A high-hardness Ge-Sb-Se chalcogenide glass and its preparation method and application, infrared lens and its application

Abstract

The present invention provides a high-hardness Ge-Sb-Se chalcogenide glass, a preparation method and application thereof, an infrared lens and application thereof, and belongs to the technical field of special glass. The present invention purifies the raw materials for preparation, removes excess impurities in the raw materials, and reduces the non-intrinsic absorption of the chalcogenide glass in the infrared region; the components are evenly mixed by melting, and a short-range ordered and long-range disordered glass is formed by quenching treatment; the uneven permanent thermal stress formed by the chalcogenide glass during the quenching process can be reduced or eliminated by annealing treatment, and the mechanical properties such as hardness and thermal stability of the chalcogenide glass are improved, thereby obtaining a high-hardness Ge-Sb-Se chalcogenide glass, and the hardness of the chalcogenide glass is as high as 236.7kg·mm ‑2 , infrared window transmittance is up to 55%.

Description

Technical Field

[0001] The present invention belongs to the technical field of special glass, and in particular relates to a high-hardness Ge-Sb-Se chalcogenide glass and a preparation method and application thereof, an infrared lens and an application thereof. Background Art

[0002] Chalcogenide glass has the characteristics of low cost and adjustable composition, so that the lenses made of chalcogenide glass have gradually replaced the expensive single crystal Ge lenses, and have a very broad application prospect in the fields of infrared vehicles, military weapons, smart homes, etc. Among them, the hardness of the most widely used commercial chalcogenide glass As2Se3 is only 157kg mm -2 The hardness of chalcogenide glass is much lower than that of single crystal Ge lens, which limits its application in more scenarios. The hardness of chalcogenide glass can be improved by doping it with multiple elements and microcrystallization.

[0003] For example, Chinese patent CN113998896A discloses an efficient synthesis method of chalcogenide glass powder. According to the chemical composition of the chalcogenide glass powder, each single substance raw material with a particle size of less than 500 μm is mixed, and protective gas and liquid nitrogen are introduced for low-temperature ball milling to obtain chalcogenide glass powder. The chalcogenide glass powder synthesized by the above method has high purity and small particle size, and can be used to prepare bulk chalcogenide glass with high optical quality. However, the hardness of the chalcogenide glass made from the chalcogenide glass powder synthesized by the above method does not exceed 200 kg·mm -2 , its hardness is small. Summary of the invention

[0004] In view of this, an object of the present invention is to provide a high-hardness Ge-Sb-Se chalcogenide glass and a preparation method and application thereof, an infrared lens and an application thereof. The Ge-Sb-Se chalcogenide glass prepared by the present invention has high hardness.

[0005] In order to achieve the above object, the present invention adopts the following technical solution:

[0006] The present invention provides a method for preparing a high-hardness Ge-Sb-Se chalcogenide glass, comprising the following steps:

[0007] Purifying the raw materials to obtain a purified mixture; the raw materials include Ge, Sb and Se;

[0008] The purified mixture is sequentially melted, quenched and annealed to obtain a Ge-Sb-Se chalcogenide glass with high hardness.

[0009] Preferably, the raw materials for preparation include: Ge 30-45at%, Sb 1-15at% and Se 40-55at%.

[0010] Preferably, the purification is performed by vacuum distillation or vacuum distillation combined with deoxidizer purification.

[0011] Preferably, the melting temperature is 800-900° C. and the melting time is 30-35 hours.

[0012] Preferably, the quenching temperature is 450-600° C.; the quenching is liquid nitrogen quenching.

[0013] Preferably, the annealing includes sequentially performing heat preservation annealing and cooling annealing; the temperature of the heat preservation annealing is 300-450°C, and the time is 4-8h; the cooling rate of the cooling annealing is 2-10°C / h.

[0014] Preferably, the deoxidizer used in the vacuum distillation combined with the deoxidizer method comprises Mg and / or Al.

[0015] The present invention also provides a high-hardness Ge-Sb-Se chalcogenide glass obtained by the preparation method described in the above technical solution, wherein the hardness of the high-hardness Ge-Sb-Se chalcogenide glass is 220 to 280 kg·mm -2 .

[0016] The present invention also provides an infrared lens, comprising the high-hardness Ge-Sb-Se chalcogenide glass described in the above technical solution.

[0017] The present invention also provides application of the high-hardness Ge-Sb-Se chalcogenide glass or the infrared lens in infrared optics.

[0018] The present invention purifies the raw materials for preparation, removes excess impurities in the raw materials, reduces the non-intrinsic absorption of the chalcogenide glass in the infrared region, and the prepared chalcogenide glass has high transmittance; the components are evenly mixed by melting, and a short-range ordered and long-range disordered glass is formed by quenching treatment. The uneven permanent thermal stress formed by the chalcogenide glass during the quenching process can be reduced or eliminated by annealing treatment, thereby improving the hardness, anti-scratch friction ability and thermal stability of the chalcogenide glass, and then obtaining a high-hardness Ge-Sb-Se chalcogenide glass, which can be used to prepare infrared lenses and has a good application prospect in the field of infrared optics. Moreover, the preparation method provided by the present invention is simple to operate, easy to process, and suitable for large-scale industrial production.

[0019] Furthermore, the high-hardness Ge-Sb-Se chalcogenide glass provided by the present invention has a high coordination number of Ge and Sb elements and many covalent bonds. The present invention optimizes the components of the chalcogenide glass, increases the proportion of Ge and Sb elements in the chalcogenide glass, increases the number of covalent bonds inside the glass, and thereby improves the hardness of the Ge-Sb-Se chalcogenide glass. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0021] Figure 1 Schematic diagram of the structure of the preparation device used in the embodiment of the present invention; wherein the device is named H-type double-tube quartz ampoule, tube A is the purification tube, and tube B is the raw material tube;

[0022] Figure 2 This is the infrared window transmission curve of the high hardness Ge-Sb-Se chalcogenide glass prepared in Example 1. DETAILED DESCRIPTION

[0023] The present invention provides a method for preparing a high-hardness Ge-Sb-Se chalcogenide glass, comprising the following steps:

[0024] Purifying the raw materials to obtain a purified mixture; the raw materials include Ge, Sb and Se;

[0025] The purified mixture is sequentially melted, quenched and annealed to obtain a Ge-Sb-Se chalcogenide glass with high hardness.

[0026] In the present invention, unless otherwise specified, all raw material components are commercially available products well known to those skilled in the art.

[0027] The invention purifies the preparation raw materials to obtain a purified mixture; the preparation raw materials include Ge single substance, Sb single substance and Se single substance.

[0028] In the present invention, the raw materials include: Ge single substance is preferably 30-45at%, more preferably 32-40at%, most preferably 35-40at%; Sb single substance is preferably 1-15at%, more preferably 5-15at%, most preferably 5-10at%; Se single substance is preferably 40-55at%, more preferably 50-55at%, most preferably 50-53at%. In the present invention, the purity of the Ge single substance, Sb single substance and Se single substance is independently preferably ≥5N, more preferably 5-6N, and most preferably 5N. In the present invention, the particle size of the Ge single substance, Sb single substance and Se single substance is independently preferably not larger than the caliber of the reaction container. The present invention uses high-purity Ge single substance, Sb single substance and Se single substance as the raw materials for preparation, which can reduce the content of impurities and oxides in the raw materials for preparation and further improve the purity of the chalcogenide glass.

[0029] In the present invention, the purification is preferably performed by vacuum distillation or vacuum distillation combined with deoxidizer purification, more preferably vacuum distillation combined with deoxidizer purification. The present invention can eliminate [-OH] and [HOH] impurities in the chalcogenide glass by purifying the raw materials for preparation, and reduce the influence of the non-intrinsic absorption loss in the chalcogenide glass on its infrared transmission effect.

[0030] In the present invention, the vacuum distillation purification preferably comprises the following steps: vacuum distilling and purifying Ge, Sb and Se to obtain a purified mixture. In the present invention, the vacuum distillation purification preferably comprises: placing the pre-purified mixture in a quartz reactor, and then placing the quartz reactor in a dual-temperature zone distillation furnace for vacuum distillation purification.

[0031] In the present invention, 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 and a purification tube connected to the raw material tube through a connecting tube, and one end of the raw material tube is provided with an opening, or one end of the raw material tube and one end of the purification tube are both provided with openings. The present invention adopts the above-mentioned device to facilitate the sealing of the opening of the raw material tube during purification, thereby providing a vacuum environment for the preparation raw materials and deoxidizer placed in the H-type double-tube quartz ampoule, avoiding oxidation of the preparation raw materials and the introduction of impurities, thereby causing the extrinsic absorption of the chalcogenide glass to increase in the infrared region.

[0032] In the present invention, the quartz reactor is preferably pretreated by dehydroxylation before use; the process of the dehydroxylation pretreatment preferably includes: washing the quartz reactor with hydrofluoric acid, water and alcohol in sequence and then drying; the mass percentage concentration of the hydrofluoric acid is preferably 30-50%, more preferably 35-45%, and most preferably 40-45%; the water is preferably deionized water; the alcohol is preferably anhydrous ethanol; the drying temperature is preferably 90-110°C, more preferably 95-105°C, and most preferably 95-100°C. The present invention does not specifically limit the drying time, and it can be dried to constant weight, and the drying is preferably carried out in an oven. The present invention can avoid the quartz reactor from bringing impurity oxygen to the reaction by pretreating the quartz reactor by dehydroxylation.

[0033] In the present invention, the quartz reactor is preferably preheated and evacuated before the vacuum distillation purification; the preheating and evacuation are preferably performed simultaneously. In the present invention, the vacuum degree of the evacuation is preferably ≥5×10 -5 Pa, more preferably 5×10 -5 ~1×10 -3 Pa, the most preferred is 5×10 -4 ~1×10 -3Pa; the vacuuming time is preferably ≥3h, more preferably 3-5h, and most preferably 3h. In the present invention, the preheating temperature is preferably 50-100°C, more preferably 80-95°C, and most preferably 90-95°C; the preheating time is preferably to stop preheating when the vacuum degree reaches the requirement. The present invention preheats and vacuumizes the quartz reactor to meet the requirements; and purifies in a vacuum atmosphere to avoid the influence of oxygen in the air.

[0034] In the present invention, when one end of the raw material tube is provided with an opening, the vacuuming method is preferably: adding the prepared raw material into the raw material tube through the opening on the raw material tube of the quartz reactor, and sealing the opening on the raw material tube after vacuuming; when one end of the raw material tube and one end of the purification tube are both provided with openings, the vacuuming method is preferably: adding the prepared raw material into the raw material tube through the opening on the raw material tube of the quartz reactor, sealing the opening on the raw material tube, and then vacuuming through the opening on the purification tube, and finally sealing the opening on the purification tube. In the present invention, hydrogen-oxygen flame or oxyacetylene flame sealing is preferably used for the sealing. The present invention can avoid the introduction of impurity oxygen in the sealing process and the reduction of glass transmittance by adopting the above-mentioned method for sealing.

[0035] In the present invention, the cold end temperature of the dual-temperature zone distillation furnace is preferably 300-500° C., more preferably 350-450° C., and most preferably 400-450° C.; the hot end temperature of the dual-temperature zone distillation furnace is preferably 850-950° C., more preferably 900-950° C., and most preferably 920-950° C. The present invention performs purification in a dual-temperature zone distillation furnace, utilizing the characteristic that the vapor pressure of Ge, Sb and Se in the raw materials and their oxides at a certain temperature has a large difference, and performs distillation treatment on them to remove oxygen and other non-volatile impurities, thereby achieving a deoxygenation effect.

[0036] In the present invention, the vacuum distillation combined with deoxidizer method preferably comprises the following steps: mixing Ge, Sb, Se and a deoxidizer, and performing vacuum distillation purification to obtain a purified mixture.

[0037] In the present invention, the deoxidizer preferably includes Mg and / or Al; the mass of the deoxidizer is preferably 0.03-0.1wt% of the total mass of Ge, Sb and Se, more preferably 0.05-0.1wt%, and most preferably 0.08-0.1wt%. In the present invention, the conditions of the vacuum distillation purification are preferably the same as the conditions of the vacuum distillation purification, which will not be repeated here. The present invention uses Mg and / or Al, both of which are active elements, as deoxidizers, which have the ability to preferentially bond with oxygen, so that the XO bonds that exist in the chalcogenide glass and cause a series of harmful absorptions in the near, mid and far infrared regions can be eliminated. By controlling the amount of the deoxidizer, the present invention can avoid the problem that the oxygen impurities in the chalcogenide glass cannot be fully removed due to too little amount, and can also avoid the reaction of part of the raw materials with the deoxidizer due to too much deoxidizer, thereby avoiding deviations in the glass components.

[0038] After obtaining the purified mixture, the present invention sequentially melts, quenches and anneals the purified mixture to obtain a Ge-Sb-Se chalcogenide glass with high hardness.

[0039] In the present invention, the melting temperature is preferably 800-900°C, more preferably 850-900°C, and most preferably 850-875°C; the melting time is preferably 30-35h, more preferably 32-35h, and most preferably 33-35h; the melting container is preferably the raw material tube. The present invention can fully melt the Ge element by controlling the melting temperature and time, ensuring that the Ge-containing raw materials are completely melted and mixed together to form a glass liquid state, thereby forming a short-range ordered and long-range disordered chalcogenide glass.

[0040] After the melting is completed, the present invention preferably further comprises: cooling the molten glass to the quenching temperature, and then performing subsequent quenching. The present invention has no special limitation on the cooling method, and a cooling method well known to those skilled in the art can be used, such as natural cooling.

[0041] In the present invention, the quenching temperature is preferably 450-600°C, more preferably 500-600°C, and most preferably 500-550°C; the quenching is preferably liquid nitrogen quenching, and the quenching time is preferably ≤10s. In the present invention, the liquid nitrogen quenching is preferably: placing the raw material tube horizontally in liquid nitrogen for quenching. In the conventional sulfur-based glass melting process, the furnace quenching is often carried out by air cooling or water cooling. The present invention uses liquid nitrogen quenching to obtain glass components outside the conventional glass-forming zone, the glass-forming zone is larger, the hardness of the glass itself is improved, and by adjusting the proportion of each element in the glass, a glass with good stability and transmittance is obtained.

[0042] In the present invention, the annealing preferably includes heat preservation annealing and cooling annealing in sequence; the temperature of the heat preservation annealing is preferably 300-450°C, more preferably 340-450°C, and most preferably 340-350°C; the time of the heat preservation annealing is preferably 4-8h, more preferably 5-7h, and most preferably 6h; the cooling rate of the cooling annealing is preferably 2-10°C / h, more preferably 5-10°C / h, and most preferably 8-10°C / h; the end point of the cooling annealing is preferably 25-35°C, more preferably 30-35°C, and most preferably 30°C. The present invention can reduce or eliminate the uneven permanent thermal stress formed by the chalcogenide glass during the quenching process by annealing the quenched glass obtained by the quenching, thereby improving the mechanical strength and thermal stability of the chalcogenide glass.

[0043] After the annealing is completed, the present invention preferably further comprises ball milling the annealed glass obtained by the annealing to obtain glass powder, and hot pressing the glass powder to obtain high-hardness Ge-Sb-Se chalcogenide glass. In the present invention, the hot pressing temperature is preferably 350-400°C, more preferably 370-390°C, and most preferably 385°C; the time is preferably 10-20 minutes, more preferably 15-20 minutes, and most preferably 15 minutes; the hot pressing pressure is preferably 30-35 MPa, more preferably 30-32 MPa, and most preferably 30 MPa.

[0044] The present invention also provides a high-hardness Ge-Sb-Se chalcogenide glass obtained by the preparation method described in the above technical solution, wherein the hardness of the high-hardness Ge-Sb-Se chalcogenide glass is 220 to 280 kg·mm -2 . In the present invention, the high-hardness Ge-Sb-Se chalcogenide glass preferably includes the following components: Ge is preferably 30-45at%, more preferably 32-40at%, and most preferably 35-40at%; Sb is preferably 1-15at%, more preferably 5-15at%, and most preferably 5-10at%; Se is preferably 40-55at%, more preferably 50-55at%, and most preferably 50-53at%. The high-hardness Ge-Sb-Se chalcogenide glass provided by the present invention has a hardness more than twice that of commercial As2Se3 glass, and has high hardness, which can improve the defect of weak hardness of chalcogenide glass on the market.

[0045] The present invention also provides an infrared lens, comprising the high-hardness Ge-Sb-Se chalcogenide glass described in the above technical solution.

[0046] The present invention also provides the application of the high-hardness Ge-Sb-Se chalcogenide glass or the infrared lens in infrared optics. In the present invention, the application of the high-hardness Ge-Sb-Se chalcogenide glass in infrared optics preferably includes the application in military or civilian infrared lenses, vehicle-mounted infrared or infrared probes.

[0047] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0048] In the following examples and comparative examples, the purity of Ge, Sb and Se is 5N, and the particle size is ≤1 cm; the deoxidizer is Mg; the quartz reactor is pretreated by dehydroxylation, and the dehydroxylation pretreatment process is to clean the quartz reactor with hydrofluoric acid, deionized water and anhydrous ethanol in sequence, and finally put it in a dry oven to completely dry. Figure 1 The apparatus shown is used to prepare high-hardness Ge-Sb-Se chalcogenide glass.

[0049] Example 1

[0050] 11.09 g Ge, 2.32 g Sb, 16.58 g Se and 0.03 g Mg were mixed to obtain a mixture to be purified. The mixture to be purified was added into the raw material tube through the opening on the raw material tube of the H-type double-tube quartz ampoule, and preheated at 90 °C while evacuating. When the vacuum degree reached 1×10 -3 Pa, the vacuuming and preheating are completed, the opening on the raw material tube is sealed, and the quartz reactor is placed in a double-temperature zone distillation furnace for purification. The cold end temperature of the double-temperature zone distillation furnace is 400°C, and the hot end temperature is 950°C.

[0051] The purified mixture was melted at 900°C for 35h, naturally cooled to 550°C and quenched in liquid nitrogen. The liquid nitrogen quenching was stopped when the product was detached from the wall. Finally, the temperature was raised to 350°C for annealing, kept warm for 6h, and then cooled to 30°C at a rate of 10°C / h, ball-milled, and hot-pressed at 385°C and 30MPa for 15min to obtain high hardness Ge-Sb-Se chalcogenide glass (Ge 40at%, Sb 5at%, Se 55at%).

[0052] The transmittance of the high-hardness Ge-Sb-Se chalcogenide glass prepared in Example 1 was tested using a Fourier transform infrared spectrometer (model: American Nicolet 380). The prepared chalcogenide glass was cut into glass sheets with a diameter of 20 mm and a thickness of 2 mm. The glass sheets were polished on both sides and then placed in a Fourier transform infrared spectrometer for testing. Figure 2 This is the infrared window transmission curve of the high hardness Ge-Sb-Se chalcogenide glass prepared in this example. Figure 2 It can be seen that the high-hardness Ge-Sb-Se chalcogenide glass prepared by the present invention has a transmittance of 55% in the infrared window, which is good. Moreover, compared with the product obtained by not using vacuum distillation combined with deoxidizer method for purification, the Ge-O absorption peak of the purified glass of the present invention is significantly reduced, and the glass transmittance effect is better.

[0053] The hardness of the prepared high-hardness Ge-Sb-Se chalcogenide glass was tested using an indenter. The cut glass piece was placed on the glass slide and kept under a load of 50g for 5 seconds. The test was repeated 5 times to obtain the average hardness. The result was 234.6kg·mm -2 The hardness of commercial As2Se3 glass is increased by 50% and is higher than that of ZnS crystal. The hardness is increased while maintaining good transmittance of the glass.

[0054] Example 2

[0055] 9.17 g Ge, 6.59 g Sb, 14.24 g Se and 0.03 g Mg were mixed to obtain a mixture to be purified. The mixture to be purified was added into the raw material tube through the opening on the raw material tube of the H-type double-tube quartz ampoule, and vacuum was drawn (the vacuum degree was 1×10 -3 Pa, time is 3h) and preheating is carried out at 90℃. When the vacuum degree reaches 1×10 -3 Pa, the vacuuming and preheating are completed, the opening on the raw material tube is sealed, and the quartz reactor is placed in a double-temperature zone distillation furnace for purification. The cold end temperature of the double-temperature zone distillation furnace is 400°C, and the hot end temperature is 950°C.

[0056] The purified mixture was melted at 900°C for 30 h, naturally cooled to 600°C and quenched in liquid nitrogen, and finally heated to 350°C for annealing, kept warm for 6 h, and then cooled to 30°C at a rate of 10°C / h, ball-milled, and hot-pressed at 385°C and 30 MPa for 15 min to obtain high hardness Ge-Sb-Se chalcogenide glass (Ge 35at%, Sb 15at%, Se 50at%).

[0057] The hardness of the prepared high-hardness Ge-Sb-Se chalcogenide glass was tested, and the result was 236.7 kg·mm -2 , indicating that the high-hardness Ge-Sb-Se chalcogenide glass prepared by the present invention has high hardness.

[0058] Example 3

[0059] 8.36 g Ge, 6.57 g Sb, 15.06 g Se and 0.03 g Mg were mixed to obtain a mixture to be purified. The mixture to be purified was added into the raw material tube through the opening on the raw material tube of the H-type double-tube quartz ampoule, and vacuum was drawn (the vacuum degree was 1×10 -3 Pa, time is 3h) and preheating is carried out at 90℃. When the vacuum degree reaches 1×10 -3 Pa, the vacuuming and preheating are completed, the opening on the raw material tube is sealed, and the quartz reactor is placed in a double-temperature zone distillation furnace for purification. The cold end temperature of the double-temperature zone distillation furnace is 400°C, and the hot end temperature is 950°C.

[0060] The purified mixture was melted at 900°C for 30 h, naturally cooled to 600°C and quenched in liquid nitrogen, and finally heated to 340°C for annealing, kept warm for 6 h, and then cooled to 30°C at a rate of 10°C / h, ball-milled, and hot-pressed at 365°C and 30 MPa for 15 min to obtain high hardness Ge-Sb-Se chalcogenide glass (Ge 32at%, Sb 15at%, Se 53at%).

[0061] The hardness of the prepared high-hardness Ge-Sb-Se chalcogenide glass was tested, and the result was 225.6 kg·mm -2 , indicating that the high-hardness Ge-Sb-Se chalcogenide glass prepared by the present invention has high hardness.

[0062] Comparative Example 1

[0063] 3.68 g Ge, 10.29 g Sb, 16.02 g Se and 0.03 g Mg were mixed to obtain a mixture to be purified. The mixture to be purified was added into the raw material tube through the opening on the raw material tube of the H-type double-tube quartz ampoule, and vacuum was drawn (the vacuum degree was 1×10 -3 Pa, time is 3h) and preheating is carried out at 90℃. When the vacuum degree reaches 1×10 -3 Pa, the vacuuming and preheating are completed, the opening on the raw material tube is sealed, and the quartz reactor is placed in a double-temperature zone distillation furnace for purification. The cold end temperature of the double-temperature zone distillation furnace is 400°C, and the hot end temperature is 950°C.

[0064] The purified mixture was melted at 900°C for 30 h, naturally cooled to 450°C for air-cooling quenching, and finally heated to 240°C for annealing, kept warm for 6 h, and then cooled to 30°C at a rate of 5°C / h, ball-milled, and hot-pressed at 385°C and 30 MPa for 15 min to obtain high hardness Ge-Sb-Se chalcogenide glass (Ge 15at%, Sb 25at%, Se 60at%).

[0065] The hardness of the prepared high-hardness Ge-Sb-Se chalcogenide glass was tested, and the result was 161.3 kg·mm -2 .

[0066] Comparative Example 2

[0067] 5.05 g Ge, 8.47 g Sb, 16.48 g Se and 0.03 g Mg were mixed to obtain a mixture to be purified. The mixture to be purified was added into the raw material tube through the opening on the raw material tube of the H-type double-tube quartz ampoule, and vacuum was drawn (the vacuum degree was 1×10 -3 Pa, time is 3h) and preheating is carried out at 90℃. When the vacuum degree reaches 1×10 -3 Pa, the vacuuming and preheating are completed, the opening on the raw material tube is sealed, and the quartz reactor is placed in a double-temperature zone distillation furnace for purification. The cold end temperature of the double-temperature zone distillation furnace is 400°C, and the hot end temperature is 950°C.

[0068] The purified mixture was melted at 900°C for 30 h, naturally cooled to 450°C for air-cooling quenching, and finally heated to 250°C for annealing, kept warm for 6 h, and then cooled to 30°C at a rate of 5°C / h, ball-milled, and hot-pressed at 385°C and 30 MPa for 15 min to obtain high hardness Ge-Sb-Se chalcogenide glass (Ge 20at%, Sb 20at%, Se 60at%).

[0069] The hardness of the prepared high-hardness Ge-Sb-Se chalcogenide glass was tested, and the result was 172.7 kg·mm -2 .

[0070] By comparing Examples 1 to 3 and Comparative Examples 1 to 2, it can be seen that as the coordination number in the chalcogenide glass decreases, the hardness of the chalcogenide glass decreases significantly. When the Se content is higher than 55%, the hardness of the prepared chalcogenide glass is low and does not have an advantage in the commercial glass market. In addition, liquid nitrogen quenching cools the glass faster and is easier to form glass, and can prepare glass that cannot be obtained by air cooling.

[0071] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A high-hardness Ge-Sb-Se chalcogenide glass, characterized in that: The hardness of the high-hardness Ge-Sb-Se chalcogenide glass is 220-280 kg·mm -2 ; The method for preparing the high-hardness Ge-Sb-Se chalcogenide glass comprises the following steps: Purifying the raw materials to obtain a purified mixture; the raw materials include: Ge 30-45at%, Sb 1-15at% and Se40-55at%; The purified mixture is sequentially melted, quenched and annealed, the annealed glass obtained by the annealing is ball-milled to obtain glass powder, and the glass powder is hot-pressed to obtain high-hardness Ge-Sb-Se chalcogenide glass; The quenching is liquid nitrogen quenching; the annealing includes sequentially performing heat preservation annealing and cooling annealing; the temperature of the heat preservation annealing is 300-450°C and the time is 4-8h; The hot pressing temperature is 350-400° C., the time is 10-20 min, and the pressure is 30-35 MPa.

2. The high-hardness Ge-Sb-Se chalcogenide glass according to claim 1, characterized in that: The purification is performed by vacuum distillation or vacuum distillation combined with deoxidizer purification.

3. The high-hardness Ge-Sb-Se chalcogenide glass according to claim 1, characterized in that: The melting temperature is 800-900° C. and the melting time is 30-35 hours.

4. The high-hardness Ge-Sb-Se chalcogenide glass according to claim 1, characterized in that: The quenching temperature is 450-600°C.

5. The high-hardness Ge-Sb-Se chalcogenide glass according to claim 1, characterized in that: The cooling rate of the temperature-drop annealing is 2-10°C / h.

6. The high-hardness Ge-Sb-Se chalcogenide glass according to claim 2, characterized in that: The deoxidizer used in the vacuum distillation combined with deoxidizer purification method includes Mg and / or Al.

7. An infrared lens, characterized in that: The invention comprises the high-hardness Ge-Sb-Se chalcogenide glass as described in any one of claims 1 to 6.

8. Use of the high-hardness Ge-Sb-Se chalcogenide glass according to any one of claims 1 to 6 or the infrared lens according to claim 7 in infrared optics.

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