CN113929300A - Preparation of Chalcogenide Glass by a High-Pressure In-situ Synthesis Technology - Google Patents
Preparation of Chalcogenide Glass by a High-Pressure In-situ Synthesis Technology Download PDFInfo
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- 239000005387 chalcogenide glass Substances 0.000 title claims abstract description 96
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 48
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims description 20
- 238000005516 engineering process Methods 0.000 title description 9
- 238000011065 in-situ storage Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000001816 cooling Methods 0.000 claims abstract description 37
- 239000011669 selenium Substances 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 238000003825 pressing Methods 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 7
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 7
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 6
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000004770 chalcogenides Chemical class 0.000 claims abstract description 5
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000011812 mixed powder Substances 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- 238000001308 synthesis method Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229910052582 BN Inorganic materials 0.000 claims description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 5
- 239000012212 insulator Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 36
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- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 10
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000013307 optical fiber Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
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- 238000000137 annealing Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
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- 230000008018 melting Effects 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000013590 bulk material Substances 0.000 description 5
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- 239000011261 inert gas Substances 0.000 description 4
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- 229910017000 As2Se3 Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229940123973 Oxygen scavenger Drugs 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005816 glass manufacturing process Methods 0.000 description 2
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- 229910052958 orpiment Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003463 sulfur Chemical class 0.000 description 2
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- 239000012620 biological material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007516 diamond turning Methods 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
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- 230000020169 heat generation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000012782 phase change material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000001931 thermography Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
- C03B19/063—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction by hot-pressing powders
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
本公开提供一种块体硫系玻璃的制备方法，制备了As2Se3、As2S3和Ge33As12Se55块体硫系玻璃。主要是提高硫系玻璃材料的物理机械性能，扩大其应用范围。本公开以硫系单质(硫(S)、硒(Se)、碲(Te))粉末和非硫系单质(镓(Ga)、锗(Ge)、砷(As)等)粉末为原料，经混合、预压、组装、高压高温合成、冷却等工艺过程制备出块体硫系玻璃材料。所述的混料、预压是将硫系和非硫系单质粉末按照特定的摩尔比混合均匀，然后根据合成腔体大小压制成块状。所述的高温高压合成是在高压装置上完成，合成压力1.0‑6.0GPa、温度800‑1400K。经保温保压后以大于100K/min小于300K/min的冷却速度降至室温。本公开合成的硫系玻璃材料具有非晶态结构，致密度高，机械强度大，适合在恶劣环境中使用。
The present disclosure provides a method for preparing a bulk chalcogenide glass, and As 2 Se 3 , As 2 S 3 and Ge 33 As 12 Se 55 bulk chalcogenide glasses are prepared. The main purpose is to improve the physical and mechanical properties of chalcogenide glass materials and expand its application range. The present disclosure uses chalcogenide (sulfur (S), selenium (Se), tellurium (Te)) powders and non-chalcogenide (gallium (Ga), germanium (Ge), arsenic (As), etc.) powders as raw materials. The bulk chalcogenide glass material is prepared through the processes of mixing, pre-pressing, assembly, high-pressure high-temperature synthesis, and cooling. The mixing and pre-pressing is to mix the sulfur-based and non-sulfur-based elemental powders uniformly according to a specific molar ratio, and then press them into blocks according to the size of the synthesis cavity. The high-temperature and high-pressure synthesis is completed on a high-pressure device with a synthesis pressure of 1.0-6.0GPa and a temperature of 800-1400K. After heat preservation and pressure preservation, the cooling rate is greater than 100K/min and less than 300K/min to room temperature. The chalcogenide glass material synthesized in the present disclosure has an amorphous structure, high density and high mechanical strength, and is suitable for use in harsh environments.
Description
Technical Field
The disclosure relates to the technical field of infrared glass preparation, in particular to a preparation method of chalcogenide glass.
Background
The infrared light is a kind of electromagnetic wave, and is invisible light between visible light and microwave, and its wavelength range is 0.75-1000 μm. When infrared light irradiates the surface of an object, absorption, reflection, transmission, refraction, scattering and other phenomena occur, so that with the development of science and technology and the progress of society, the application of infrared technologies such as infrared photography, infrared spectroscopy, infrared thermal imaging and the like is speen out like spring shoots in the rainy season.
In the 50's of the last century, infrared technology has been widely applied and popularized in the military field, and has become an important tactical means for protecting the home and defense in modern war. However, the infrared technology in China starts to be researched later, and with the popularization of the infrared technology in military and civil fields in recent years, the mastering of the advanced infrared technology becomes an important requirement for national development and people's life. Therefore, it is very important to develop chalcogenide glass materials with proprietary intellectual property rights.
Chalcogenide glass is one of the candidate materials which are found to be ideal for replacing the traditional infrared materials, and refers to an amorphous optical material which contains one or more oxygen elements except oxygen, such As S, Se, Te and the like, and is formed by adding one or more elements with weak electronegativity, such As As, Ge, Si, Sb and the like. At present, compared with the non-spherical surface processing of infrared crystal materials which can only adopt single-point diamond turning, chalcogenide glass has the advantage of precision compression molding which is not possessed by crystal materials, and the processing cost can be greatly reduced when large-scale compression molding production is carried out. Chalcogenide glass was developed in the first 50 s of the last century, and through the development of most centuries, the variety of chalcogenide glass has been developedThe infrared energy-saving film has a very wide infrared transmission range (more than 20 mu m) and lower phonon energy (less than 350 cm)-1) High nonlinear optical coefficient [ n ]2＝(2～20)×10-18m2/W)]The optical fiber is easy to be changed into optical fiber, and the like, and the optical fiber can be greatly concerned and widely applied in the fields of biosensing, mid-infrared photon integration, optical fiber light sources, phase change materials and the like.
The preparation of chalcogenide glass can be divided into block preparation, optical fiber processing and film preparation. The fusion-quenching method is the oldest and most widely used chalcogenide glass manufacturing method, and is generally used for manufacturing bulk chalcogenide glass. The chalcogenide glass optical fiber prepared by using the chalcogenide glass material not only keeps the characteristics of small volume, good flexibility and the like of the traditional optical fiber, but also has the characteristics of chalcogenide glass, such as excellent transmission performance in a longer infrared band. The existing optical fiber preparation method mainly comprises a double-crucible method, an extrusion method and an in-tube casting method. The chalcogenide glass film is prepared by chalcogenide glass, and most of chalcogenide glass is prepared into a film material by using bulk chalcogenide glass as a raw material through a certain technical means. The common preparation methods include a thermal evaporation method, a magnetron sputtering method, a pulse laser deposition method and the like.
In recent years, researchers have seen a lot of research on the preparation of chalcogenide glass.
For example, a patent with the application number of CN 201510945081.7 discloses Ge-Sn-S chalcogenide glass and a preparation method thereof based on a chalcogenide glass regulation and control model and glass structure dynamics research, and the synthesis steps are as follows: firstly, weighing Ge, Sn and S raw materials according to a proportion, uniformly mixing, packaging the uniformly mixed raw materials in a quartz tube, and then vacuumizing the quartz tube to 10 DEG-4～10-6Pa; then, putting the quartz tube packaged with the raw materials into a heating furnace for high-temperature melting, wherein the heating temperature is 800-1250 ℃, the heating time is 12-60 hours, obtaining a melt in the quartz tube after heating, then immersing the quartz tube into distilled water at-5-45 ℃ to quench the packaged melt, and taking out immediately after wall removal, namely obtaining a semi-finished product of Ge-Sn-S chalcogenide glass in the quartz tube; finally, the semi-finished product of the Ge-Sn-S chalcogenide glass and the quartz tube are processedAnd annealing together, wherein the annealing temperature is 200-280 ℃, the annealing time is 1-6 h, after the annealing is finished, the temperature of the quartz tube and the semi-finished product of the Ge-Sn-S chalcogenide glass is reduced to room temperature at the speed of 1-20 ℃/h, and the Ge-Sn-S chalcogenide glass is obtained by opening the quartz tube. The Ge-Sb-Se chalcogenide glass is prepared by adopting a melting-quenching method, the chalcogenide glass is good in glass forming property, has good middle and far infrared transmission capacity and near infrared transmission characteristic, and is low in efficiency, high in energy consumption and the like due to the fact that the reaction time is too long.
Such as the patent application No. 202011642926.2, provides a Ge24TexSe(76-x)The chalcogenide glass and the preparation method thereof have the following preparation processes: the method comprises the following steps: loading, namely weighing raw materials Ge, Te and Se according to the component proportion in a glove box, loading into a prepared container, adding an oxygen scavenger (magnesium strips or aluminum strips) and a hydrogen scavenger (aluminum chloride) at the upper part of the container, and loading the raw materials at the lower part of the container; step two: performing vacuum treatment, namely performing vacuum pumping treatment on the container under the protection of nitrogen, and then sealing the container; step three: melting, namely putting the container into a swinging furnace, heating to 850-960 ℃, and swinging for 25-30 h while melting; step four: quenching, namely cooling the rocking furnace to 500-600 ℃, taking out the container and quenching with compressed air to obtain a semi-finished product; step five: annealing, annealing the quenched container and the chalcogenide glass semi-finished product, keeping the temperature at 170-200 ℃ for 5-10 h, slowly and uniformly cooling to room temperature after the heat preservation is finished, and sawing the container to obtain Ge with excellent transmittance24TexSe(76-x)A chalcogenide glass. However, the preparation method provided by the publication needs to strictly control the oxygen concentration (if oxygen exists in the container, the raw material reacts with the oxygen to generate absorption bonds related to the oxygen, and further reduce the transmittance), so in addition to the operations of vacuumizing the container and the like, magnesium strips or aluminum strips are also needed to be used as oxygen scavengers, and the magnesium strips and the aluminum strips are relatively active metals, so that certain potential safety hazards exist during use. In addition, the chalcogenide glass prepared by the method has not been researched with respect to the quality of the mechanical properties.
In conclusion, aiming at the defects existing in the prior art, in particular to the problems of long reaction time, complex operation and poor mechanical property of the finished product in the preparation process of chalcogenide glass: the problems of low efficiency, high energy consumption and the like can be caused by overlong reaction time, and the mass production is not facilitated; the poor mechanical properties of the finished chalcogenide glass make its use in complex and diverse environments very limited. Therefore, development is urgently needed for a method for preparing chalcogenide glass with higher efficiency and better physical and mechanical properties.
Disclosure of Invention
The present disclosure provides a method for preparing chalcogenide glass block material, i.e. high-pressure in-situ synthesis method, with low cost, simple process and high production efficiency, to solve the problems of low efficiency, large energy consumption and poor mechanical properties in the prior art.
The bulk chalcogenide glass material is prepared by taking chalcogenide simple substances (sulfur (S), selenium (Se), tellurium (Te)) and non-chalcogenide simple substances (gallium (Ga), germanium (Ge) and arsenic (As)) As raw materials through the processes of mixing, prepressing, assembling, high-temperature high-pressure synthesis, cooling and the like.
One of the ideas of the present disclosure is to directly mix elemental sulfur (S), selenium (Se), tellurium (Te)) powder and elemental non-sulfur (gallium (Ga), germanium (Ge), arsenic (As)) powder As raw materials, without pretreatment of the raw materials, and the operation is simple.
Further, another concept of the present disclosure is to pre-press the mixed powdered raw material to make the mixed powder cold-pressed into a block shape according to the size of the synthesis cavity, wherein the pre-pressing is to make the powdered raw material into a block shape.
Further, another idea of the present disclosure is to assemble the pre-pressed block raw materials in an indirect heating type assembly manner.
The reaction material of side hot type equipment and graphite pipe heat-generating body between be separated by one deck insulating tube, the package assembly is stable relatively, so for the homogeneity and the stability of temperature obtain guaranteeing in the cavity, also make the temperature control more easily simultaneously, and then, the reaction material is heated more evenly, more is favorable to improving product quality's stability.
The insulating tube can adopt solid oxide, nitride and carbide.
The solid oxide can be magnesium oxide and aluminum oxide, and because the magnesium oxide and the aluminum oxide both have higher heat conductivity coefficient, good electrical insulation and low price, products with excellent performance can be obtained while the production cost is reduced.
The nitride and the carbide can be aluminum nitride, boron nitride and silicon nitride, the carbide can be silicon carbide, the nitride and the carbide all have an atomic crystal form and a compact structure, the thermal conductivity is high, the reaction materials are uniformly heated, the heat utilization rate is high, the heat loss in the reaction process is greatly reduced, and the production efficiency is improved.
Still further, another concept of the present disclosure is to place the assembled high pressure unit on a domestic cubic press for high temperature and high pressure synthesis.
The cubic press is provided by Luoyang Jinlu hard alloy tools Co., Ltd, is the most widely used large-cavity press, has the advantages of low manufacturing cost, easy operation and the like, and is widely applied to the fields of superconducting materials, superhard materials, ceramic materials, insulating materials, magnetic materials, glass materials, ferroelectric materials, biological materials, rare earth materials and the like.
By using the lateral hot assembly of the cubic press, the temperature distribution mode in the cavity can be adjusted to be that the central temperature of the cavity is low and the peripheral temperature is high, and the gradient direction of the temperature is the same as that of the pressure, so that the state that the pressure is matched with the temperature is achieved, the driving force of the crystal growth in the synthetic cavity is kept highly consistent, and finally a high-quality product is obtained.
The poor mechanical properties of chalcogenide glass materials are directly related to the internal bulk structure thereof. The method realizes regulation and control of the internal atomic layer of chalcogenide glass by controlling the high-pressure and high-temperature synthesis conditions, so that the atomic arrangement is tighter, and the bonding force among atoms is greatly enhanced, thereby achieving the purpose of improving the physical and mechanical properties of chalcogenide glass materials.
Furthermore, after the product is synthesized for a certain time at high temperature and high pressure, the product is subjected to heat preservation and pressure maintaining treatment and is cooled.
The key operation of the cooling is the regulation and control of the cooling rate, and the influence of the cooling rate on the integrity of the chalcogenide glass block plays a crucial role.
The technical scheme adopted by the disclosure is as follows: the high-pressure in-situ synthesis method for preparing chalcogenide glass comprises the following specific steps:
1) mixing: mixing sulfur series simple substances with the purity of 99.999 percent and non-sulfur series simple substances according to the molar ratio of 1:3-5: 6;
the sulfur elementary substances refer to sulfur (S), selenium (Se) and tellurium (Te).
The non-sulfur elementary substance refers to gallium (Ga), germanium (Ge) and arsenic (As).
2) Pre-pressing: the method comprises the steps of putting uniformly mixed powder into a high-temperature-resistant metal shielding cup, filling inert gas into the cup, and then pressurizing and sealing the cup to enable the mixed powder to be cold-pressed into blocks according to the size of a synthesis cavity;
the inert gas is argon (Ar) and has the function of preventing raw materials from being oxidized in the high-temperature high-pressure synthesis process.
The pressurization refers to the pressure of 20-40 MPa.
The cold pressing comprises the following specific operations: putting a certain amount of powder into a mold, applying pressure of 20-40MPa in inert atmosphere to press the powder into a cylindrical shape, then putting the cylindrical shape into a metal shielding cup, and then putting the metal shielding cup into the mold to be cold-pressed and sealed in the inert atmosphere to obtain a block-shaped material.
3) Assembling: loading the block material in the second step into a high-pressure unit;
the assembly is to adopt an indirectly heated assembly mode to assemble raw materials, and the matching degree of pressure and temperature is higher.
The high-voltage unit adopts a graphite tube as a heating body and magnesium oxide or hexagonal boron nitride as an insulator.
4) High-temperature high-pressure synthesis: the high-pressure unit is arranged on a domestic cubic press, the synthesis pressure is 1.0-6.0GPa, and the synthesis temperature is 800-1400K.
The chalcogenide glass is mainly in a chain structure formed by covalent bonds between weak two-coordinate chalcogen elements, is assisted by a cross-linking network formed by three-coordinate or four-coordinate IV-group and V-group elements, and the weak van der Waals force between chains causes the mechanical property and the thermal stability of the chalcogenide glass to be poor, so that the application of the chalcogenide glass is limited to a certain extent. The synthesis pressure can reduce the internal atomic distance of the chalcogenide glass material, and further influences the physical and mechanical properties of the material, such as density, hardness, strength and the like. The density is low due to too low pressure, so that the transmittance of the glass is reduced; too high a pressure can create significant residual stress in the glass resulting in glass fracture. Experimental results show that the optimal synthetic pressure range is 2.0-5.0GPa, and the complete and high-density glass block can be obtained in the pressure range. The synthesis temperature is an important factor influencing the crystallization behavior of the chalcogenide glass material, the temperature is too low and does not reach the melting temperature of the raw materials, and the reaction can only generate crystals but not form glass; when the temperature is too high, the raw materials react with the metal shielding cup to pollute the glass. The experimental results show that the optimal synthesis temperature range is 800-1100K.
5) And (3) cooling: and (4) after the high-pressure unit in the step (4) is subjected to heat preservation and pressure maintaining, cooling to room temperature at a cooling rate of more than 100K/min and less than 300K/min.
And the heat preservation and pressure maintaining are that the heating is stopped after the temperature and the pressure are kept within the range of 10-80 minutes in the step three.
The cooling rate is a main factor influencing the integrity of the chalcogenide glass block, the cooling rate can be controlled by controlling the temperature and the flow of the refrigerant, the glass generates great residual stress and is cracked when the cooling rate is too high, the glass generates crystallization phenomenon and loses the infrared transparency performance when the cooling rate is too low, and the experimental result shows that the optimal cooling rate range is 120-250K/min.
Compared with the conventional technology, the present disclosure has the advantages that:
1) the production cost is low, the utilization rate of the raw materials can reach 100 percent, and no raw material is wasted.
2) The method has simple process, the raw materials can be directly used for experiments, the raw materials do not need to be pretreated, and the block chalcogenide glass can be synthesized without complicated operation procedures.
3) The use of the cubic apparatus press indirectly heated type assembly process has the advantages of low energy consumption, high efficiency and greatly improved stability of product quality.
4) The synthetic chalcogenide glass material has good comprehensive performance, and is mainly characterized in that the compactness is improved by 0.1-1.0%, the hardness is improved by 50-200%, and the elastic modulus is improved by 20-50%.
Drawings
FIG. 1 As synthesized according to the parameters of the present disclosure2Se3XRD phase detection image of chalcogenide glass.
FIG. 2 As synthesized according to the parameters of the present disclosure2Se3The Vickers hardness and elastic modulus of chalcogenide glass are compared with those of the conventional method.
FIG. 3 As synthesized according to the parameters of the present disclosure2S3Sulfur series
The vickers hardness and the elastic modulus of the glass are plotted in comparison with the conventional method.
FIG. 4 shows Ge synthesized using parameters specific to the present disclosure33As12Se55XRD phase detection image of chalcogenide glass.
FIG. 5 Ge parametric synthesis specific to the present disclosure33As12Se55The Vickers hardness and the elastic modulus of the chalcogenide glass are compared with those of the chalcogenide glass synthesized by the traditional method.
FIG. 6 As synthesized in the comparative example with a cooling rate of 50K/min2Se3XRD phase detection image of chalcogenide glass.
Detailed Description
In order to make the objects, technical solutions and advantages of the present disclosure more apparent, the present disclosure is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the disclosure and are not intended to limit the disclosure.
In some embodiments, As is prepared according to the disclosed chalcogenide glass making methods2Se3The chalcogenide glass block material comprises the following steps: the method comprises the following steps: mixing, namely weighing simple substances of As powder and Se powder with the purity of 99.999% according to the molar ratio of 1:3-5:6, and then mixing; step two: pre-pressing, thePutting the uniformly mixed As powder and Se powder into a high-temperature-resistant metal shielding cup, filling inert gas argon, pressurizing to 20-40MPa, and then sealing to make the mixed powder cold-pressed into blocks according to the size of a synthesis cavity; step three: assembling, namely filling the blocky raw materials into a high-voltage unit, wherein the high-voltage unit adopts a graphite tube as a heating body and magnesium oxide or hexagonal boron nitride as an insulator; step four: high-temperature high-pressure synthesis, namely placing the high-pressure unit on a domestic cubic press, wherein the synthesis pressure is 1.0-6.0GPa, and the synthesis temperature is 800-1400K; step five: cooling, namely cooling to room temperature at a cooling rate of more than 100K/min and less than 300K/min after keeping the temperature and pressure of the high-pressure unit in the step four to obtain the glassy As2Se3A bulk material.
Preferably, in the first step, the ratio of As powder to Se powder is 2: 3, uniformly mixing.
Preferably, in the third step, the As powder and the Se powder are assembled by an indirect heating type assembly method, the assembly structure of the indirect heating type assembly method is relatively stable, the temperature change is not large when the heating conditions are the same, and the change is large when the direct heating type assembly method is adopted. Compared with a direct heating type heating mode, the indirect heating type heating mode has great advantages in uniform temperature distribution in the synthetic cavity, the stability of the temperature in the cavity is ensured more easily, and the stability of the product quality is improved.
Preferably, magnesium oxide (MgO) is used as the insulating material in step three.
Preferably, the synthesis pressure in the fourth step is 4.5GPa, the synthesis temperature is 890K, and the heat preservation time is 20 min.
Preferably, the cooling rate in the fifth step is 150K/min to the room temperature.
As shown in FIG. 1, synthesized according to the above specific parameters of the present disclosure2Se3XRD phase detection diagram of chalcogenide glass, from which the synthesized As2Se3The chalcogenide glass has an amorphous structure.
For comparison, the assembly method in the third step adopts direct heating type assembly. The cavity of the direct-heating type assembly has the advantages that the resistivity changes along with the reaction, the heat generation rate greatly fluctuates, the heating difference at different positions in the glass is large, the physical and mechanical properties of the glass are greatly reduced, and the direct-heating type assembly cannot be applied to actual life and production.
In the fourth step, by contrast, the synthesis temperature was set to 800K at a synthesis pressure of 1GPa and 1400K at a synthesis pressure of 6GPa, respectively, and high-temperature and high-pressure synthesis was performed. The experimental results show that only materials with crystal structures can be formed under the conditions of lower pressure and temperature, and glass cannot be formed. Although glass can be formed under higher pressure and temperature, the glass can generate fragmentation phenomena with different degrees, and the glass cannot be applied to actual production and life.
For comparison, in step five, the materials are cooled to room temperature at the rates of 50K/min, 100K/min, 300K/min and 350K/min respectively.
The products obtained at cooling rates of 50K/min and 100K/min, the crystallization of the glass occurred due to the slower cooling rate. As produced at a cooling rate of 50K/min As shown in FIG. 62Se3As can be seen from the figure, the bulk material did not form chalcogenide glass due to a too low cooling rate. The products obtained at cooling rates of 300K/min and 350K/min have different degrees of fracture due to the residual stress generated by the faster cooling rate.
In some embodiments, As is prepared according to the disclosed chalcogenide glass making methods2S3The chalcogenide glass block material comprises the following steps: the method comprises the following steps: mixing, namely weighing the As powder with the purity of 99.999 percent and the S powder simple substance according to the molar ratio of 1:3-5:6, and then mixing; step two: pre-pressing, namely putting the uniformly mixed As powder and S powder into a high-temperature-resistant metal shielding cup, filling argon, pressurizing to 20-40MPa, and then sealing to make the mixed powder cold-pressed into blocks according to the size of a synthesis cavity; step three: and (3) assembling, namely loading the blocky raw materials into a high-voltage unit, wherein the high-voltage unit adopts a graphite tube as a heating body and magnesium oxide as an insulator. Step four: high-temperature high-pressure synthesis, namely placing the high-pressure unit on a domestic cubic press, wherein the synthesis pressure is 1.0-6.0GPa, and the temperature is 50K above the highest melting point of the used raw materials; step five: cooling, after the high-pressure unit in the step four is subjected to heat preservation and pressure maintaining, the temperature is increased by 100 ℃ and 300K/minCooling to room temperature to obtain the glassy As2S3A bulk material.
Preferably, in the step one, the As powder and the S powder are mixed according to a molar ratio of 2: 3, uniformly mixing.
Preferably, the synthesis pressure in the fourth step is 5.5GPa, the synthesis temperature is 900K, and the heat preservation time is 20 min.
Preferably, the cooling rate of 130K/min is reduced to room temperature in the fifth step.
In still other embodiments, Ge is prepared according to the disclosed chalcogenide glass preparation method33As12Se55The chalcogenide glass block material comprises the following steps: the method comprises the following steps: mixing, namely mixing Ge powder, As powder and Se powder with the purity of 99.999% according to a molar ratio of 33: 12: 55, mixing uniformly; step two: prepressing, namely putting the uniformly mixed powder into a high-temperature-resistant metal shielding cup, filling inert gas, pressurizing to 20-40MPa, and sealing to make the mixed powder cold-pressed into blocks according to the size of a synthesis cavity; step three: assembling, namely loading the blocky raw materials into a high-voltage unit, wherein the high-voltage unit adopts a graphite tube as a heating body and hexagonal boron nitride (hBN) as an insulator; step four: high-temperature high-pressure synthesis, namely placing the high-pressure unit on a domestic cubic press, wherein the synthesis pressure is 1.0-6.0GPa, and the temperature is 50K above the highest melting point of the used raw materials; step five: cooling, after the high-pressure unit in the step four is subjected to heat preservation and pressure maintaining, cooling to room temperature at the cooling rate of 100-33As12Se55A bulk material.
Preferably, the synthesis pressure in the fourth step is 5.5GPa, the synthesis temperature is 1300K, and the heat preservation time is 30 min.
Preferably, the cooling rate in step five is 200K/min to room temperature.
Ge synthesized according to the above preferred scheme as shown in FIG. 433As12Se55XRD phase detection diagram of chalcogenide glass block material, which can be obtained from diagram, and synthesized Ge33As12Se55The chalcogenide glass bulk material has an amorphous structure.
By contrast, a conventional method is adoptedBy the method respectively preparing As2Se3、As2S3And Ge33As12Se55A chalcogenide glass block material.
FIG. 2 shows As synthesized by high-temperature high-pressure synthesis2Se3Comparison of Vickers hardness and elastic modulus of chalcogenide glass with those of conventional method, As synthesized by high-temperature high-pressure synthesis method2Se3The Vickers hardness of the chalcogenide glass is higher than 50 percent of that of the chalcogenide glass prepared by the traditional method, and the elastic modulus of the chalcogenide glass is 4.8GPa higher than that of the chalcogenide glass prepared by the traditional method.
FIG. 3 shows As synthesized by the high-temperature high-pressure synthesis method2S3Comparison of Vickers hardness and elastic modulus of chalcogenide glass with those of conventional method, As synthesized by high-temperature high-pressure synthesis method2S3The Vickers hardness of the chalcogenide glass is greatly higher than that of As synthesized by the traditional method2S3The elastic modulus of the chalcogenide glass is 6.5GPa higher than that of the chalcogenide glass prepared by the traditional method.
FIG. 5 shows Ge synthesized by high temperature and high pressure synthesis33As12Se55Comparison of Vickers hardness and elastic modulus of chalcogenide glass with those of conventional method, and Ge synthesized by high-temperature high-pressure synthesis method33As12Se55The Vickers hardness of the chalcogenide glass is 1.35GPa higher than that of the chalcogenide glass prepared by the traditional method, and the elastic modulus of the chalcogenide glass is 5.4GPa higher than that of the chalcogenide glass prepared by the traditional method.
In conclusion, the chalcogenide glass synthesized by the high-temperature high-pressure synthesis method has an amorphous structure and good mechanical properties, and can be widely applied to actual life and production. Compared with the traditional preparation method, the preparation method has the advantages of simple process, convenience in implementation and higher production efficiency.
Claims (8)
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106637105A (en) * | 2016-12-27 | 2017-05-10 | 江西科泰新材料有限公司 | Production process of chalcogenide glass or phase change storage material germanium arsenic selenium tellurium target material |
| CN109573979A (en) * | 2019-01-25 | 2019-04-05 | 燕山大学 | A kind of preparation method of novel glass carbon |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106637105A (en) * | 2016-12-27 | 2017-05-10 | 江西科泰新材料有限公司 | Production process of chalcogenide glass or phase change storage material germanium arsenic selenium tellurium target material |
| CN109573979A (en) * | 2019-01-25 | 2019-04-05 | 燕山大学 | A kind of preparation method of novel glass carbon |
Non-Patent Citations (2)
| Title |
|---|
| BINGKE QIN等: "High-pressure preparation and structural analysis of Se-S-As ternary system compounds", 《JOURNAL OF PHYSICS: CONFERENCE SERIES》 * |
| V.V.BRAZHKIN等: "AsS：Bulk inorganic molecular-based chalcogenide glass", 《APPLIED PHYSICS LETTERS》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116594088A (en) * | 2023-03-29 | 2023-08-15 | 暨南大学 | Infrared light field regulating device and preparation method thereof |
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