description 36
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000010453 quartz Substances 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003708 ampul Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims description 53
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000010583 slow cooling Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000012856 weighed raw material Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000004821 distillation Methods 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 1
- 238000004904 shortening Methods 0.000 abstract 1
- 239000011669 selenium Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004433 infrared transmission spectrum Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/235—Heating the glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- 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
- C03C3/00—Glass compositions
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
- C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/10—Compositions for glass with special properties for infrared transmitting glass
-
- 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
Abstract
A process for preparing the As-Se chalcogenide glass with low absorption in mid-infrared band includes such steps As preparing the particles of high-purity raw material, low-hydroxy quartz ampoule bottle, special heating element structure and special heat treating. Aiming at the mid-infrared region at the wave band of 2-8 um, the method can obviously reduce the impurity absorption; meanwhile, compared with the traditional preparation (distillation technology) of high-purity chalcogenide glass, the method has the advantages of greatly shortening the production period, simplifying the complicated process, having high efficiency, low energy consumption and the like, and providing powerful guarantee for commercial mass production.
Description
Technical Field
The invention relates to the technical field of selenium-based chalcogenide glass, in particular to a preparation method of intermediate infrared band low-absorption As-Se chalcogenide glass.
Background
At present, the infrared chalcogenide glass products marketed at home and abroad can realize athermalization design, and the working temperature is as follows: the infrared transmission rate is more than 80 percent at the temperature of between 40 ℃ below zero and 80 ℃ below zero, and the number of the commercial brands is not less than six, wherein As 40 Se 60 The sulfur-based glass has a material cost of about 1/2 of the cost of the other two materials, and As because the glass component does not contain expensive element germanium 40 Se 60 The chalcogenide glass has excellent optical performance, high refractive index and Abbe number, and low refractive index and temperature coefficient determine that the chalcogenide glass is the most used optical lens material at present.
The existence of impurities in the chalcogenide glass seriously affects the infrared transmission performance of the chalcogenide glass, especially the absorption peak of hydroxyl and water at the wave band of 2-8 um, and the wave band is the most important infrared wave band in military at present, and the mid-infrared material based on the working wave band plays an important role in modern defense and photoelectric countermeasure technologies. With the continuous development of infrared technology, higher requirements are also put on the comprehensive performance of the mid-infrared material, for example, the mid-infrared material has high optical quality, low scattering and thermal distortion in the working band; can withstand erosion of rain sand in high-speed flight; the thermal shock resistance is good; in addition, the material must be optically isotropic; easy realization of large-size high optical quality, preparation of complex shape, low cost, etc.
The earliest university of Ningbo invented a closed distillation method (a device and a method for preparing high-purity chalcogenide glass, authorized bulletin number: CN 1014922358B), mainly aiming at oxygen impurities between 8 and 12 um; then, an deoxidizer and a dehydrogenation agent are combined with a twice distillation method (a dynamic total distillation purification method of low-hydroxyl high-purity chalcogenide glass, an authorized publication number CN 102531335B) to mainly aim at hydroxyl impurities between 3 and 5um, and the process is relatively complex. Gallium chloride invented by Jiangsu university is used as a dehydrogenation agent and is matched with a traditional deoxidizer to be combined with a dynamic distillation method (a preparation method of high-purity low-loss chalcogenide glass, authorized publication number CN 103332851B), and because the ultra-dry gallium chloride which is easy to deliquesce and oxidize is adopted, the requirement on the operation environment is high, the whole process is required to be carried out in a dry inert gas environment, and the process is complex.
Therefore, it is not easy to find a high-efficiency simple infrared glass preparation method, and meanwhile, the commercial large-size chalcogenide glass which can meet the requirements of low impurity absorption defects and is easy to realize high optical quality, low cost and mass production can be obtained.
Disclosure of Invention
In order to solve the technical problems, the invention provides the preparation method of the As-Se chalcogenide glass which is simple to operate and can meet the low absorption of the mid-infrared band under the condition of the original complex preparation process of full dynamic distillation and purification. The method is a mode of combining a heating furnace structure suitable for mass production and a certain heat treatment process system curve, and particularly has obvious improvement effect on absorption of hydroxyl and water at a wave band of 2-8 um.
The preparation method of the As-Se chalcogenide glass with low absorption in the mid-infrared band comprises the following steps:
step one: selecting a plurality of quartz ampoule bottles with low hydroxyl content (below 3 ppm), firstly soaking the quartz ampoule bottles with 25-30wt% of hydrofluoric acid for 20-30 min, then cleaning the quartz ampoule bottles with deionized water and absolute ethyl alcohol in sequence, and drying the quartz ampoule bottles in a vacuum drying oven at 150-200 ℃ for 10 hours.
Step two: high purity (99.9999%) As and Se are placed in a glove box protected by high purity nitrogen (99.999%) and according to the chemical component As of the prepared As-Se chalcogenide glass 40-x Se 60+x And (0) x is more than or equal to 1.4), calculating the mass of each raw material, and weighing.
Step three: putting the weighed raw materials into quartzThe ampoule bottle is placed into a heating furnace device for pre-vacuumizing under the protection of high-purity inert gas, a mechanical pump in a molecular pump unit is started, residual gas on the inner wall of a quartz tube is gradually pumped out, and the mechanical pump is pumped to be vacuumized to 10 -3 Pa for 1 hour, then starting the heating furnace, gradually heating from room temperature to 200deg.C, gradually pumping out the bound water and adsorbed water adsorbed between the surfaces of the raw materials, and simultaneously starting the molecular pump until the vacuum degree is 10 -5 Pa, preserving heat for 2 hours, and sealing the quartz tube in a melting way.
Step four: and (3) melting in a swinging furnace, wherein the melting comprises seven stages:
the first stage: heating stage, heating rate: 1.83-2.75 ℃/min, cooling the raw materials and the quartz tube fitting which are sealed in the quartz ampoule bottle to room temperature, taking out from the vacuum chamber, moving to a swinging furnace for heating, heating to 350 ℃ from room temperature for 2-3 h, and preserving heat for 30min, namely starting swinging;
and a second stage: heating stage, heating rate: heating to 450 ℃ from 350 ℃ at 1.67 ℃/min for 1h, and preserving heat for 30min;
and a third stage: heating stage, heating rate: heating to 550deg.C from 450deg.C at 1.67 deg.C/min for 1h, and maintaining for 30min;
fourth stage: heating stage, heating rate: heating to 750 ℃ from 550 ℃ at 1.67 ℃/min for 2h;
fifth stage: a heat preservation smelting stage, wherein the heat preservation time is 12 hours at 750 ℃; ensuring that the raw materials are completely melted and fully mixed uniformly;
sixth stage: cooling stage, cooling rate: 2.5 ℃/min, cooling time: 1h, cooling to 600 ℃ from 750 ℃ and stopping swinging;
seventh stage: after stopping swinging, centralizing the swinging furnace, standing for 1.5-2h, and cooling from 600 ℃ to 550 ℃ to prepare for discharging and cooling.
Step five: and (5) discharging, cooling, and annealing and forming.
The annealing process is as follows:
the first stage: heating stage, heating rate: heating from 20 ℃ to 190 ℃ at a speed of 21.25 ℃/h for 8h, and preserving heat for 5h;
and a second stage: slow cooling stage, cooling rate: 2.5 ℃/h, cooling time is 20h, cooling from 190 ℃ to 140 ℃, and preserving heat for 1h;
and a third stage: and in the rapid cooling stage, the cooling rate is as follows: 6 ℃/h and 20h of cooling time, cooling to 20 ℃ from 140 ℃, and taking out to obtain the As-Se chalcogenide glass with low absorption in the mid-infrared band.
In the early research of the applicant (a preparation method of high-purity Ge-Sb-Se system infrared chalcogenide glass, publication No. CN 112608025A) an efficient purification and impurity removal process is provided, and Al is introduced 2 O 3 As deoxidizing agent, teCl 4 As a water scavenger, the process is relatively complex. The As-Se chalcogenide glass provided by the invention has the advantages that the fact that the glass component contains the serious poison As (arsenic) is considered, and the extremely toxic As gas volatilized out by improper operation is very harmful to human bodies, so that a distillation method is not suggested. In addition, the process of secondary transition and the like in the distillation process needs tube breaking remelting, is harmful to human bodies, and is extremely easy to adsorb impurities for secondary introduction, therefore, the invention provides an improvement method based on the original method, a one-step heating furnace heating and a corresponding operation method are added in the vacuumizing process, and a specific heat treatment process system is adopted, and As, se and H are utilized 2 The melting point of O and the saturated air pressure difference of the gas state at the same temperature are different, the heat preservation is properly added in the heating process, the effect of the too low temperature in the heating process is not obvious, and the too high temperature can be already extracted and reacted in the glass system. Therefore, the invention has a limit on the heating temperature, and the impurity absorption of As-Se chalcogenide glass at the middle infrared band of 2-8 um is mainly reflected in the absorption of-OH at 2.3um and H at 6.4um 2 O absorption, analysis of its origin is mainly H in the raw material 2 O, secondly introduced during operation, the invention is therefore directed to H 2 Some improvement was made in the source of O. The disadvantage of the present invention is that, relative to the distillation process, only for-OH and H at 2-8 um 2 The absorption of O has obvious improvement effect, but has no obvious effect on the absorption of As-O bonds at 10.1um except 2-8 um.
The advantages are that: the method reduces the harm of toxic gas As volatilization to human body, can obtain As-Se glass with better spectrum by one-time smelting, greatly shortens the production period, simplifies the complicated process, and has the advantages of high efficiency, low energy consumption and the like.
And 2-8 um is also the current military and civil infrared technical field and relates to a plurality of wave bands, and the invention has certain significance for absorbing As-Se chalcogenide glass at the wave band of 2-8 um.
Drawings
FIG. 1 is a schematic view of a heating furnace device according to the present invention;
FIG. 2 is a graph showing the comparison of infrared transmission spectra of examples 1-3 of the present invention and comparative examples 1-2.
Detailed Description
The invention is further illustrated, but is not limited to, the following examples.
Example 1: as is prepared by the method of the invention 40 Se 60 Infrared chalcogenide glass
Step one: 2 quartz ampoule bottles with low hydroxyl content (below 3 ppm) are selected, firstly, hydrofluoric acid with industrial concentration of 22.5mol/L and solute mass fraction of 25% is used for soaking for 30min, then deionized water and absolute ethyl alcohol are used for cleaning in sequence, and the quartz ampoule bottles are placed in a vacuum drying oven for drying at 200 ℃ for 10 hours.
Step two: high-purity As and Se with purity of 99.9999% are placed in a glove box protected by high-purity nitrogen with purity of 99.999%, and according to chemical component As 40 Se 60 The mass of each raw material was calculated, and 500g was weighed.
Step three: putting the weighed raw materials into a quartz ampoule bottle, under the protection of high-purity inert gas, putting into a heating furnace device for pre-vacuumizing, starting a mechanical pump in a molecular pump unit, gradually pumping out the residual gas on the inner wall of a quartz tube, and mechanically pumping out until the vacuum is 10 -3 Pa for 1 hour, then starting the heating furnace, gradually heating from room temperature to 200deg.C, gradually pumping out the bound water and adsorbed water adsorbed between the surfaces of the raw materials, and simultaneously starting the molecular pump until the vacuum degree is 10 -5 Pa, preserving heat for 2 hours, and sealing the quartz tube in a melting way.
Step four: and (3) melting in a swinging furnace, wherein the melting comprises seven stages:
the first stage: heating stage, heating rate: 2.75 ℃/min, cooling the raw materials and the quartz tube fitting which are sealed in the quartz ampoule bottle to room temperature, taking out from the vacuum chamber, moving to a swinging furnace for heating, heating to 350 ℃ from room temperature for 2h, and preserving heat for 30min, namely starting swinging;
and a second stage: heating stage, heating rate: heating to 450 ℃ from 350 ℃ at 1.67 ℃/min for 1h, and preserving heat for 30min;
and a third stage: heating stage, heating rate: heating to 550deg.C from 450deg.C at 1.67 deg.C/min for 1h, and maintaining for 30min;
fourth stage: heating stage, heating rate: heating to 750 ℃ from 550 ℃ at 1.67 ℃/min for 2h;
fifth stage: a heat preservation smelting stage, wherein the heat preservation time is 12 hours at 750 ℃; ensuring that the raw materials are completely melted and fully mixed uniformly;
sixth stage: cooling stage, cooling rate: 2.5 ℃/min, cooling time: 1h, cooling to 600 ℃ from 750 ℃ and stopping swinging;
seventh stage: after stopping swinging, centralizing the swinging furnace, standing for 2 hours, and when the temperature is reduced from 600 ℃ to 550 ℃, preparing to discharge and cool.
Step five: and (5) discharging, cooling, and annealing and forming.
The annealing process is as follows:
the first stage: heating stage, heating rate: heating from 20 ℃ to 190 ℃ at a speed of 21.25 ℃/h for 8h, and preserving heat for 5h;
and a second stage: slow cooling stage, cooling rate: 2.5 ℃/h, cooling time is 20h, cooling from 190 ℃ to 140 ℃, and preserving heat for 1h;
and a third stage: and in the rapid cooling stage, the cooling rate is as follows: 6 ℃/h and 20h of cooling time, cooling to 20 ℃ from 140 ℃, and taking out to obtain the As-Se chalcogenide glass with low absorption in the mid-infrared band. The spectroscopic test is shown in fig. 2.
Example 2: as is prepared by the method of the invention 39.3 Se 60.7 Infrared chalcogenide glass
The preparation process is the same as in example 1, except that preparation As 39.3 Se 60.7 Infrared chalcogenide glass.
Example 3: as is prepared by the method of the invention 38.6 Se 61.4 Infrared chalcogenide glass
The preparation process was the same As in example 1, except that As was prepared 38.6 Se 61.4 Infrared chalcogenide glass.
Comparative example 1: preparation of As 40 Se 60 Infrared chalcogenide glass
And step three, heating by a heating furnace is not adopted, a vacuum molecular pump unit is directly adopted for vacuumizing operation, the following swinging furnace is adopted for smelting, and the rest processes are the same as those of the embodiment 1.
Step four: and (3) melting in a swinging furnace, wherein the melting is divided into five stages.
The first stage: heating stage, heating rate: 1.83 ℃/min, cooling the raw materials and the quartz tube fitting which are sealed in the quartz ampoule bottle to room temperature, taking out from the vacuum chamber, moving to a swinging furnace for heating, heating to 350 ℃ from room temperature for 3h, and preserving heat for 30min, namely starting swinging;
and a second stage: heating stage, heating rate: heating to 750deg.C from 350deg.C at 1.67 deg.C/min for 4 h;
and a third stage: a heat preservation smelting stage, wherein the heat preservation time is 12 hours at 750 ℃ to ensure that the raw materials are completely melted and fully and uniformly mixed;
fourth stage: cooling stage, cooling rate: 2.5 ℃/min, cooling for 1h, cooling from 750 ℃ to 600 ℃, and stopping swinging;
fifth stage: after stopping swinging, centralizing the swinging furnace, standing for 2 hours, cooling to 550 ℃ from 600 ℃, and preparing to be discharged and cooled.
Comparative example 2: preparation of As 38.6 Se 61.4 Infrared chalcogenide glass
And step three, heating by a heating furnace is not adopted, a vacuum molecular pump unit is directly adopted for vacuumizing operation, the following swinging furnace is adopted for smelting, and the rest processes are the same as those of the embodiment 3.
Step four: and (3) melting in a swinging furnace, wherein the melting is divided into five stages.
The first stage: heating stage, heating rate: 1.83 ℃/min, cooling the raw materials and the quartz tube fitting which are sealed in the quartz ampoule bottle to room temperature, taking out from the vacuum chamber, moving to a swinging furnace for heating, heating to 350 ℃ from room temperature for 3h, and preserving heat for 30min, namely starting swinging;
and a second stage: heating stage, heating rate: heating to 750deg.C from 350deg.C at 1.67 deg.C/min for 4 h;
and a third stage: a heat preservation smelting stage, wherein the heat preservation time is 12 hours at 750 ℃ to ensure that the raw materials are completely melted and fully and uniformly mixed;
fourth stage: cooling stage, cooling rate: 2.5 ℃/min, cooling for 1h, cooling from 750 ℃ to 600 ℃, and stopping swinging;
fifth stage: after stopping swinging, centralizing the swinging furnace, standing for 1.5h, cooling to 550 ℃ from 600 ℃, and preparing to discharge and cool.
Table 1 comparison of data for examples 1-3 and comparative examples 1-2
The results show that: as is apparent from Table 1 in combination with FIG. 2, the infrared transmittance of examples 1-3 and comparative examples 1-2 is almost 60% in the wavelength range of 2 to 8. Mu.m. Wherein examples 1-3 were treated with a furnace in combination with corresponding methods of operation and specific heat treatment protocol, while comparative examples 1-2 were not treated with a furnace, at 2.3 um-OH and at 6.4um H 2 The absorption peak of O is obviously better than that of comparative examples 1-2, so the preparation method of the As-Se chalcogenide glass provided by the invention can meet the condition that the spectral transmittance of a mid-infrared band is more than 60 percent, and the heating treatment of a heating furnace can be matched with a corresponding operation method to carry out the preparation of the As-Se chalcogenide glass on-OH and H 2 The absorption of O has obvious improvement effect.
It should be understood that the above-described embodiments of the present invention are provided by way of example only and are not intended to limit the scope of the invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. Not all embodiments are exhaustive. All obvious changes or modifications which come within the spirit of the invention are desired to be protected.
Claims (1)
1. The preparation method of the As-Se chalcogenide glass with low absorption in the mid-infrared band is characterized by comprising the following steps:
step one: selecting a plurality of quartz ampoule bottles with low hydroxyl content, firstly soaking the quartz ampoule bottles with 25-30wt% of hydrofluoric acid for 20-30 min, then cleaning the quartz ampoule bottles with deionized water and absolute ethyl alcohol in sequence, and drying the quartz ampoule bottles in a vacuum drying oven at 150-200 ℃ for 10 hours; the low hydroxyl content is below 3 ppm;
step two: placing high-purity As and Se in a glove box protected by high-purity nitrogen, and according to the chemical composition As of the prepared As-Se chalcogenide glass 40-x Se 60+x Wherein x is more than or equal to 0 and less than or equal to 1.4, calculating the mass of each raw material, and weighing; the purity of the high-purity As and Se is 99.9999 percent; the purity of the high-purity nitrogen is 99.999%;
step three: putting the weighed raw materials into a quartz ampoule bottle, under the protection of high-purity inert gas, putting into a heating furnace device for pre-vacuumizing, starting a mechanical pump in a molecular pump unit, gradually pumping out the residual gas on the inner wall of a quartz tube, and mechanically pumping out until the vacuum is 10 -3 Pa for 1 hour, then starting the heating furnace, gradually heating from room temperature to 200deg.C, gradually pumping out the bound water and adsorbed water adsorbed between the surfaces of the raw materials, and simultaneously starting the molecular pump until the vacuum degree is 10 -5 Pa, preserving heat for 2 hours, and sealing the quartz tube in a melting way;
step four: and (3) melting in a swinging furnace, wherein the melting comprises seven stages:
the first stage: heating stage, heating rate: 1.83-2.75 ℃/min, cooling the raw materials and the quartz tube fitting which are sealed in the quartz ampoule bottle to room temperature, taking out from the vacuum chamber, moving to a swinging furnace for heating, heating to 350 ℃ from room temperature for 2-3 h, and preserving heat for 30min, namely starting swinging;
and a second stage: heating stage, heating rate: heating to 450 ℃ from 350 ℃ at 1.67 ℃/min for 1h, and preserving heat for 30min;
and a third stage: heating stage, heating rate: heating to 550deg.C from 450deg.C at 1.67 deg.C/min for 1h, and maintaining for 30min;
fourth stage: heating stage, heating rate: heating to 750 ℃ from 550 ℃ at 1.67 ℃/min for 2h;
fifth stage: a heat preservation smelting stage, wherein the heat preservation time is 12 hours at 750 ℃;
sixth stage: cooling stage, cooling rate: 2.5 ℃/min, cooling time: 1h, cooling to 600 ℃ from 750 ℃ and stopping swinging;
seventh stage: after stopping swinging, centralizing the swinging furnace, standing for 1.5-2h, and when the temperature is reduced from 600 ℃ to 550 ℃, preparing to discharge and cool;
step five: discharging from the furnace, cooling, and annealing and forming;
the annealing process is as follows:
the first stage: heating stage, heating rate: heating from 20 ℃ to 190 ℃ at a speed of 21.25 ℃/h for 8h, and preserving heat for 5h;
and a second stage: slow cooling stage, cooling rate: 2.5 ℃/h, cooling time is 20h, cooling from 190 ℃ to 140 ℃, and preserving heat for 1h;
and a third stage: and in the rapid cooling stage, the cooling rate is as follows: 6 ℃/h and 20h of cooling time, cooling to 20 ℃ from 140 ℃, and taking out to obtain the As-Se chalcogenide glass with low absorption in the mid-infrared band.
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| CN101445323A (en) * | 2008-12-31 | 2009-06-03 | 西安工业大学 | Chalcogenide infrared glass and preparation process thereof |
| CN103319070A (en) * | 2013-05-22 | 2013-09-25 | 中国建筑材料科学研究总院 | Purification method for preparing high-purity infrared chalcogenide glass, and apparatus thereof |
| CN105502935A (en) * | 2015-12-25 | 2016-04-20 | 宁波大学 | Preparation method for high-purity chalcogenide glass |
| CN105502937A (en) * | 2016-02-23 | 2016-04-20 | 北京玻璃研究院 | Preparation method of high-purity chalcogenide infrared glass |
| CN106927673A (en) * | 2017-01-13 | 2017-07-07 | 宁波大学 | A kind of optical fiber preparation method of high-purity chalcogenide glass |
| JP2018012617A (en) * | 2016-07-20 | 2018-01-25 | 日本電気硝子株式会社 | Manufacturing method for infrared permeable lens |
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Patent Citations (6)
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| CN101445323A (en) * | 2008-12-31 | 2009-06-03 | 西安工业大学 | Chalcogenide infrared glass and preparation process thereof |
| CN103319070A (en) * | 2013-05-22 | 2013-09-25 | 中国建筑材料科学研究总院 | Purification method for preparing high-purity infrared chalcogenide glass, and apparatus thereof |
| CN105502935A (en) * | 2015-12-25 | 2016-04-20 | 宁波大学 | Preparation method for high-purity chalcogenide glass |
| CN105502937A (en) * | 2016-02-23 | 2016-04-20 | 北京玻璃研究院 | Preparation method of high-purity chalcogenide infrared glass |
| JP2018012617A (en) * | 2016-07-20 | 2018-01-25 | 日本電気硝子株式会社 | Manufacturing method for infrared permeable lens |
| CN106927673A (en) * | 2017-01-13 | 2017-07-07 | 宁波大学 | A kind of optical fiber preparation method of high-purity chalcogenide glass |
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