CN115626771B - High-hardness Ge-As-Se chalcogenide glass and preparation method and application thereof - Google Patents
High-hardness Ge-As-Se chalcogenide glass and preparation method and application thereof Download PDFInfo
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- CN115626771B CN115626771B CN202211309067.4A CN202211309067A CN115626771B CN 115626771 B CN115626771 B CN 115626771B CN 202211309067 A CN202211309067 A CN 202211309067A CN 115626771 B CN115626771 B CN 115626771B
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- 239000005387 chalcogenide glass Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000126 substance Substances 0.000 claims description 81
- 239000002994 raw material Substances 0.000 claims description 50
- 238000010791 quenching Methods 0.000 claims description 42
- 230000000171 quenching effect Effects 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 40
- 238000000137 annealing Methods 0.000 claims description 37
- 238000002844 melting Methods 0.000 claims description 35
- 230000008018 melting Effects 0.000 claims description 35
- 238000001816 cooling Methods 0.000 claims description 33
- 238000000746 purification Methods 0.000 claims description 33
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 24
- 238000005292 vacuum distillation Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012264 purified product Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 33
- 229910052711 selenium Inorganic materials 0.000 abstract description 15
- 238000002834 transmittance Methods 0.000 abstract description 15
- 229910052732 germanium Inorganic materials 0.000 abstract description 7
- 229910052785 arsenic Inorganic materials 0.000 abstract description 6
- 239000011669 selenium Substances 0.000 description 96
- 239000000203 mixture Substances 0.000 description 47
- 239000010453 quartz Substances 0.000 description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 47
- 238000004821 distillation Methods 0.000 description 24
- 238000007789 sealing Methods 0.000 description 20
- 238000005906 dihydroxylation reaction Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 14
- 238000002156 mixing Methods 0.000 description 12
- 239000003708 ampul Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010981 drying operation Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
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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
- C03C4/00—Compositions for glass with special properties
- C03C4/10—Compositions for glass with special properties for infrared transmitting glass
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention provides high-hardness Ge-As-Se chalcogenide glass and a preparation method and application thereof, and belongs to the technical field of chalcogenide glass. The high refractive index Ge-As-Se chalcogenide glass provided by the invention comprises the following components in percentage by atom: ge: 35-55%, as: 10-50% and Se: 1-30%. According to the invention, the hardness of the glass is improved by adding Ge and As elements with higher coordination numbers into the glass; the content of Ge and As elements is increased to increase the coordination number of the glass, so that the hardness of the glass is increased, the proportion of each element is adjusted to further increase the hardness of the glass, and the glass has good stability and transmittance. Experimental results show that the high-hardness Ge-As-Se chalcogenide glass provided by the invention has 53% transmittance in an infrared window and 300-420 kg.mm Vickers hardness ‑2 Has good transmittance and higher hardness.
Description
Technical Field
The invention relates to the technical field of chalcogenide glass, in particular to high-hardness Ge-As-Se chalcogenide glass and a preparation method and application thereof.
Background
The chalcogenide glass is gradually developed and applied as an infrared material in the fifty years of the last century, has the advantages of low phonon energy, high refractive index, high infrared transmittance and the like, and is widely applied to military and civil use. However, the hardness of the chalcogenide glass currently on the market is not more than 300 kg mm -2 The surface is easily scratched or even broken, and commercial glass As is the most widely used 2 Se 3 Has a hardness of only 157kgmm -2 It is difficult to meet the requirement of high hardness.
Currently, in order to increase the hardness of chalcogenide glass, methods such as doping with various elements and microcrystallization are generally used, but there is still a defect that the hardness of chalcogenide glass is weak. Therefore, providing a chalcogenide glass with higher hardness is a technical problem to be solved in the art.
Disclosure of Invention
The invention aims to provide high-hardness Ge-As-Se chalcogenide glass As well As a preparation method and application thereof. The high-hardness Ge-As-Se chalcogenide glass provided by the invention has higher hardness and is commercial glass As 2 Se 3 The defect of weaker hardness of the sulfur glass in the market can be relieved by more than twice.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides high-hardness Ge-As-Se chalcogenide glass, which comprises the following components in percentage by atom: ge: 35-55%, as: 10-50% and Se: 1-30%.
Preferably, the high hardness Ge-As-Se chalcogenide glass includes, in atomic percent: ge: 40-45%, as: 30-40% and Se: 15-20%.
Preferably, the high hardness Ge-As-Se chalcogenide glass has a Vickers hardness of 300-420 kg-mm -2 。
The invention provides a preparation method of the high-hardness Ge-As-Se chalcogenide glass, which comprises the following steps:
(1) Purifying the raw materials to obtain a purified product;
(2) And (3) sequentially melting, quenching and annealing the purified product obtained in the step (1) to obtain the high-hardness Ge-As-Se chalcogenide glass.
Preferably, the purification mode in the step (1) is any one of a vacuum distillation method, an oxygen scavenger method and a vacuum distillation combined oxygen scavenger method.
Preferably, the purification is carried out by vacuum distillation in combination with an oxygen scavenger process.
Preferably, the melting temperature in the step (2) is 850-950 ℃, and the melting time is 30-35 h.
Preferably, the quenching temperature in the step (2) is 650-750 ℃, and the quenching cooling mode is water cooling.
Preferably, the annealing temperature in the step (2) is 300-450 ℃, and the cooling rate of the annealing is 2-10 ℃/h.
The invention provides the application of the high-hardness Ge-As-Se chalcogenide glass in infrared optics.
The invention provides high-hardness Ge-As-Se chalcogenide glass, which comprises the following components in percentage by atom: ge: 35-55%, as: 10-50% and Se: 1-30%. The high-hardness Ge-As-Se chalcogenide glass provided by the invention has the advantages that the hardness of the glass is improved by adding Ge and As elements with higher coordination numbers into the glass; the content of Ge and As elements is increased to increase the coordination number of the glass, so that the hardness of the glass is increased, the proportion of each element is adjusted to further increase the hardness of the glass, and the glass has good stability and transmittance. Experimental results show that the high-hardness Ge-As-Se chalcogenide glass provided by the invention has 53% transmittance in an infrared window and 300-420 kg.mm Vickers hardness -2 Has good transmittance and higher hardness than the prior commercial infrared chalcogenide glass materials.
Drawings
FIG. 1 is a graph showing the infrared window transmittance of a high hardness Ge-As-Se chalcogenide glass As prepared in example 1 of the present invention.
Detailed Description
The invention provides high-hardness Ge-As-Se chalcogenide glass, which comprises the following components in percentage by atom: ge: 30-55%, as: 10-50% and Se: 1-30%.
The Ge-As-Se chalcogenide glass provided by the invention comprises the following components in percentage by atom: 30 to 55%, preferably 40 to 45%, more preferably 42%. In the invention, germanium atoms have higher coordination numbers, and the hardness of the glass can be improved by adding the germanium atoms into chalcogenide glass; by controlling the content of germanium element within the above range, it is possible to ensure that the chalcogenide glass has a high hardness.
The Ge-As-Se chalcogenide glass provided by the invention comprises the following components in percentage by atom: 10 to 50%, preferably 30 to 40%, more preferably 35%. In the invention, arsenic atoms have higher coordination numbers, and the hardness of the glass can be improved by adding the arsenic atoms into chalcogenide glass; by controlling the content of arsenic element within the above range, it is possible to ensure that the chalcogenide glass has a high hardness.
The Ge-As-Se chalcogenide glass provided by the invention comprises Se in atomic percent: 1 to 30%, preferably 15 to 20%, more preferably 18%. In the invention, selenium is added into the glass to ensure that the glass has good infrared transmittance and stability, but the excessive selenium content can reduce the hardness of the glass; by controlling the content of selenium element in the above range, the sulfur glass can have higher hardness under the condition of good infrared transmittance.
In the invention, the high-hardness Ge-As-Se chalcogenide glass has a hardness of 300-420 kg.mm -2 . Compared with the prior commercial infrared chalcogenide glass materials, the chalcogenide glass provided by the invention has higher hardness.
The Ge and As elements with high coordination numbers in the high-hardness Ge-As-Se chalcogenide glass can improve the hardness of the chalcogenide glass, and the Ge-As-Se chalcogenide glass not only has high hardness, but also has good infrared transmittance and stability by limiting the content of the Ge, as and Se elements.
The invention also provides a preparation method of the high-hardness Ge-As-Se chalcogenide glass, which comprises the following steps:
(1) Purifying the raw materials to obtain a purified product;
(2) And (3) sequentially melting, quenching and annealing the purified product obtained in the step (1) to obtain the high-hardness Ge-As-Se chalcogenide glass.
The invention purifies the raw materials to obtain a purified product.
In the invention, the raw materials are preferably Ge simple substance, as simple substance and Se simple substance; the purity of the Ge simple substance, the As simple substance and the Se simple substance is independently preferably more than or equal to 5N. According to the invention, the simple substance is selected as the raw material, and the purity of the raw material is limited to the range, so that the content of impurities and oxides in the raw material can be reduced, and the purity of the glass is further improved.
In the present invention, the purification is preferably performed in a quartz reactor; the quartz reactor is preferably an H-type double tube quartz ampoule. In the present invention, the H-type double tube quartz ampoule preferably includes a raw material tube, a purification tube, and a connection tube connecting the raw material tube and the purification tube; one end of the raw material pipe is provided with an opening or one end of the raw material pipe and one end of the purifying pipe are provided with openings. The device is convenient for sealing the opening of the raw material pipe in a melting way during purification, thereby providing a vacuum environment for the mixture and the deoxidizer which are placed in the H-shaped double-tube quartz ampoule, avoiding the raw material from being oxidized to introduce impurities, and reducing the extrinsic absorption of the chalcogenide glass in the infrared region.
In the present invention, the quartz reactor is preferably subjected to dehydroxylation pretreatment and drying in sequence before use.
In the present invention, the dehydroxylation pretreatment preferably includes: the quartz reactor is cleaned with hydrofluoric acid, deionized water and absolute ethyl alcohol in sequence. The cleaning operation is not particularly limited in the present invention, and a conventional cleaning operation in the art may be employed. The invention can avoid impurity oxygen brought to the reaction by the quartz reactor through the dehydroxylation pretreatment.
In the present invention, the drying is preferably performed in an oven. The drying operation is not particularly limited, and the drying operation commonly used in the art can be adopted. The invention can avoid introducing impurity oxygen in the reaction by drying.
The quartz reactor is preferably preheated and vacuumized before purification; the preheating and evacuating are preferably performed simultaneously.
In the present invention, the temperature of the preheating is preferably 50 to 100 ℃, more preferably 80 to 90 ℃. The invention can be used for facilitating the subsequent melting of glass by limiting the preheating temperature to be within the range.
In the present invention, the degree of vacuum of the evacuation is preferably 5X 10 or more -5 Pa, more preferably 5X 10 -5 ～1 ×10 - 3 Pa; the time of vacuumizing is preferably more than or equal to 3 hours. The invention is realized by the vacuum pumpingAnd the air is empty, so that the influence caused by oxygen in the air in the purification process can be avoided. The invention can make the vacuum degree of the quartz reactor meet the requirement by limiting the vacuum degree to the above range.
In the present invention, when an opening is provided at one end of the raw material pipe of the quartz reactor, the vacuum pumping mode is preferably as follows: the raw materials are added into the raw material pipe through an opening on the raw material pipe of the quartz reactor, then vacuum is pumped, and finally the opening on the raw material pipe is sealed.
In the present invention, when the openings are provided at one end of the raw material pipe and one end of the purifying pipe of the quartz reactor, the vacuum pumping mode is preferably as follows: the method comprises the steps of adding raw materials into a raw material pipe through an opening on the raw material pipe of a quartz reactor, sealing the opening on the raw material pipe in a sealing mode, vacuumizing through the opening on a purifying pipe, and sealing the opening on the purifying pipe in a sealing mode.
In the present invention, oxyhydrogen flame or oxy-acetylene flame is preferably used for the sealing. By adopting the mode for sealing, the invention can reduce impurity oxygen brought to the reaction in the sealing process.
In the present invention, the purification means is preferably any one of a vacuum distillation method, an oxygen scavenger method, and a vacuum distillation combined oxygen scavenger method, and more preferably a vacuum distillation combined oxygen scavenger method. The invention can eliminate [ -OH ] and [ H-O-H ] impurities in the chalcogenide glass by purifying the raw materials, and reduce the influence of extrinsic absorption loss in the chalcogenide glass on the infrared characteristics of the chalcogenide glass.
In the present invention, the purification by vacuum distillation in combination with the oxygen scavenger method preferably comprises the steps of:
1) Mixing Ge simple substance, as simple substance and Se simple substance to obtain a mixture, and adding an deoxidizer to mix to obtain a mixture to be purified;
2) And 3) adding the mixture to be purified obtained in the step 1) into a quartz reactor, and then placing the quartz reactor into a double-temperature-zone distillation furnace for purification to obtain a purified mixture.
The method is characterized in that Ge simple substance, as simple substance and Se simple substance are preferably mixed to obtain a mixture, and then an deoxidizer is added to mix to obtain a mixture to be purified.
In the present invention, the oxygen scavenger is preferably elemental Mg or elemental Al. In the present invention, the amount of the oxygen scavenger is preferably 0.03 to 0.1wt% of the mixture, more preferably 0.05 to 0.08wt%. The invention adopts the simple substance Mg or the simple substance Al as the deoxidizer, and the simple substance Mg or the simple substance Al is active elements and has the capability of preferentially combining with oxygen to form bonds, so that a series of harmful absorbed X-O bonds in a near infrared region, a middle infrared region and a far infrared region are eliminated, and oxides generated by the deoxidizer have lower vapor pressure, can volatilize and not remain in the chalcogenide glass, and avoid influencing the components of the chalcogenide glass. The invention can avoid the problem that oxygen impurities in the chalcogenide glass cannot be sufficiently removed due to too small amount of the deoxidizer, and can also avoid the problem that glass is crystallized and devitrified during glass drawing due to too large amount of the deoxidizer by limiting the amount of the deoxidizer to be within the range.
The invention is not particularly limited to the above-mentioned mixing operation, and the raw materials are uniformly mixed by adopting the conventional mixing operation in the field.
After the mixture to be purified is obtained, the mixture to be purified is preferably added into a quartz reactor, and then placed into a double-temperature-zone distillation furnace for purification, so that the purified mixture is obtained.
In the invention, the cold end temperature of the double temperature zone distillation furnace is preferably 300-500 ℃, more preferably 350-450 ℃, and even more preferably 400 ℃; the hot end temperature of the double temperature zone distillation furnace is preferably 850 to 950 ℃, more preferably 870 to 920 ℃, and even more preferably 900 ℃. According to the invention, purification is carried out in a double-temperature-zone distillation furnace, and distillation treatment is carried out on the raw materials by utilizing the characteristic that the vapor pressure of simple substances and oxides thereof in the raw materials is greatly different at a certain temperature, so that oxygen and other non-volatile impurities are removed, and the oxygen removal effect is expected to be achieved.
After the purified product is obtained, the purified product is sequentially melted, quenched and annealed to obtain the high-hardness Ge-As-Se chalcogenide glass.
In the present invention, the melting is preferably performed under vacuum conditions; the vacuum isThe vacuum degree of the condition is preferably not less than 5X 10 -5 Pa, more preferably 5X 10 -5 ～1×10 -3 Pa. In the present invention, the melting temperature is preferably 850 to 950 ℃, more preferably 900 to 950 ℃; the melting time is preferably 30 to 35 hours, more preferably 32 hours. The invention can lead the raw materials to be completely melted and mixed together by limiting the melting temperature and the melting time within the range so as to form a molten glass state, thereby forming the short-range ordered and long-range unordered chalcogenide glass.
After the melting is finished, the invention preferably naturally cools the melted product to the quenching temperature for quenching. The natural cooling mode is not particularly limited, and may be determined according to the technical common knowledge of a person skilled in the art.
In the present invention, the quenching is preferably performed under vacuum conditions; the vacuum degree of the vacuum condition is preferably not less than 5 multiplied by 10 -5 Pa, more preferably 5X 10 -5 ～1×10 -3 Pa. In the present invention, the quenching temperature is preferably 650 to 750 ℃, more preferably 700 ℃; the quenching is preferably performed by water cooling. The quenching time is not particularly limited, and the quenching can be performed until the room temperature is reached. The invention can eliminate internal stress of glass through quenching treatment, and can ensure that the structure of the glass is ordered in a short range and disordered in a long range, thereby having excellent performance.
In the present invention, the annealing is preferably performed under vacuum conditions; the vacuum degree of the vacuum condition is preferably not less than 5 multiplied by 10 -5 Pa, more preferably 5X 10 -5 ～1×10 -3 Pa. In the present invention, the annealing temperature is preferably 300 to 450 ℃, more preferably 400 to 430 ℃; the cooling rate of the annealing is preferably 2 to 10℃per hour, more preferably 8℃per hour. The invention reduces or eliminates the uneven permanent thermal stress formed in the quenching process of the chalcogenide glass through annealing treatment, thereby improving the mechanical strength and the thermal stability of the chalcogenide glass.
According to the invention, the raw materials are purified, so that redundant impurities in the raw materials are removed, and the hardness and the red infrared transmittance of the glass are improved; the glass with ordered short range and disordered long range is formed by carrying out melting, quenching and annealing treatment and adjusting the technological parameters of the melting, quenching and annealing treatment, so that the hardness of the glass is further improved.
The invention provides the application of the high-hardness Ge-As-Se chalcogenide glass in infrared optics. The application of the high-hardness Ge-As-Se chalcogenide glass is not particularly limited, and the high-hardness Ge-As-Se chalcogenide glass is determined according to the technical common knowledge of a person skilled in the art.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The high-hardness Ge-As-Se chalcogenide glass comprises the following components in percentage by atom: ge:45%, as:35% and Se:20% of a base;
the preparation method of the high-hardness Ge-As-Se chalcogenide glass comprises the following steps:
(1) Purifying the Ge simple substance, the As simple substance and the Se simple substance by adopting a vacuum distillation combined oxygen scavenger method to obtain a purification mixture;
(2) Melting the purification mixture obtained in the step (1), naturally cooling to a quenching temperature for quenching, and finally heating to an annealing temperature for annealing to obtain the high-hardness Ge-As-Se chalcogenide glass; the melting temperature is 950 ℃, and the melting time is 35 hours; the quenching temperature is 700 ℃, and the quenching cooling mode is water cooling; the annealing temperature is 430 ℃, and the cooling rate of the annealing is 10 ℃/h;
the vacuum distillation combined oxygen scavenger method comprises the following steps:
1) Mixing Ge simple substance, as simple substance and Se simple substance to obtain a mixture, and adding an deoxidizer to mix to obtain a mixture to be purified; the purity of the Ge simple substance, the As simple substance and the Se simple substance is 5N; the deoxidizer is simple substance Mg, and the dosage of the deoxidizer is 0.1wt% of the mixture;
2) Adding the mixture to be purified obtained in the step 1) into a raw material pipe through an opening on the raw material pipe of the H-shaped double-pipe quartz ampoule, vacuumizing and simultaneously preheating, finally sealing the opening on the raw material pipe in a sealing manner, and then placing the quartz reactor into a double-temperature-zone distillation furnace for purification; the quartz reactor is subjected to dehydroxylation pretreatment, wherein the process of the dehydroxylation pretreatment is to clean the quartz reactor sequentially by hydrofluoric acid, deionized water and absolute ethyl alcohol, and finally, the quartz reactor is put into a drying oven for complete drying; the temperature of the preheating is 90 ℃; the vacuum degree of the vacuumized air is 1 multiplied by 10 -3 Pa, and vacuumizing for 3 hours; the cold end temperature of the double-temperature-zone distillation furnace is 400 ℃, and the hot end temperature of the double-temperature-zone distillation furnace is 950 ℃.
The performance of the high hardness Ge-As-Se chalcogenide glass prepared in example 1 was tested, and the results are shown in FIG. 1. As can be seen from FIG. 1, the infrared window transmittance of the high-hardness Ge-As-Se chalcogenide glass prepared in example 1 reaches 53%.
The transmittance of the high-hardness Ge-As-Se chalcogenide glass prepared by the method reaches 53% in an infrared window; the hardness of the high-hardness Ge-As-Se chalcogenide glass was measured to be 398.2 kg.multidot.mm -2 Is As 2 Se 3 2.5 times of glass.
Example 2
The high-hardness Ge-As-Se chalcogenide glass comprises the following components in percentage by atom: ge:40%, as:40% and Se:20% of a base;
the preparation method of the high-hardness Ge-As-Se chalcogenide glass comprises the following steps:
(1) Purifying the Ge simple substance, the As simple substance and the Se simple substance by adopting a vacuum distillation combined oxygen scavenger method to obtain a purification mixture;
(2) Melting the purification mixture obtained in the step (1), naturally cooling to a quenching temperature for quenching, and finally heating to an annealing temperature for annealing to obtain the high-hardness Ge-As-Se chalcogenide glass; the melting temperature is 950 ℃, and the melting time is 30 hours; the quenching temperature is 700 ℃, and the quenching cooling mode is water cooling; the annealing temperature is 420 ℃, and the cooling rate of the annealing is 10 ℃/h;
the vacuum distillation combined oxygen scavenger method comprises the following steps:
1) Mixing Ge simple substance, as simple substance and Se simple substance to obtain a mixture, and adding an deoxidizer to mix to obtain a mixture to be purified; the purity of the Ge simple substance, the As simple substance and the Se simple substance is 5N; the deoxidizer is simple substance Mg, and the dosage of the deoxidizer is 0.1wt% of the mixture;
2) Adding the mixture to be purified obtained in the step 1) into a raw material pipe through an opening on the raw material pipe of the H-shaped double-pipe quartz ampoule, vacuumizing and simultaneously preheating, finally sealing the opening on the raw material pipe in a sealing manner, and then placing the quartz reactor into a double-temperature-zone distillation furnace for purification; the quartz reactor is subjected to dehydroxylation pretreatment, wherein the process of the dehydroxylation pretreatment is to clean the quartz reactor sequentially by hydrofluoric acid, deionized water and absolute ethyl alcohol, and finally, the quartz reactor is put into a drying oven for complete drying; the temperature of the preheating is 90 ℃; the vacuum degree of the vacuumized air is 1 multiplied by 10 -3 Pa, and vacuumizing for 3 hours; the cold end temperature of the double-temperature-zone distillation furnace is 400 ℃, and the hot end temperature of the double-temperature-zone distillation furnace is 950 ℃.
The hardness of the high-hardness Ge-As-Se chalcogenide glass was measured to be 367. kg.mm -2 。
Example 3
The high-hardness Ge-As-Se chalcogenide glass comprises the following components in percentage by atom: ge:50%, as:20% and Se:30%;
the preparation method of the high-hardness Ge-As-Se chalcogenide glass comprises the following steps:
(1) Purifying the Ge simple substance, the As simple substance and the Se simple substance by adopting a vacuum distillation combined oxygen scavenger method to obtain a purification mixture;
(2) Melting the purification mixture obtained in the step (1), naturally cooling to a quenching temperature for quenching, and finally heating to an annealing temperature for annealing to obtain the high-hardness Ge-As-Se chalcogenide glass; the melting temperature is 950 ℃, and the melting time is 30 hours; the quenching temperature is 700 ℃, and the quenching cooling mode is water cooling; the annealing temperature is 430 ℃, and the cooling rate of the annealing is 10 ℃/h;
the vacuum distillation combined oxygen scavenger method comprises the following steps:
1) Mixing Ge simple substance, as simple substance and Se simple substance to obtain a mixture, and adding an deoxidizer to mix to obtain a mixture to be purified; the purity of the Ge simple substance, the As simple substance and the Se simple substance is 5N; the deoxidizer is simple substance Mg, and the dosage of the deoxidizer is 0.1wt% of the mixture;
2) Adding the mixture to be purified obtained in the step 1) into a raw material pipe through an opening on the raw material pipe of the H-shaped double-pipe quartz ampoule, vacuumizing and simultaneously preheating, finally sealing the opening on the raw material pipe in a sealing manner, and then placing the quartz reactor into a double-temperature-zone distillation furnace for purification; the quartz reactor is subjected to dehydroxylation pretreatment, wherein the process of the dehydroxylation pretreatment is to clean the quartz reactor sequentially by hydrofluoric acid, deionized water and absolute ethyl alcohol, and finally, the quartz reactor is put into a drying oven for complete drying; the temperature of the preheating is 90 ℃; the vacuum degree of the vacuumized air is 1 multiplied by 10 -3 Pa, and vacuumizing for 3 hours; the cold end temperature of the double-temperature-zone distillation furnace is 400 ℃, and the hot end temperature of the double-temperature-zone distillation furnace is 950 ℃.
The hardness of the high-hardness Ge-As-Se chalcogenide glass was measured to be 362.3 kg mm -2 。
Example 4
The high-hardness Ge-As-Se chalcogenide glass comprises the following components in percentage by atom: ge:35%, as:45% and Se:20% of a base;
the preparation method of the high-hardness Ge-As-Se chalcogenide glass comprises the following steps:
(1) Purifying the Ge simple substance, the As simple substance and the Se simple substance by adopting a vacuum distillation combined oxygen scavenger method to obtain a purification mixture;
(2) Melting the purification mixture obtained in the step (1), naturally cooling to a quenching temperature for quenching, and finally heating to an annealing temperature for annealing to obtain the high-hardness Ge-As-Se chalcogenide glass; the melting temperature is 950 ℃, and the melting time is 30 hours; the quenching temperature is 700 ℃, and the quenching cooling mode is water cooling; the annealing temperature is 430 ℃, and the cooling rate of the annealing is 10 ℃/h;
the vacuum distillation combined oxygen scavenger method comprises the following steps:
1) Mixing the Ge simple substance, the As simple substance and the Se simple substance to obtain a mixture, and adding an deoxidizer for mixing to obtain a mixture to be purified; the purity of the Ge simple substance, the As simple substance and the Se simple substance is 5N; the deoxidizer is simple substance Mg, and the dosage of the deoxidizer is 0.1wt% of the mixture;
2) Adding the mixture to be purified obtained in the step 1) into a raw material pipe through an opening on the raw material pipe of the H-shaped double-pipe quartz ampoule, vacuumizing and simultaneously preheating, finally sealing the opening on the raw material pipe in a sealing manner, and then placing the quartz reactor into a double-temperature-zone distillation furnace for purification; the quartz reactor is subjected to dehydroxylation pretreatment, wherein the process of the dehydroxylation pretreatment is to clean the quartz reactor sequentially by hydrofluoric acid, deionized water and absolute ethyl alcohol, and finally, the quartz reactor is put into a drying oven for complete drying; the temperature of the preheating is 90 ℃; the vacuum degree of the vacuumized air is 1 multiplied by 10 -3 Pa, and vacuumizing for 3 hours; the cold end temperature of the double-temperature-zone distillation furnace is 400 ℃, and the hot end temperature of the double-temperature-zone distillation furnace is 950 ℃.
The hardness of the high-hardness Ge-As-Se chalcogenide glass was measured to be 356.7 kg mm -2 。
Comparative example 1
The high-hardness Ge-As-Se chalcogenide glass comprises the following components in percentage by atom: ge:10%, as:30% and Se:60 percent;
the preparation method of the high-hardness Ge-As-Se chalcogenide glass comprises the following steps:
(1) Purifying the Ge simple substance, the As simple substance and the Se simple substance by adopting a vacuum distillation combined oxygen scavenger method to obtain a purification mixture;
(2) Melting the purification mixture obtained in the step (1), naturally cooling to a quenching temperature for quenching, and finally heating to an annealing temperature for annealing to obtain the high-hardness Ge-As-Se chalcogenide glass; the melting temperature is 900 ℃, and the melting time is 30 hours; the quenching temperature is 550 ℃, and the quenching cooling mode is water cooling; the annealing temperature is 200 ℃, and the cooling rate of annealing is 5 ℃/h;
the vacuum distillation combined oxygen scavenger method comprises the following steps:
1) Mixing the Ge simple substance, the As simple substance and the Se simple substance to obtain a mixture, and adding an deoxidizer for mixing to obtain a mixture to be purified; the purity of the Ge simple substance, the As simple substance and the Se simple substance is 5N; the deoxidizer is simple substance Mg, and the dosage of the deoxidizer is 0.1wt% of the mixture; 2) Adding the mixture to be purified obtained in the step 1) into a raw material pipe through an opening on the raw material pipe of the H-shaped double-pipe quartz ampoule, vacuumizing and simultaneously preheating, finally sealing the opening on the raw material pipe in a sealing manner, and then placing the quartz reactor into a double-temperature-zone distillation furnace for purification; the quartz reactor is subjected to dehydroxylation pretreatment, wherein the process of the dehydroxylation pretreatment is to clean the quartz reactor sequentially by hydrofluoric acid, deionized water and absolute ethyl alcohol, and finally, the quartz reactor is put into a drying oven for complete drying; the temperature of the preheating is 90 ℃; the vacuum degree of the vacuumized air is 1 multiplied by 10 -3 Pa, and vacuumizing for 3 hours; the cold end temperature of the double-temperature-zone distillation furnace is 400 ℃, and the hot end temperature of the double-temperature-zone distillation furnace is 950 ℃.
The hardness of the high-hardness Ge-As-Se chalcogenide glass was measured to be 176.1 kg mm -2 。
Comparative example 2
The high-hardness Ge-As-Se chalcogenide glass comprises the following components in percentage by atom: ge:30%, as:30% and Se:40%;
the preparation method of the high-hardness Ge-As-Se chalcogenide glass comprises the following steps:
(1) Purifying the Ge simple substance, the As simple substance and the Se simple substance by adopting a vacuum distillation combined oxygen scavenger method to obtain a purification mixture;
(2) Melting the purification mixture obtained in the step (1), naturally cooling to a quenching temperature for quenching, and finally heating to an annealing temperature for annealing to obtain the high-hardness Ge-As-Se chalcogenide glass; the melting temperature is 900 ℃, and the melting time is 30 hours; the quenching temperature is 550 ℃, and the quenching cooling mode is water cooling; the annealing temperature is 220 ℃, and the cooling rate of annealing is 5 ℃/h;
the vacuum distillation combined oxygen scavenger method comprises the following steps:
1) Mixing the Ge simple substance, the As simple substance and the Se simple substance to obtain a mixture, and adding an deoxidizer for mixing to obtain a mixture to be purified; the purity of the Ge simple substance, the As simple substance and the Se simple substance is 5N; the deoxidizer is simple substance Mg, and the dosage of the deoxidizer is 0.1wt% of the mixture;
2) Adding the mixture to be purified obtained in the step 1) into a raw material pipe through an opening on the raw material pipe of the H-shaped double-pipe quartz ampoule, vacuumizing and simultaneously preheating, finally sealing the opening on the raw material pipe in a sealing manner, and then placing the quartz reactor into a double-temperature-zone distillation furnace for purification; the quartz reactor is subjected to dehydroxylation pretreatment, wherein the process of the dehydroxylation pretreatment is to clean the quartz reactor sequentially by hydrofluoric acid, deionized water and absolute ethyl alcohol, and finally, the quartz reactor is put into a drying oven for complete drying; the temperature of the preheating is 90 ℃; the vacuum degree of the vacuumized air is 1 multiplied by 10 -3 Pa, and vacuumizing for 3 hours; the cold end temperature of the double-temperature-zone distillation furnace is 400 ℃, and the hot end temperature of the double-temperature-zone distillation furnace is 950 ℃.
The hardness of the high-hardness Ge-As-Se chalcogenide glass was measured and found to be 294. kg.mm -2 。
As can be seen from the comparison of examples 1 to 4 and comparative examples 1 and 2, the high hardness Ge-As-Se chalcogenide glass prepared by the invention has a transmittance of 50% in an infrared window and a Vickers hardness of 300-420 kg.mm -2 Has the characteristic of high hardness, and according to the comparison with comparative examples 1 and 2, it can be seen that sulfur as coordination number in the chalcogenide glass decreasesThe hardness of the sulfur glass is obviously reduced, and when the Se element content is higher than 30%, the prepared sulfur glass has no advantage of high hardness in the market.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A high hardness Ge-As-Se chalcogenide glass comprising in atomic percent: ge: 40-55%, as: 30-40% of Se: 15-20%;
the high-hardness Ge-As-Se chalcogenide glass has a Vickers hardness of 300-420 kg-mm -2 。
2. The method for producing a high-hardness Ge-As-Se chalcogenide glass according to claim 1, comprising the steps of:
(1) Purifying the raw materials to obtain a purified product; the raw materials are Ge simple substance, as simple substance and Se simple substance;
(2) And (3) sequentially melting, quenching and annealing the purified product obtained in the step (1) to obtain the high-hardness Ge-As-Se chalcogenide glass.
3. The method according to claim 2, wherein the purification in the step (1) is performed by any one of a vacuum distillation method, an oxygen scavenger method and a vacuum distillation combined oxygen scavenger method.
4. A method of preparation according to claim 3 wherein the purification is by vacuum distillation in combination with oxygen scavenger.
5. The method according to claim 2, wherein the melting temperature in the step (2) is 850-950 ℃ and the melting time is 30-35 h.
6. The preparation method of claim 2, wherein the quenching temperature in the step (2) is 650-750 ℃, and the quenching cooling mode is water cooling.
7. The method according to claim 2, wherein the annealing temperature in the step (2) is 300-450 ℃, and the cooling rate of the annealing is 2-10 ℃/h.
8. The use of a high hardness Ge-As-Se chalcogenide glass As defined in claim 1 or a high hardness Ge-As-Se chalcogenide glass As defined in any one of claims 2 to 7 in infrared optics.
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| CN104926119A (en) * | 2014-03-21 | 2015-09-23 | 徐州斯梅尔光电科技有限公司 | High performance infrared chalcogenide glass and preparation method thereof |
| CN111015432A (en) * | 2019-11-26 | 2020-04-17 | 天津津航技术物理研究所 | Chemical mechanical processing method for improving optical surface quality of Ge-As-Se chalcogenide glass |
| CN111187005A (en) * | 2020-02-28 | 2020-05-22 | 成都光明光电有限责任公司 | Chalcogenide infrared microcrystalline glass and preparation method thereof |
| CN114956553A (en) * | 2021-02-22 | 2022-08-30 | 上海超摩光电科技有限公司 | Holmium-doped chalcogenide glass and preparation method thereof |
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| CN104926119A (en) * | 2014-03-21 | 2015-09-23 | 徐州斯梅尔光电科技有限公司 | High performance infrared chalcogenide glass and preparation method thereof |
| CN111015432A (en) * | 2019-11-26 | 2020-04-17 | 天津津航技术物理研究所 | Chemical mechanical processing method for improving optical surface quality of Ge-As-Se chalcogenide glass |
| CN111187005A (en) * | 2020-02-28 | 2020-05-22 | 成都光明光电有限责任公司 | Chalcogenide infrared microcrystalline glass and preparation method thereof |
| CN114956553A (en) * | 2021-02-22 | 2022-08-30 | 上海超摩光电科技有限公司 | Holmium-doped chalcogenide glass and preparation method thereof |
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