CN113929300B - Preparation of chalcogenide glass by high-pressure in-situ synthesis technology - Google Patents
Preparation of chalcogenide glass by high-pressure in-situ synthesis technology Download PDFInfo
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- 239000005387 chalcogenide glass Substances 0.000 title claims abstract description 79
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 43
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 18
- 238000005516 engineering process Methods 0.000 title description 8
- 238000011065 in-situ storage Methods 0.000 title description 4
- 238000001816 cooling Methods 0.000 claims abstract description 41
- 239000011669 selenium Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 7
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 6
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 6
- 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
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052714 tellurium Inorganic materials 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 21
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 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 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 238000011068 loading method Methods 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 34
- 239000011521 glass Substances 0.000 abstract description 23
- 238000004321 preservation Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 10
- 239000010453 quartz Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000007796 conventional method Methods 0.000 description 8
- 239000013307 optical fiber Substances 0.000 description 8
- 238000001308 synthesis method Methods 0.000 description 8
- 238000011049 filling Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000013590 bulk material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000011265 semifinished product Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 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
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007516 diamond turning Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012782 phase change material 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
- 238000011160 research Methods 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
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000001931 thermography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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
The disclosure provides a method for preparing bulk chalcogenide glass, which prepares As 2 Se 3 、As 2 S 3 And Ge (Ge) 33 As 12 Se 55 Bulk chalcogenide glass. Mainly improves the physical and mechanical properties of the chalcogenide glass material and expands the application range thereof. The method takes sulfur-series simple substance (S), selenium (Se), tellurium (Te)) powder and non-sulfur-series simple substance (Ga), germanium (Ge), arsenic (As) powder As raw materials, and prepares the bulk sulfur-series glass material through the technological processes of mixing, prepressing, assembling, high-pressure high-temperature synthesis, cooling and the like. The mixing and pre-pressing are to uniformly mix the sulfur-based and non-sulfur-based simple substance powder according to a specific molar ratio, and then press the powder into blocks according to the size of the synthetic cavity. The high-temperature high-pressure synthesis is completed on a high-pressure device, the synthesis pressure is 1.0-6.0GPa, and the temperature is 800-1400K. After heat preservation and pressure maintaining, cooling to room temperature at a cooling speed of more than 100K/min and less than 300K/min. The chalcogenide glass material synthesized by the method has an amorphous structure, high density and high mechanical strength, and is suitable for being used in severe environments.
Description
Technical Field
The disclosure relates to the technical field of infrared glass preparation, in particular to a chalcogenide glass preparation method.
Background
Infrared light is one type of electromagnetic wave, and is invisible light between visible light and microwaves, and the wavelength range thereof is between 0.75 and 1 000 μm. When infrared light irradiates on the surface of an object, phenomena such as absorption, reflection, transmission, refraction and scattering can occur, so that with the development of technology and the progress of society, the application of related infrared technologies such as infrared photography, infrared spectrum, infrared thermal imaging and the like, such as the phenomenon of bamboo shoots after raining and spring.
In the 50 s of the last century, infrared technology was widely applied and popularized in the military field, and became an important tactical means for modern war insurance home and guard. However, research on infrared technology in China starts later, and along with popularization of infrared technology in military and civil fields in recent years, mastering advanced infrared technology has become an important requirement for national development and people's life. Therefore, it is important to develop chalcogenide glass materials with independent intellectual property rights.
Chalcogenide glass is one of the ideal candidate materials for replacing the traditional infrared materials, and refers to an amorphous optical material formed by adding one or more elements with weaker electronegativity, such as As, ge, si, sb, and the like, and containing one or more oxygen group elements such as S, se, te and the like besides oxygen. At present, compared with the infrared crystal material which can only adopt the aspheric surface processing of single-point diamond turning, the chalcogenide glass has the advantage of precise compression molding which is not possessed by the crystal material, and the processing cost can be greatly reduced when mass compression molding production is carried out. Chalcogenide glasses were developed in the earliest 50 s of the last century, and through the development of the last century, the variety of chalcogenide glasses is now very diverse, with ultra-wide infrared transmission ranges (up to 20 μm or more), low phonon energies (less than 350 cm) -1 ) High nonlinear optical coefficient n 2 ＝(2～20)×10 -18 m 2 /W)]And the optical fiber is easy to be made into optical fibers, and the like, and the optical fiber can be greatly focused and widely applied in the fields of biological sensing, mid-infrared light sub-assembly, optical fiber light sources, phase change materials and the like.
The preparation of chalcogenide glass can be classified into block preparation, optical fiber processing, and film preparation. The melt-quench method is the oldest and most widely used method of preparing chalcogenide glass, and is generally used to prepare bulk chalcogenide glass. The chalcogenide glass optical fiber prepared by using the chalcogenide glass material not only maintains 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 using chalcogenide glass, and most of chalcogenide glass is prepared into a film material by taking bulk chalcogenide glass as a raw material and adopting a certain technical means. Common preparation methods include thermal evaporation, magnetron sputtering, and pulse laser deposition.
In recent years, the study of chalcogenide glass preparation by students has been endless.
The patent with the application number of CN 201510945081.7 discloses a Ge-Sn-S chalcogenide glass and a preparation method thereof based on a chalcogenide glass regulation model and a glass structure dynamics study, 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 into a quartz tube, and vacuumizing the quartz tube to 10 -4 ～10 -6 Pa; 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 the temperature of minus 5-45 ℃ for quenching the packaged melt, and immediately taking out the quartz tube after wall removal, namely obtaining a semi-finished product of Ge-Sn-S chalcogenide glass in the quartz tube; and finally, annealing the semi-finished product of the Ge-Sn-S chalcogenide glass together with the quartz tube at the annealing temperature of 200-280 ℃ for 1-6 hours, cooling the quartz tube and the semi-finished product of the Ge-Sn-S chalcogenide glass to room temperature at the speed of 1-20 ℃/h after the annealing is finished, and opening the quartz tube to obtain the Ge-Sn-S chalcogenide glass. The Ge-Sb-Se chalcogenide glass is prepared by a melting-quenching method, is good in glass forming, has good medium-far infrared transmission capacity and near infrared transmission characteristics, and has the problems of low efficiency, high energy consumption and the like caused by overlong reaction time.
Such as application number202011642926.2 provides a Ge 24 Te x Se (76-x) The preparation process of the chalcogenide glass comprises the following steps: step one: charging, namely weighing raw materials Ge, te and Se according to the component proportion in a glove box, charging into a prepared container, adding an deoxidizer (magnesium strip or aluminum strip) and a dehydrogenation agent (aluminum chloride) at the upper part of the container, and placing the raw materials at the lower part of the container; step two: vacuum processing, namely vacuumizing the container under the protection of nitrogen, and sealing the container; step three: melting, namely placing the container into a swinging furnace, heating to 850-960 ℃, and swinging for 25-30 h while melting; step four: quenching, namely cooling the swinging furnace to 500-600 ℃, taking out the container, and quenching with compressed air to obtain a semi-finished product; step five: annealing, namely annealing the quenched container and the chalcogenide glass semi-finished product, preserving heat for 5-10 hours at 170-200 ℃, slowly and uniformly cooling to room temperature after the heat preservation is finished, and sawing the container to obtain Ge with excellent transmittance 24 Te x Se (76-x) A chalcogenide glass. However, the preparation method provided by the publication needs to control the concentration of oxygen very severely (if oxygen exists in the container, raw materials react with the oxygen to generate oxygen-related absorption bonds so as to reduce the transmissivity), so that besides the operations of vacuumizing the container and the like, magnesium strips or aluminum strips are used as deoxidizers, 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 studied for the mechanical properties.
In summary, the problems of long reaction time, complex operation and poor mechanical properties of finished products in the preparation process of the chalcogenide glass are solved in order to overcome the defects of the prior art: the long reaction time can cause the problems of low efficiency, high energy consumption and the like, and is not beneficial to mass production; the mechanical properties of the finished chalcogenide glass are poor, so that the application of the chalcogenide glass in complex and variable environments is greatly limited. Therefore, development is needed for a preparation method of 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 materials, namely a high-pressure in-situ synthesis method, which has the advantages of low cost, simple process and high production efficiency, and solves the problems of low efficiency, high energy consumption and poor mechanical properties in the prior art.
The method takes a sulfur-series simple substance (sulfur (S), selenium (Se), tellurium (Te)) and a non-sulfur-series simple substance (gallium (Ga), germanium (Ge), arsenic (As)) As raw materials, and prepares the bulk sulfur-series glass material through the technological processes of mixing, prepressing, assembling, high-temperature high-pressure synthesis, cooling and the like.
One of the concepts of the present disclosure is to directly mix a powder of a sulfur-based simple substance (sulfur (S), selenium (Se), tellurium (Te)) and a powder of a non-sulfur-based simple substance (gallium (Ga), germanium (Ge), arsenic (As)) As raw materials without pretreatment of the raw materials, and to operate simply.
Further, another concept of the present disclosure is to pre-press the mixed powdery raw materials to make the mixed powder into a block shape according to the size of the synthesis cavity, and the pre-pressing is to make the powdery raw materials into a block shape.
Further, another concept of the present disclosure is to assemble the pre-pressed bulk raw material in a side heating type assembly manner.
The reaction material and the graphite tube heating body are separated by the insulating tube, and the assembly structure is relatively stable, so that the uniformity and stability of the temperature in the cavity are ensured, the temperature is easier to control, and the reaction material is heated more uniformly, thereby being more beneficial to improving the stability of the product quality.
The insulating tube can be made of solid oxide, nitride or carbide.
The solid oxide can be magnesium oxide and aluminum oxide, and has high heat conductivity, good electrical insulation and low price, so that the product 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, and the carbide can be silicon carbide, and has an atomic crystal form and a compact structure, so that the thermal conductivity is high, the heat utilization rate is high while the reaction materials are uniformly heated, 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 hexahedral top press for high-temperature and high-pressure synthesis.
The hexahedral press is provided by Luoyang Jin Lu hard alloy tools limited company, is the most widely used large-cavity press, has the advantages of low 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 cubic press side heating type assembly, the temperature distribution mode in the cavity can be adjusted to be low in the center temperature and high in the periphery temperature of the cavity, and the gradient direction of the temperature is the same as the gradient direction of the pressure, so that the state that the pressure is matched with the temperature is achieved, the driving force of crystal growth in the synthesis 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 their internal bulk structure. The method mainly realizes the regulation and control of the atomic layer in the chalcogenide glass by controlling the high-pressure high-temperature synthesis conditions, so that the atomic arrangement is more compact and the bonding force among atoms is greatly enhanced, thereby achieving the purpose of improving the physical and mechanical properties of the chalcogenide glass material.
Further, after the product is subjected to high-temperature high-pressure synthesis for a certain time, 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 cooling rate plays a crucial role in influencing the integrity of the chalcogenide glass block.
The technical scheme adopted by the present disclosure is as follows: a high-pressure in-situ synthesis method for preparing chalcogenide glass comprises the following specific steps:
1) Mixing: mixing the sulfur-series and non-sulfur-series simple substances with the purity of 99.999 percent according to the molar ratio of 1:3-5:6;
the sulfur-based simple substance refers to sulfur (S), selenium (Se) and tellurium (Te).
The non-sulfur element refers to gallium (Ga), germanium (Ge) and arsenic (As).
2) Prepressing: the method is that the evenly mixed powder is put into a high temperature resistant metal shielding cup, inert gas is filled in, and then the mixture is pressurized and sealed, so that the mixed powder is cold-pressed into blocks according to the size of a synthetic cavity;
the inert gas is argon (Ar) and has the function of preventing raw materials from being oxidized in the high-temperature high-pressure compression process.
The pressurization means that the pressure is 20-40MPa.
The cold pressing comprises the following specific operations: and (3) filling a certain amount of powder into a mould, applying a pressure of 20-40MPa in an inert atmosphere to press into a cylinder, then placing the cylinder into a metal shielding cup, and then placing the metal shielding cup into the mould to perform cold pressing and sealing in the inert atmosphere to obtain the block material.
3) And (3) assembling: loading the block material in the second step into a high-pressure unit;
the assembly is carried out by adopting a bypass type 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 placed on a domestic hexahedral top 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 a weak covalent bond between two chalcogenides and is assisted by a cross-linked network formed by three or four coordination elements in groups IV and V, and the weak van der Waals force between the chains leads to poor mechanical properties and thermal stability of the glass, which limits the application of the chalcogenide glass to a certain extent. The synthesis pressure can reduce the internal atomic distance of the chalcogenide glass material, thereby affecting the physical and mechanical properties of the material, such as compact density, hardness, strength and the like. Too low pressure can cause lower density and lower transmittance of the glass; too high a pressure can create significant residual stresses in the glass that can lead to glass breakage. Experimental results show that the optimal synthesis 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, the melting temperature of the raw materials is not reached, and the reaction can only generate crystals but not form glass; the temperature is too high, and the raw materials react with the metal shielding cup to pollute the glass. Experimental results show that the optimal synthesis temperature range is 800-1100K.
5) And (3) cooling: and (3) 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.
The heat preservation and pressure maintaining means that heating is stopped after the temperature and the pressure are maintained for 10-80 minutes in the pressure and temperature range described in the third step.
The cooling rate is a main factor affecting the integrity of the chalcogenide glass block, the cooling rate can be controlled by controlling the temperature and the flow of a cooling medium, the excessive cooling rate can cause the glass to generate great residual stress to crack, the excessive cooling rate can cause the glass to generate crystallization phenomenon to lose infrared transparency, and the experimental result shows that the optimal cooling rate range is 120-250K/min.
Compared with the prior art, the method has the advantages that:
1) The production cost is low, the utilization rate of raw materials can reach 100 percent, and no raw materials are wasted.
2) The process is simple, the raw materials can be directly used for experiments, pretreatment of the raw materials is not needed, and complex operation procedures are not needed, so that the bulk chalcogenide glass can be synthesized.
3) By using the hexahedral top press side heating type assembly process, the energy consumption is low, the efficiency is high, and the stability of the product quality is greatly improved.
4) The synthesized 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 with specific parameters of the present disclosure 2 Se 3 XRD phase detection of chalcogenide glassA drawing.
FIG. 2. As synthesized with specific parameters of the present disclosure 2 Se 3 The vickers hardness and elastic modulus of the chalcogenide glass are compared with those of the conventional method.
FIG. 3 As for the specific parametric synthesis of the present disclosure 2 S 3 Sulfur series
The vickers hardness and elastic modulus of the glass are compared with those of the conventional method.
FIG. 4 Ge for specific parametric synthesis of the present disclosure 33 As 12 Se 55 XRD phase detection pattern of chalcogenide glass.
FIG. 5 Ge for specific parametric synthesis of the present disclosure 33 As 12 Se 55 The Vickers hardness and elastic modulus of chalcogenide glass are compared with the synthetic properties of conventional methods.
FIG. 6 compares As synthesized at a cooling rate of 50K/min in the scheme 2 Se 3 XRD phase detection pattern of chalcogenide glass.
Detailed Description
In order to make the objects, technical solutions and advantages of the present disclosure more apparent, the present disclosure will be further described in detail with reference to the following examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present disclosure.
In some embodiments, as is prepared according to the methods of preparing chalcogenide glasses of the present disclosure 2 Se 3 A chalcogenide glass block material comprising the steps of: step one: mixing, namely weighing the As powder with the purity of 99.999% and the simple substance Se powder according to the molar ratio of 1:3-5:6, and mixing; step two: pre-pressing, namely filling 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 enable the mixed powder to be cold-pressed into blocks according to the size of a synthetic cavity; step three: assembling, namely loading the block-shaped 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 hexahedral top press, wherein the synthesis pressure is 1.0-6.0GPa, and the synthesis temperature is 800-1400K; step five: the cooling is carried out,after the high-pressure unit in the fourth step 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 to obtain glassy As 2 Se 3 A bulk material.
Preferably, in the first step, the mole ratio of As powder to Se powder is 2:3, uniformly mixing.
Preferably, in the third step, the assembly is performed by adopting a bypass type assembly method, the assembly structure of the bypass type assembly method is relatively stable, and when the heating conditions are the same, the temperature change is small, and when the direct type assembly method is adopted, the change is large. The side heating type heating mode has great advantages over the direct heating type heating mode in uniformly synthesizing the temperature distribution in the cavity, so that 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 20min.
Preferably, in step five, the temperature is reduced to room temperature at a cooling rate of 150K/min.
As synthesized by the above specific parameters of the present disclosure As shown in FIG. 1 2 Se 3 XRD phase detection patterns of chalcogenide glasses, from which the synthesized As can be obtained 2 Se 3 The chalcogenide glass has an amorphous structure.
In contrast, the assembly mode in the third step adopts direct heating type assembly. The directly-heated assembled cavity has the advantages that the resistivity is changed along with the progress of the reaction, the heat generation rate is greatly fluctuated, the heated difference of different positions in the glass is large, the physical and mechanical properties of the glass are greatly reduced, and the directly-heated assembled cavity cannot be applied to actual life and production.
In contrast, in the fourth step, high-temperature and high-pressure synthesis was performed at a synthesis temperature of 800K at a synthesis pressure of 1GPa and 1400K at a synthesis pressure of 6GPa, respectively. Experimental results show that only materials with a crystalline structure can be formed under lower pressure and temperature conditions, and glass cannot be formed. Although glass can be formed under higher pressure and temperature, the glass can generate different degrees of fragmentation phenomena, and the glass cannot be applied to actual production and life.
In contrast, in step five, cooling was performed at rates of 50K/min, 100K/min, 300K/min, 350K/min, respectively, to room temperature.
The products obtained at cooling rates of 50K/min and 100K/min, due to the slower cooling rate, show crystallization of the glass. As obtained with a cooling rate of 50K/min is shown in FIG. 6 2 Se 3 The bulk material, as can be seen from the figure, does not form chalcogenide glass due to the too low cooling rate. The products obtained at cooling rates of 300K/min and 350K/min are cracked to different degrees due to the residual stresses generated by the faster cooling rates.
In some embodiments, as is prepared according to the methods of preparing chalcogenide glasses of the present disclosure 2 S 3 A chalcogenide glass block material comprising the steps of: step one: mixing, namely weighing the As powder with the purity of 99.999% and the simple substance of the S powder according to the molar ratio of 1:3-5:6, and mixing; step two: pre-pressing, namely filling 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 enable the mixed powder to be cold-pressed into blocks according to the size of a synthetic cavity; step three: assembling, namely loading the block 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 hexahedral top 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, namely, after the high-pressure unit in the fourth step is subjected to heat preservation and pressure maintaining, cooling to room temperature at a cooling rate of 100-300K/min to obtain glassy As 2 S 3 A bulk material.
Preferably, in the first step, 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 20min.
Preferably, in step five, the temperature is reduced to room temperature at a cooling rate of 130K/min.
In other embodiments, sulfur according to the present disclosurePreparation method of glass system, ge is prepared 33 As 12 Se 55 A chalcogenide glass block material comprising the steps of: step one: mixing Ge powder, as powder and Se powder with purity of 99.999 percent according to a mole ratio of 33:12:55, uniformly mixing; step two: prepressing, filling the uniformly mixed powder into a high-temperature-resistant metal shielding cup, filling inert gas, pressurizing to 20-40MPa, and then sealing to enable the mixed powder to be cold-pressed into blocks according to the size of a synthetic cavity; step three: assembling, namely loading the block-shaped 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 hexahedral top 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, namely, after the high-voltage unit in the fourth step is subjected to heat preservation and pressure maintaining, cooling to room temperature at a cooling rate of 100-300K/min to obtain the glassy Ge 33 As 12 Se 55 A bulk material.
Preferably, the synthesis pressure in the fourth step is 5.5GPa, the synthesis temperature is 1300K, and the heat preservation time is 30min.
Preferably, in step five, the temperature is reduced to room temperature at a cooling rate of 200K/min.
As shown in FIG. 4, the Ge synthesized in the above preferred embodiment 33 As 12 Se 55 XRD phase detection diagram of chalcogenide glass bulk material, obtained from the diagram, synthesized Ge 33 As 12 Se 55 The chalcogenide glass bulk material has an amorphous structure.
As for comparison, as was prepared by conventional methods 2 Se 3 、As 2 S 3 And Ge (Ge) 33 As 12 Se 55 Chalcogenide glass block material.
As synthesized by the high temperature high pressure synthesis method is shown in FIG. 2 2 Se 3 A graph comparing Vickers hardness and elastic modulus of chalcogenide glass with those of conventional method is obtained from graph, and As synthesized by high-temperature high-pressure synthesis method is adopted 2 Se 3 Chalcogenide glass has a Vickers hardness higher than 50% and an elastic modulus 4.8GP higher than that of conventional glassa。
As synthesized by the high temperature high pressure synthesis method is shown in FIG. 3 2 S 3 A graph comparing Vickers hardness and elastic modulus of chalcogenide glass with those of conventional method is obtained from graph, and As synthesized by high-temperature high-pressure synthesis method is adopted 2 S 3 Chalcogenide glass has a Vickers hardness substantially higher than that of As synthesized by conventional methods 2 S 3 The elastic modulus of the chalcogenide glass is 6.5GPa higher than that of the chalcogenide glass prepared by the traditional method.
As shown in FIG. 5, ge is synthesized by high temperature high pressure synthesis 33 As 12 Se 55 Comparison of Vickers hardness and elastic modulus of chalcogenide glass with conventional methods, from which can be obtained, ge synthesized by high-temperature high-pressure synthesis method 33 As 12 Se 55 The chalcogenide glass has a Vickers hardness 1.35GPa higher than that prepared by the traditional method and an elastic modulus 5.4GPa higher than that 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, convenient implementation and higher production efficiency.
Claims (3)
1. A preparation method of chalcogenide glass is characterized in that: the method comprises the following steps:
1) And (3) assembling: loading the block-shaped raw materials into a high-pressure cavity;
2) High-temperature high-pressure synthesis: the high-temperature synthesis temperature is 800-1300K, and the high-pressure synthesis pressure is 2.0-5.0GPa;
3) And (3) cooling: after the steps are finished, cooling to room temperature at a cooling rate of 120-250K/min to obtain chalcogenide glass;
prior to step 1), mixing and pre-pressing are included;
the mixing is that non-sulfur elemental gallium (Ga), germanium (Ge), arsenic (As) powder and sulfur elemental sulfur (S), selenium (Se) and tellurium (Te) powder are mixed uniformly according to the mol ratio of 1:3-5:6; the assembly is to assemble raw materials by adopting a bypass type assembly mode; the pre-pressing is to put the mixed powder into a high temperature resistant metal shielding cup, so that the mixed powder is cold-pressed into blocks according to the size of the synthesized cavity.
2. The method for producing a chalcogenide glass according to claim 1, wherein: the high-pressure cavity adopts a graphite tube as a heating body and magnesium oxide or hexagonal boron nitride as an insulator.
3. The method for producing a chalcogenide glass according to claim 1, wherein: in the step 2), the high-temperature high-pressure pressing is completed on a hexahedral top press.
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| 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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| 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 (3)
| Title |
|---|
| AsS：Bulk inorganic molecular-based chalcogenide glass;V.V.Brazhkin等;《Applied Physics Letters》;20070719;第91卷;第013912-1~3页 * |
| High-pressure preparation and structural analysis of Se-S-As ternary system compounds;Bingke Qin等;《Journal of Physics: Conference Series》;20211019;第012041-1~5页 * |
| V.V.Brazhkin等.AsS：Bulk inorganic molecular-based chalcogenide glass.《Applied Physics Letters》.2007,第91卷第013912-1~3页. * |
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