A method for preparing high-purity chalcogenide glass with ultra-low particle scattering

Abstract

The invention relates to a method for preparing high-purity sulfide glass with ultra-low particle scattering. A filtering device for filtering particles is arranged in a connecting tube between a glass raw material tube and a distillation transition tube of a high-purity quartz ampoule device, so that the sulfur-based element in the sulfur-based element raw material is subjected to secondary distillation in sequence and then enters a glass melting tube in the form of vapor through the glass raw material tube and the distillation transition tube. The particle impurities in the sulfur-based element raw material are filtered out by the filtering device and cannot enter the distillation transition tube. The non-sulfur-based element raw material constituting the chemical formula of the high-purity sulfide glass enters the glass melting tube in the form of vapor after primary distillation. The particle impurities in the non-sulfur-based element raw material are retained in the distillation transition tube, so that the particle impurities are not introduced into the glass melting tube. While retaining the advantage of the traditional metal reduction method in reducing the absorption of impurities, the particle scattering caused by the presence of the particle impurities in the sulfide glass prepared subsequently is prevented, thereby improving the purity of the obtained sulfide glass.

Description

Technical Field

[0001] The invention relates to the field of optical fiber preforms, and in particular to a method for preparing high-purity chalcogenide glass with ultra-low particle scattering. Background Art

[0002] Chalcogenide glass refers to a binary or ternary oxygen-free glass composed mainly of sulfur (S), selenium (Se) and tellurium (Te) in Group VIA of the periodic table, with a certain amount of other metal elements (As, Ge or Ga, etc.) introduced. Chalcogenide glass has an ultra-wide infrared transmission spectrum range, extremely high optical nonlinearity and extremely low phonon energy. Therefore, chalcogenide glass is not only an ideal infrared lens material, but also a potential matrix material for mid-infrared supercontinuum light sources, mid-infrared laser transmission and fiber amplifiers.

[0003] Nowadays, metal reduction is usually used to prepare chalcogenide glass to prepare chalcogenide glass of the required purity. The use of metal reduction can effectively purify the purity of raw materials for preparing chalcogenide glass and significantly reduce the content of impurities such as oxides (As-O, Ge-O, Si-O, etc.) and hydroxyls (H2O, OH, etc.) in chalcogenide glass.

[0004] However, the current method of preparing chalcogenide glass by metal reduction has shortcomings: it cannot solve the problem of micron-sized metal oxide particles (such as MgO, Al2O3) produced during the metal reduction purification process being introduced into the chalcogenide glass melt, which increases the loss of the optical fiber substrate drawn from the chalcogenide glass and limits the application of chalcogenide glass optical fiber. In addition, the infrared transmission performance of chalcogenide glass is easily affected by the particle scattering of the introduced micron-sized metal oxide particles, which not only causes the transmission spectrum to tilt at short wavelengths, but also reduces the transmittance of chalcogenide glass in the entire mid-infrared region due to the oxide particles acting as a deliquescence source, which will have an adverse effect on the service life of chalcogenide glass in the industrial and scientific research fields. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a method for preparing high-purity chalcogenide glass with ultra-low particle scattering in view of the above-mentioned prior art.

[0006] The technical solution adopted by the present invention to solve the above technical problems is: a method for preparing high-purity chalcogenide glass with ultra-low particle scattering, characterized in that it comprises the following steps:

[0007] Step 1, preparing a group of high-purity quartz ampoule devices including a glass raw material tube, a distillation transition tube and a glass melting tube, and performing a dehydroxylation pretreatment on the high-purity quartz ampoule device; wherein the upper end of the glass raw material tube is open, the upper and lower ends of the distillation transition tube are both open, the upper and lower ends of the glass melting tube are both open, the upper end opening of the glass raw material tube is connected to the lower end opening of the distillation transition tube through a first connecting tube, a filtering device for filtering particles is arranged in the first connecting tube, the upper end opening of the distillation transition tube is connected to the lower end opening of the glass melting tube through a second connecting tube, and the upper end opening of the glass melting tube is connected to a vacuum pump;

[0008] Step 2, weighing a sulfur-based elemental raw material in a broken block form according to the chemical formula of the high-purity sulfur-based glass to be prepared, and weighing a metal deoxidizer, and mixing the weighed sulfur-based elemental raw material and the metal deoxidizer evenly to obtain a mixture;

[0009] Step 3, heating the obtained mixture at a predetermined reaction temperature for a predetermined reaction time, so that the metal deoxidizer in the mixture reacts with the sulfur-based elemental raw material to undergo a dehydroxylation reaction, thereby completing the dehydroxylation treatment of the sulfur-based elemental raw material by the metal deoxidizer;

[0010] Step 4, starting the vacuum pump, loading the mixture after the dehydroxylation reaction into the glass raw material tube, and loading the non-sulfur-based single material constituting the chemical formula of the high-purity sulfur-based glass to be prepared into the distillation transition tube, and heating and heat-insulating the distillation transition tube and the glass melting tube respectively;

[0011] Step 5, placing the glass raw material tube into a tubular heating furnace for high-temperature heating and slowly raising the temperature of the glass raw material tube to a first preset temperature range, so that the sulfur-based vapor formed by the sulfur-based element after being subjected to high temperature slowly passes through the filtering device and is distilled into the distillation transition tube. After all the raw materials in the glass raw material tube are distilled, the first connecting tube between the glass raw material tube and the distillation transition tube is sealed with a hydrogen-oxygen flame;

[0012] Step 6, using a tubular heating furnace to heat the distillation transition tube and slowly raising the temperature of the distillation transition tube to a second preset temperature range, so as to slowly distill the sulfur-based vapor formed by the sulfur-based element after being subjected to high temperature and the non-sulfur-based vapor formed by the non-sulfur-based element into the glass melting tube, and after all the raw materials in the distillation transition tube are distilled, the second connecting tube is sealed with a hydrogen-oxygen flame;

[0013] Step 7, put the glass melting tube into the swing furnace for heating and slowly raise the temperature of the glass melting tube to the third preset temperature range and then perform swing melting for a preset time, take out the glass melting tube for air cooling and wall removal treatment, and anneal the chalcogenide glass obtained by the air cooling and wall removal treatment, so as to obtain the high-purity chalcogenide glass with ultra-low particle scattering to be prepared.

[0014] Improved, in the method for preparing high-purity chalcogenide glass with ultra-low particle scattering, the heat preservation treatment is to heat the outside of the distillation transition tube by wrapping a heating tape and to heat the outside of the glass melting tube by wrapping a heating tape.

[0015] As a further improvement, in the method for preparing the high-purity chalcogenide glass with ultra-low particle scattering, the filtering device is made of SiO2 or Al2O3, and the pore size of the filtering holes is in the size range of 10 μm to 100 μm.

[0016] Furthermore, in the method for preparing high-purity sulfide glass with ultra-low particle scattering, the weighed amount of the metal deoxidizer is 0.03-0.1wt% of the total amount of the mixture; the predetermined reaction temperature is 650°C, and the predetermined reaction time is 10 hours; the first preset temperature range is 550-600°C, and the distillation time of the sulfide vapor is 6 hours; the second preset temperature range is 500-550°C, and the distillation time of the sulfide vapor and non-sulfur vapor is 3 hours; the third preset temperature range is 650-700°C, and the preset time of the swing melting is 12-18 hours.

[0017] As a further improvement, in the method for preparing the high-purity chalcogenide glass with ultra-low particle scattering, the annealing treatment is to keep the chalcogenide glass at a glass transition point temperature of ±5°C for 2 hours, and then cool the chalcogenide glass to room temperature within 10 hours.

[0018] Compared with the prior art, the advantages of the present invention are as follows: in the method for preparing high-purity chalcogenide glass with ultra-low particle scattering of the invention patent application, since the high-purity quartz ampoule device is provided with a filtering device for filtering micron-sized particles, the chalcogenide elements in the chalcogenide element raw material are sequentially subjected to secondary distillation and then enter the glass melting tube in the form of vapor through the glass raw material tube and the distillation transition tube, and the particulate impurities in the chalcogenide element raw material are filtered out by the filtering device and cannot enter the distillation transition tube, and the non-chalcogenide element raw material constituting the chemical formula of the high-purity chalcogenide glass is also subjected to primary distillation and then enters the glass melting tube in the form of vapor, and the particulate impurities in the non-chalcogenide element raw material are retained in the distillation transition tube, so that no particulate impurities are introduced into the glass melting tube, thus retaining the advantage of the traditional metal reduction method in reducing the absorption of impurities, preventing the introduction of particulate impurities into the materials required for the subsequent preparation of the chalcogenide glass, avoiding the particle scattering caused by these particulate impurities, improving the purity of the prepared chalcogenide glass, reducing the optical fiber base loss, avoiding the inclination of the transmission spectrum at the short wavelength, and improving the optical properties of the obtained chalcogenide glass. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 Schematic diagram of the structure of the high-purity quartz ampoule device in the present invention;

[0020] Figure 2It is a schematic flow chart of a method for preparing high-purity chalcogenide glass with ultra-low particle scattering in the present invention;

[0021] Figure 3 Schematic diagram of infrared spectrum performance test of the chalcogenide glass sample obtained in Example 1, the chalcogenide glass sample obtained in Example 2 and a common chalcogenide glass sample;

[0022] Figure 4 The figure is a performance test diagram of infrared spectroscopy performance test performed on the chalcogenide glass sample obtained in Example 3, the chalcogenide glass sample obtained in Example 4 and a common chalcogenide glass sample. DETAILED DESCRIPTION

[0023] The present invention is further described in detail below with reference to the accompanying drawings.

[0024] Embodiment 1

[0025] In the first embodiment, the chemical formula of the ultra-low particle scattering high-purity chalcogenide glass to be prepared is As 35 Se 65 Specifically, the method for preparing high-purity chalcogenide glass with ultra-low particle scattering comprises the following steps:

[0026] Step 1, prepare a set of high-purity quartz ampoule devices containing a glass raw material tube 1, a distillation transition tube 2 and a glass melting tube 3, and perform dehydroxylation pretreatment on the high-purity quartz ampoule device; wherein, refer to Figure 1 As shown, the upper end of the glass raw material tube 1 is open, the upper and lower ends of the distillation transition tube 2 are open, and the upper and lower ends of the glass melting tube 3 are open. The upper end opening of the glass raw material tube 1 is connected to the lower end opening of the distillation transition tube 2 through a first connecting tube 4. A filtering device 5 for filtering particles is arranged in the first connecting tube 4. The filtering device 5 is made of SiO2 or Al2O3. The filtering device 5 is micron-grade. For example, the pore size of the filtering hole of the filtering device 5 is 100μm. According to actual needs, multiple filtering devices 5 can be loaded in sequence in the first connecting tube 4 for multiple purifications, so as to obtain purer glass. The upper end opening of the distillation transition tube 2 is connected to the lower end opening of the glass melting tube 3 through a second connecting tube 6. The upper end opening of the glass melting tube 3 is connected to a vacuum pump 7. The glass raw material tube 1, the distillation transition tube 2 and the glass melting tube 3 of the high-purity quartz ampoule device are all pre-treated for dehydroxylation.

[0027] Step 2: According to the chemical formula of the high-purity chalcogenide glass to be prepared, As 35 Se 65Weighing a selenium (Se) single substance raw material in a broken block shape with a purity of not less than 99.999%, and weighing an aluminum strip (Al) as a metal deoxidizer, and mixing the weighed selenium (Se) single substance raw material and the metal deoxidizer aluminum strip (Al) uniformly to obtain a mixture; wherein the weighed amount of the metal deoxidizer aluminum strip (Al) is 0.03wt% of the total amount of the mixture;

[0028] Step 3, heating the obtained mixture at a predetermined reaction temperature of 650° C. for a predetermined reaction time of 10 hours, so that the metal deoxidizer aluminum strip (Al) in the mixture undergoes a dehydroxylation reaction with the selenium (Se) element, thereby completing the dehydroxylation treatment of the metal deoxidizer aluminum strip (Al) on the selenium (Se) element;

[0029] Step 4, start the vacuum pump 7, load the mixture after the dehydroxylation reaction (i.e., the mixture of the metal deoxidizer aluminum strip (Al) and the selenium raw material) into the glass raw material tube 1, and load the non-sulfur elemental arsenic (As) raw material constituting the chemical formula of the high-purity sulfur-based glass to be prepared into the distillation transition tube 2, and perform heating and heat preservation treatment on the distillation transition tube 2 and the glass melting tube 3 respectively; wherein the heating and heat preservation treatment here is to wrap a heating belt around the outer side of the distillation transition tube 2 for heating and wrap a heating belt around the outer side of the glass melting tube 3 for heating;

[0030] It should be noted that by wrapping the heating tape around the distillation transition tube 2 for heating, water molecules and volatile oxides attached to the surface of the raw materials in the mixed material in the distillation transition tube can be eliminated; of course, by wrapping the heating tape around the glass melting tube 3 for heating, water molecules and volatile oxides attached to the surface of the arsenic (As) raw material in the glass melting tube can be eliminated;

[0031] Step 5, placing the glass raw material tube 1 into a tubular heating furnace for high-temperature heating and slowly raising the temperature of the glass raw material tube 1 to a first preset temperature range of 550-600°C, so that the selenium (Se) vapor formed by the selenium (Se) element being subjected to high temperature slowly passes through the filtering device 5 and is distilled into the distillation transition tube 2, and impurities such as carbon (C), SiO2 and MgO with high boiling points in the mixture remain in the glass raw material tube 1. The distillation is continued for 6 hours. After all the raw materials in the glass raw material tube 1 are distilled, the first connecting tube 4 between the glass raw material tube 1 and the distillation transition tube 2 is sealed with a hydrogen-oxygen flame; here, by selecting to heat the glass raw material tube in a tubular heating furnace, the tubular heating furnace can better control the heating temperature in real time to achieve the purpose of controlling the distillation rate, and observe the experimental phenomenon; for example, in this embodiment, for the first preset temperature range, the temperature of the glass raw material tube 1 is slowly raised to 550°C;

[0032] Specifically, the temperature in the tubular heating furnace is first raised to 300° C. and kept warm. When the mixed material in the glass raw material tube 1 becomes molten, the vacuum pump 7 is turned on and the vacuum degree is 1×10-3 Pa is subjected to excessive distillation, and the temperature of the glass raw material tube 1 is slowly raised to 550-600° C. within 3 hours; due to the presence of the filtering device 5, the rate at which the raw material vapor flow in the glass raw material tube 1 condenses into the distillation transition tube 2 is greatly reduced, so the first preset temperature range is set to 550-600° C.;

[0033] Step 6, using a tubular heating furnace to heat the distillation transition tube 2 and slowly raising the temperature of the distillation transition tube 2 to a second preset temperature range of 500-550° C., so as to slowly distill the selenium (Se) vapor formed by the selenium (Se) element after being subjected to high temperature and the arsenic (As) vapor formed by the non-sulfur element arsenic (As) into the glass melting tube 3, and continue the distillation for 3 hours. After all the raw materials in the distillation transition tube 2 are distilled, the second connecting tube 6 is sealed with a hydrogen-oxygen flame; for example, for the second preset temperature range, the temperature of the distillation transition tube 2 is slowly raised to 500° C.;

[0034] It should be noted that, due to the treatment in step 5, the selenium (Se) element in the original glass raw material tube 1 has been distilled into the distillation transition tube 2 in the form of vapor, and in this step 6, the temperature of the distillation transition tube 2 is slowly heated to a second preset temperature range of 500-550°C in a slow heating manner. In this way, on the premise of ensuring that the selenium (Se) vapor and the arsenic (As) vapor enter the glass melting tube 3 through the second connecting tube 6 in the form of vapor, it is possible to avoid the particulate impurities in the arsenic (As) raw material being brought into the glass melting tube 3 by the vapor in the distillation transition tube 2, thereby preventing the purity of the raw materials for subsequent reactions from being adversely affected; since no particulate impurities are introduced into the mixture formed by the subsequent reaction of selenium (Se) and arsenic (As) in the glass melting tube, the particle scattering caused by the particulate impurities in the subsequent prepared sulfur-based glass is eliminated;

[0035] Step 7, put the glass melting tube 3 into the swing furnace for heating and slowly raise the temperature of the glass melting tube 3 to the third preset temperature range of 650-700°C, and then swing melt for a preset time of 12-18 hours, take out the glass melting tube 3 for air cooling and wall removal treatment, and anneal the chalcogenide glass obtained by the air cooling and wall removal treatment, so as to obtain the high-purity chalcogenide glass with ultra-low particle scattering to be prepared. In this embodiment, the annealing treatment here is to keep the chalcogenide glass obtained after the air cooling and wall removal treatment at a glass transition point temperature of ±5°C for 2 hours, and then cool the chalcogenide glass to room temperature within 10 hours. For example, in this embodiment, for the third preset temperature range, the temperature of the glass melting tube 3 here is slowly raised to 650°C.

[0036] It should be noted that by placing the glass melting tube 3 into a rocking furnace for heating and rocking melting, the vapor selenium (Se) and vapor arsenic (As) in the glass melting tube can be fully and evenly mixed and reacted to form uniform high-quality glass.

[0037] The high-purity chalcogenide glass with ultra-low particle scattering prepared in Example 1 was taken out from the glass melting tube, cut into pieces with a thickness of more than 20 mm, and then ground and double-sided polished to obtain a chalcogenide glass sample. The infrared spectral performance test results of the chalcogenide glass sample were as follows: Figure 3 As shown in curve 2. Among them, Figure 3 Curve 1 in the figure is the infrared spectrum performance test result obtained by performing infrared spectrum performance test on the common chalcogenide glass sample; the preparation process of the common chalcogenide glass sample is as follows: in the purification and preparation process, no micron-level filtering device is used, but the traditional metal reduction distillation method is adopted, the mixture is directly distilled into a glass melting tube, and then the common chalcogenide glass is obtained by melting in a swing furnace, and then the common chalcogenide glass is cut into pieces with a thickness of more than 20 mm, and then ground and double-sided polished to obtain the sample.

[0038] Embodiment 2

[0039] In the second embodiment, the chemical formula of the ultra-low particle scattering high-purity chalcogenide glass to be prepared is As 35 Se 65 Specifically, the method for preparing high-purity chalcogenide glass with ultra-low particle scattering comprises the following steps:

[0040] Step 1, prepare a set of high-purity quartz ampoule devices containing a glass raw material tube 1, a distillation transition tube 2 and a glass melting tube 3, and perform dehydroxylation pretreatment on the high-purity quartz ampoule device; wherein, refer to Figure 1 As shown, the upper end of the glass raw material tube 1 is open, the upper and lower ends of the distillation transition tube 2 are open, and the upper and lower ends of the glass melting tube 3 are open. The upper end opening of the glass raw material tube 1 is connected to the lower end opening of the distillation transition tube 2 through a first connecting tube 4. A filtering device 5 for filtering particles is arranged in the first connecting tube 4. The filtering device 5 is made of SiO2 or Al2O3. The filtering device 5 is micron-grade. For example, the pore size of the filtering hole of the filtering device 5 is 10μm. According to actual needs, multiple filtering devices 5 can be loaded in the first connecting tube 4 in sequence for multiple purifications, so as to obtain purer glass. The upper end opening of the distillation transition tube 2 is connected to the lower end opening of the glass melting tube 3 through a second connecting tube 6. The upper end opening of the glass melting tube 3 is connected to a vacuum pump 7. The glass raw material tube 1, the distillation transition tube 2 and the glass melting tube 3 of the high-purity quartz ampoule device are all pre-treated for dehydroxylation.

[0041] Step 2: According to the chemical formula of the high-purity chalcogenide glass to be prepared, As 35 Se 65 Weighing a selenium (Se) single substance raw material in the form of fragments and having a purity of not less than 99.999%, and weighing an aluminum strip (Al) as a metal deoxidizer, and mixing the weighed selenium (Se) single substance raw material and the metal deoxidizer aluminum strip (Al) uniformly to obtain a mixture; wherein the weighed amount of the metal deoxidizer aluminum strip (Al) is 0.035wt% of the total amount of the mixture;

[0042] Step 3, heating the obtained mixture at a predetermined reaction temperature of 650° C. for a predetermined reaction time of 10 hours, so that the metal deoxidizer aluminum strip (Al) in the mixture undergoes a dehydroxylation reaction with the selenium (Se) element, thereby completing the dehydroxylation treatment of the metal deoxidizer aluminum strip (Al) on the selenium (Se) element;

[0043] Step 4, start the vacuum pump 7, load the mixture after the dehydroxylation reaction (i.e., the mixture of the metal deoxidizer aluminum strip (Al) and the selenium raw material) into the glass raw material tube 1, and load the non-sulfur elemental arsenic (As) raw material constituting the chemical formula of the high-purity sulfide glass to be prepared into the distillation transition tube 2, and perform heating and heat preservation treatment on the distillation transition tube 2 and the glass melting tube 3 respectively; wherein the heating and heat preservation treatment here is to wrap a heating belt around the outer side of the distillation transition tube 2 for heating and wrap a heating belt around the outer side of the glass melting tube 3 for heating; 6

[0044] It should be noted that by wrapping the heating tape around the distillation transition tube 2 for heating, water molecules and volatile oxides attached to the surface of the raw materials in the mixed material in the distillation transition tube can be eliminated; of course, by wrapping the heating tape around the glass melting tube 3 for heating, water molecules and volatile oxides attached to the surface of the raw materials of non-sulfur elemental arsenic (As) in the glass melting tube can be eliminated;

[0045] Step 5, placing the glass raw material tube 1 into a tubular heating furnace for high-temperature heating and slowly raising the temperature of the glass raw material tube 1 to a first preset temperature range of 550-600°C, so that the selenium (Se) vapor formed by the selenium (Se) element being subjected to high temperature slowly passes through the filtering device 5 and is distilled into the distillation transition tube 2, and impurities such as carbon (C), SiO2 and MgO with high boiling points in the mixture remain in the glass raw material tube 1. The distillation is continued for 6 hours. After all the raw materials in the glass raw material tube 1 are distilled, the first connecting tube 4 between the glass raw material tube 1 and the distillation transition tube 2 is sealed with a hydrogen-oxygen flame; here, by selecting to heat the glass raw material tube in a tubular heating furnace, the tubular heating furnace can better control the heating temperature in real time to achieve the purpose of controlling the distillation rate, and observe the experimental phenomenon; for example, in this embodiment, for the first preset temperature range, the temperature of the glass raw material tube 1 is slowly raised to 580°C;

[0046] Specifically, the temperature in the tubular heating furnace is first raised to 300° C. and kept warm. When the mixed material in the glass raw material tube 1 becomes molten, the vacuum pump 7 is turned on and the vacuum degree is 1×10 -3 Pa is subjected to excessive distillation, and the temperature of the glass raw material tube 1 is slowly raised to 550-600° C. within 3 hours; due to the presence of the filtering device 5, the rate at which the raw material vapor flow in the glass raw material tube 1 condenses into the distillation transition tube 2 is greatly reduced, so the first preset temperature range is set to 550-600° C.;

[0047] Step 6, using a tubular heating furnace to heat the distillation transition tube 2 and slowly raising the temperature of the distillation transition tube 2 to a second preset temperature range of 500-550° C., so as to slowly distill the sulfur vapor formed by the selenium (Se) element after being subjected to high temperature and the arsenic (As) vapor formed by the non-sulfur element arsenic (As) into the glass melting tube 3, and the distillation time is continued for 3 hours. After all the raw materials in the distillation transition tube 2 are distilled, the second connecting tube 6 is sealed with a hydrogen-oxygen flame; for example, for the second preset temperature range, the temperature of the distillation transition tube 2 is slowly raised to 530° C.;

[0048] It should be noted that, due to the treatment in step 5, the selenium (Se) element in the original glass raw material tube 1 has been distilled into the distillation transition tube 2 in the form of vapor, and in this step 6, the temperature of the distillation transition tube 2 is slowly heated to a second preset temperature range of 500-550°C in a slow heating manner. In this way, on the premise of ensuring that the selenium (Se) vapor and the arsenic (As) vapor enter the glass melting tube 3 through the second connecting tube 6 in the form of vapor, it is possible to avoid the particulate impurities in the arsenic (As) raw material being brought into the glass melting tube 3 by the vapor in the distillation transition tube 2, thereby preventing the purity of the raw materials for subsequent reactions from being adversely affected; since no particulate impurities are introduced into the mixture formed by the subsequent reaction of selenium (Se) and arsenic (As) in the glass melting tube, the particle scattering caused by the particulate impurities in the subsequent prepared sulfur-based glass is eliminated;

[0049] Step 7, put the glass melting tube 3 into the swing furnace for heating and slowly raise the temperature of the glass melting tube 3 to the third preset temperature range of 650-700°C, and then swing melt for a preset time of 12-18 hours, take out the glass melting tube 3 for air cooling and wall removal treatment, and anneal the chalcogenide glass obtained by the air cooling and wall removal treatment, so as to obtain the high-purity chalcogenide glass with ultra-low particle scattering to be prepared. In this embodiment, the annealing treatment here is to keep the chalcogenide glass obtained after the air cooling and wall removal treatment at a glass transition point temperature of ±5°C for 2 hours, and then cool the chalcogenide glass to room temperature within 10 hours. For example, in this embodiment, for the third preset temperature range, the temperature of the glass melting tube 3 here is slowly raised to 680°C.

[0050] It should be noted that by placing the glass melting tube 3 into a rocking furnace for heating and rocking melting, the vapor selenium (Se) and vapor arsenic (As) in the glass melting tube can be fully and evenly mixed and reacted to form uniform high-quality glass.

[0051] The high-purity chalcogenide glass with ultra-low particle scattering prepared in Example 2 was taken out from the glass melting tube, cut into pieces with a thickness of more than 20 mm, and then ground and double-sided polished to obtain a chalcogenide glass sample. The infrared spectral performance test results of the chalcogenide glass sample were as follows: Figure 3 As shown in curve 3.

[0052] Embodiment 3

[0053] In the third embodiment, the chemical formula of the ultra-low particle scattering high-purity chalcogenide glass to be prepared is set to As 40 Se 60 Specifically, the method for preparing high-purity chalcogenide glass with ultra-low particle scattering comprises the following steps:

[0054] Step 1, prepare a set of high-purity quartz ampoule devices containing a glass raw material tube 1, a distillation transition tube 2 and a glass melting tube 3, and perform dehydroxylation pretreatment on the high-purity quartz ampoule device; wherein, refer to Figure 1 As shown, the upper end of the glass raw material tube 1 is open, the upper and lower ends of the distillation transition tube 2 are open, and the upper and lower ends of the glass melting tube 3 are open. The upper end opening of the glass raw material tube 1 is connected to the lower end opening of the distillation transition tube 2 through a first connecting tube 4. A filtering device 5 for filtering particles is arranged in the first connecting tube 4. The filtering device 5 is made of Al2O3. The filtering device 5 is micron-grade. For example, the pore size of the filtering hole of the filtering device 5 is 100μm. According to actual needs, multiple filtering devices 5 can be loaded in sequence in the first connecting tube 4 for multiple purifications, so as to obtain purer glass. The upper end opening of the distillation transition tube 2 is connected to the lower end opening of the glass melting tube 3 through a second connecting tube 6. The upper end opening of the glass melting tube 3 is connected to a vacuum pump 7. The glass raw material tube 1, the distillation transition tube 2 and the glass melting tube 3 of the high-purity quartz ampoule device are all pre-treated for dehydroxylation.

[0055] Step 2: According to the chemical formula of the high-purity chalcogenide glass to be prepared, As 40 Se 60 Weighing a selenium (Se) single substance raw material in the form of fragments and having a purity of not less than 99.999%, and weighing an aluminum strip (Al) as a metal deoxidizer, and mixing the weighed selenium (Se) single substance raw material and the metal deoxidizer aluminum strip (Al) uniformly to obtain a mixture; wherein the weighed amount of the metal deoxidizer aluminum strip (Al) is 0.05wt% of the total amount of the mixture;

[0056] Step 3, heating the obtained mixture at a predetermined reaction temperature of 650° C. for a predetermined reaction time of 10 hours, so that the metal deoxidizer aluminum strip (Al) in the mixture reacts with the selenium (Se) element to undergo a dehydroxylation reaction, thereby completing the dehydroxylation treatment of the metal deoxidizer aluminum strip (Al) on the selenium (Se) element;

[0057] Step 4, start the vacuum pump 7, load the mixture after the dehydroxylation reaction (i.e., the mixture of the metal deoxidizer aluminum strip (Al) and the selenium raw material) into the glass raw material tube 1, and load the non-sulfur elemental arsenic (As) raw material constituting the chemical formula of the high-purity sulfur-based glass to be prepared into the distillation transition tube 2, and perform heating and heat preservation treatment on the distillation transition tube 2 and the glass melting tube 3 respectively; wherein the heating and heat preservation treatment here is to wrap a heating belt around the outer side of the distillation transition tube 2 for heating and wrap a heating belt around the outer side of the glass melting tube 3 for heating;

[0058] It should be noted that by wrapping the heating tape around the distillation transition tube 2 for heating, water molecules and volatile oxides attached to the surface of the raw materials in the mixed material in the distillation transition tube can be eliminated; of course, by wrapping the heating tape around the glass melting tube 3 for heating, water molecules and volatile oxides attached to the surface of the raw materials of non-sulfur elemental arsenic As in the glass melting tube can be eliminated;

[0059] Step 5, placing the glass raw material tube 1 into a tubular heating furnace for high-temperature heating and slowly raising the temperature of the glass raw material tube 1 to a first preset temperature range of 550-600°C, so that the selenium (Se) vapor formed by the selenium (Se) element being subjected to high temperature slowly passes through the filtering device 5 and is distilled into the distillation transition tube 2, and impurities such as carbon (C), SiO2 and MgO with high boiling points in the mixture remain in the glass raw material tube 1. The distillation is continued for 6 hours. After all the raw materials in the glass raw material tube 1 are distilled, the first connecting tube 4 between the glass raw material tube 1 and the distillation transition tube 2 is sealed with a hydrogen-oxygen flame; here, by selecting to heat the glass raw material tube in a tubular heating furnace, the tubular heating furnace can better control the heating temperature in real time to achieve the purpose of controlling the distillation rate, and observe the experimental phenomenon; for example, in this embodiment, for the first preset temperature range, the temperature of the glass raw material tube 1 is slowly raised to 570°C;

[0060] Specifically, the temperature in the tubular heating furnace is first raised to 300° C. and kept warm. When the mixed material in the glass raw material tube 1 becomes molten, the vacuum pump 7 is turned on and the vacuum degree is 1×10 -3 Pa is subjected to excessive distillation, and the temperature of the glass raw material tube 1 is slowly raised to 550-600° C. within 3 hours; due to the presence of the filtering device 5, the rate at which the raw material vapor flow in the glass raw material tube 1 condenses into the distillation transition tube 2 is greatly reduced, so the first preset temperature range is set to 550-600° C.;

[0061] Step 6, using a tubular heating furnace to heat the distillation transition tube 2 and slowly raising the temperature of the distillation transition tube 2 to a second preset temperature range of 500-550° C., so as to slowly distill the selenium (Se) vapor formed by the selenium (Se) element after being subjected to high temperature and the arsenic (As) vapor formed by the non-sulfur element arsenic (As) into the glass melting tube 3, and continue the distillation for 3 hours. After all the raw materials in the distillation transition tube 2 are distilled, the second connecting tube 6 is sealed with a hydrogen-oxygen flame; for example, for the second preset temperature range, the temperature of the distillation transition tube 2 is slowly raised to 540° C.;

[0062] It should be noted that, due to the treatment in step 5, the selenium (Se) element in the original glass raw material tube 1 has been distilled into the distillation transition tube 2 in the form of vapor, and in this step 6, the temperature of the distillation transition tube 2 is slowly heated to a second preset temperature range of 500-550°C in a slow heating manner. In this way, on the premise of ensuring that the selenium (Se) vapor and the arsenic (As) vapor enter the glass melting tube 3 through the second connecting tube 6 in the form of vapor, it is possible to avoid the particulate impurities in the arsenic (As) raw material being brought into the glass melting tube 3 by the vapor in the distillation transition tube 2, thereby preventing the purity of the raw materials for subsequent reactions from being adversely affected; since no particulate impurities are introduced into the mixture formed by the subsequent reaction of selenium (Se) and arsenic (As) in the glass melting tube, the particle scattering caused by the particulate impurities in the subsequent prepared sulfur-based glass is eliminated;

[0063] Step 7, put the glass melting tube 3 into the swing furnace for heating and slowly raise the temperature of the glass melting tube 3 to the third preset temperature range of 650-700°C, and then swing melt for a preset time of 12-18 hours, take out the glass melting tube 3 for air cooling and wall removal treatment, and anneal the chalcogenide glass obtained by the air cooling and wall removal treatment, so as to obtain the high-purity chalcogenide glass with ultra-low particle scattering to be prepared. In this embodiment, the annealing treatment here is to obtain the chalcogenide glass As obtained after the air cooling and wall removal treatment. 40 Se 60 The temperature is kept at the glass transition point temperature ±5°C for 2 hours, and then the chalcogenide glass is cooled to room temperature within 10 hours. For example, in this embodiment, for the third preset temperature range, the temperature of the glass melting tube 3 is slowly increased to 690°C.

[0064] It should be noted that by placing the glass melting tube 3 into a rocking furnace for heating and rocking melting, the vapor selenium (Se) and vapor arsenic (As) in the glass melting tube can be fully and evenly mixed and reacted to form uniform high-quality glass.

[0065] The high-purity chalcogenide glass with ultra-low particle scattering prepared in Example 3 was taken out from the glass melting tube, cut into pieces with a thickness of more than 20 mm, and then ground and double-sided polished to obtain a chalcogenide glass sample. The infrared spectral performance test results of the chalcogenide glass sample were as follows: Figure 4 The curve 2 is shown in Figure 2. Among them, Figure 4 Curve 1 in the figure is the performance test result obtained by performing infrared spectrum performance test on ordinary chalcogenide glass sample; the preparation process of the ordinary chalcogenide glass sample is as follows: in the purification and preparation process, no micron-level filtering device is used, but the traditional metal reduction distillation method is adopted to directly distill the mixture into a glass melting tube, and then the ordinary chalcogenide glass is obtained by melting in a swing furnace, and then the ordinary chalcogenide glass is cut into pieces with a thickness of more than 20 mm, and then ground and double-sided polished to obtain the sample.

[0066] Embodiment 4

[0067] In the fourth embodiment, the chemical formula of the ultra-low particle scattering high-purity chalcogenide glass to be prepared is As 40 Se 60 Specifically, the method for preparing high-purity chalcogenide glass with ultra-low particle scattering comprises the following steps:

[0068] Step 1, prepare a set of high-purity quartz ampoule devices containing a glass raw material tube 1, a distillation transition tube 2 and a glass melting tube 3, and perform dehydroxylation pretreatment on the high-purity quartz ampoule device; wherein, refer to Figure 1 As shown, the upper end of the glass raw material tube 1 is open, the upper and lower ends of the distillation transition tube 2 are open, and the upper and lower ends of the glass melting tube 3 are open. The upper end opening of the glass raw material tube 1 is connected to the lower end opening of the distillation transition tube 2 through a first connecting tube 4. A filtering device 5 for filtering particles is arranged in the first connecting tube 4. The filtering device 5 is made of Al2O3. The filtering device 5 is micron-grade. For example, the pore size of the filtering hole of the filtering device 5 is 10μm. According to actual needs, multiple filtering devices 5 can be loaded in sequence in the first connecting tube 4 for multiple purifications, so as to obtain purer glass. The upper end opening of the distillation transition tube 2 is connected to the lower end opening of the glass melting tube 3 through a second connecting tube 6. The upper end opening of the glass melting tube 3 is connected to a vacuum pump 7. The glass raw material tube 1, the distillation transition tube 2 and the glass melting tube 3 of the high-purity quartz ampoule device are all pre-treated for dehydroxylation.

[0069] Step 2: According to the chemical formula of the high-purity chalcogenide glass to be prepared, As 40 Se 60Weighing a selenium (Se) single substance raw material in the form of fragments and having a purity of not less than 99.999%, and weighing an aluminum strip (Al) as a metal deoxidizer, and mixing the weighed selenium (Se) single substance raw material and the metal deoxidizer aluminum strip (Al) uniformly to obtain a mixture; wherein the weighed amount of the metal deoxidizer aluminum strip (Al) is 0.1wt% of the total amount of the mixture;

[0070] Step 3, heating the obtained mixture at a predetermined reaction temperature of 650° C. for a predetermined reaction time of 10 hours, so that the metal deoxidizer aluminum strip (Al) in the mixture reacts with the selenium (Se) element to undergo a dehydroxylation reaction, thereby completing the dehydroxylation treatment of the metal deoxidizer aluminum strip (Al) on the selenium (Se) element;

[0071] Step 4, start the vacuum pump 7, load the mixture after the dehydroxylation reaction (i.e., the mixture of the metal deoxidizer aluminum strip (Al) and the selenium raw material) into the glass raw material tube 1, and load the non-sulfur elemental arsenic (As) raw material constituting the chemical formula of the high-purity sulfur-based glass to be prepared into the distillation transition tube 2, and perform heating and heat preservation treatment on the distillation transition tube 2 and the glass melting tube 3 respectively; wherein the heating and heat preservation treatment here is to wrap a heating belt around the outer side of the distillation transition tube 2 for heating and wrap a heating belt around the outer side of the glass melting tube 3 for heating;

[0072] It should be noted that by wrapping the heating tape around the distillation transition tube 2 for heating, water molecules and volatile oxides attached to the surface of the raw materials in the mixed material in the distillation transition tube can be eliminated; of course, by wrapping the heating tape around the glass melting tube 3 for heating, water molecules and volatile oxides attached to the surface of the raw materials of non-sulfur elemental arsenic As in the glass melting tube can be eliminated;

[0073] Step 5, placing the glass raw material tube 1 into a tubular heating furnace for high-temperature heating and slowly raising the temperature of the glass raw material tube 1 to a first preset temperature range of 550-600°C, so that the selenium (Se) vapor formed by the high-temperature exposure of the selenium (Se) element slowly passes through the filtering device 5 and is distilled into the distillation transition tube 2, and the impurities such as carbon (C), SiO2 and MgO with high boiling points in the mixture remain in the glass raw material tube 1. The distillation time is 6 hours. After all the raw materials in the glass raw material tube 1 are distilled, the first connecting tube 4 between the glass raw material tube 1 and the distillation transition tube 2 is sealed with a hydrogen-oxygen flame; here, by selecting to heat the glass raw material tube in a tubular heating furnace, the tubular heating furnace can better control the heating temperature in real time to achieve the purpose of controlling the distillation rate, and observe the experimental phenomenon; for example, in this embodiment, for the first preset temperature range, the temperature of the glass raw material tube 1 is slowly raised to 600°C;

[0074] Specifically, the temperature in the tubular heating furnace is first raised to 300° C. and kept warm. When the mixed material in the glass raw material tube 1 becomes molten, the vacuum pump 7 is turned on and the vacuum degree is 1×10-3 Pa is subjected to excessive distillation, and the temperature of the glass raw material tube 1 is slowly raised to 550-600° C. within 3 hours; due to the presence of the filtering device 5, the rate at which the raw material vapor flow in the glass raw material tube 1 condenses into the distillation transition tube 2 is greatly reduced, so the first preset temperature range is set to 550-600° C.;

[0075] Step 6, using a tubular heating furnace to heat the distillation transition tube 2 and slowly raising the temperature of the distillation transition tube 2 to a second preset temperature range of 500-550° C., so as to slowly distill the selenium (Se) vapor formed by the selenium (Se) element after being subjected to high temperature and the arsenic (As) vapor formed by the non-sulfur element arsenic (As) into the glass melting tube 3, and continue the distillation for 3 hours. After all the raw materials in the distillation transition tube 2 are distilled, the second connecting tube 6 is sealed with a hydrogen-oxygen flame; for example, for the second preset temperature range, the temperature of the distillation transition tube 2 is slowly raised to 550° C.;

[0076] It should be noted that, due to the treatment in step 5, the selenium (Se) element in the original glass raw material tube 1 has been distilled into the distillation transition tube 2 in the form of vapor, and in this step 6, the temperature of the distillation transition tube 2 is slowly heated to a second preset temperature range of 500-550°C in a slow heating manner. In this way, on the premise of ensuring that the selenium (Se) vapor and the arsenic (As) vapor enter the glass melting tube 3 through the second connecting tube 6 in the form of vapor, it is possible to avoid the particulate impurities in the arsenic (As) raw material being brought into the glass melting tube 3 by the vapor in the distillation transition tube 2, thereby preventing the purity of the raw materials for subsequent reactions from being adversely affected; since no particulate impurities are introduced into the mixture formed by the subsequent reaction of selenium (Se) and arsenic (As) in the glass melting tube, the particle scattering caused by the particulate impurities in the subsequent prepared sulfur-based glass is eliminated;

[0077] Step 7, put the glass melting tube 3 into the swing furnace for heating and slowly raise the temperature of the glass melting tube 3 to the third preset temperature range of 650-700°C, and then swing melt for a preset time of 12-18 hours, take out the glass melting tube 3 for air cooling and wall removal treatment, and anneal the chalcogenide glass obtained by the air cooling and wall removal treatment, so as to obtain the high-purity chalcogenide glass with ultra-low particle scattering to be prepared. In this embodiment, the annealing treatment here is to obtain the chalcogenide glass As obtained after the air cooling and wall removal treatment. 40 Se 60 The temperature is kept at the glass transition point temperature ±5°C for 2 hours, and then the chalcogenide glass is cooled to room temperature within 10 hours. For example, in this embodiment, for the third preset temperature range, the temperature of the glass melting tube 3 is slowly increased to 700°C.

[0078] It should be noted that by placing the glass melting tube 3 into a rocking furnace for heating and rocking melting, the vapor selenium (Se) and vapor arsenic (As) in the glass melting tube can be fully and evenly mixed and reacted to form uniform high-quality glass.

[0079] The high-purity chalcogenide glass with ultra-low particle scattering prepared in Example 4 was taken out from the glass melting tube, cut into pieces with a thickness of more than 20 mm, and then ground and double-sided polished to obtain a chalcogenide glass sample. The infrared spectral performance test results of the chalcogenide glass sample were as follows: Figure 4 Curve 3 shows.

[0080] from Figure 3 and Figure 4 It can be seen that the high-purity chalcogenide glass prepared in Example 1 using a 10 μm-level filtering device and the high-purity chalcogenide glass prepared in Example 3 have higher transmittance; the high-purity chalcogenide glass prepared in Example 2 using a 100 μm-level filtering device and the high-purity chalcogenide glass prepared in Example 4 also have higher transmittance than the chalcogenide glass prepared without using a filtering device (i.e., ordinary chalcogenide glass obtained by a traditional distillation method), and maintain a flat spectrum at short wavelengths (3 to 5 μm), while retaining the advantages of the metal reduction method, and the absorption peaks of impurities such as OH-, -H2O, As-O, and Se-O are significantly weakened, indicating that the high-purity chalcogenide glass preparation method in this invention application can effectively reduce the particle scattering impurities in the chalcogenide glass matrix, and can obtain a high-purity chalcogenide glass with high transmittance and flat spectrum.

[0081] Embodiment 5

[0082] In the fifth embodiment, the chemical formula of the ultra-low particle scattering high-purity chalcogenide glass to be prepared is set to As 35 S 65 Specifically, the method for preparing high-purity chalcogenide glass with ultra-low particle scattering comprises the following steps:

[0083] Step 1, prepare a set of high-purity quartz ampoule devices containing a glass raw material tube 1, a distillation transition tube 2 and a glass melting tube 3, and perform dehydroxylation pretreatment on the high-purity quartz ampoule device; wherein, refer to Figure 1As shown, the upper end of the glass raw material tube 1 is open, the upper and lower ends of the distillation transition tube 2 are open, and the upper and lower ends of the glass melting tube 3 are open. The upper end opening of the glass raw material tube 1 is connected to the lower end opening of the distillation transition tube 2 through a first connecting tube 4. A filtering device 5 for filtering particles is arranged in the first connecting tube 4. The filtering device 5 is micron-grade. For example, the filtering device 5 is made of Al2O3. The pore size of the filtering hole of the filtering device 5 is 100μm. According to actual needs, multiple filtering devices 5 can be loaded in sequence in the first connecting tube 4 for multiple purifications, so as to obtain purer glass. The upper end opening of the distillation transition tube 2 is connected to the lower end opening of the glass melting tube 3 through a second connecting tube 6. The upper end opening of the glass melting tube 3 is connected to a vacuum pump 7. The glass raw material tube 1, the distillation transition tube 2 and the glass melting tube 3 of the high-purity quartz ampoule device are all pre-treated for dehydroxylation.

[0084] Step 2: According to the chemical formula of the high-purity chalcogenide glass to be prepared, As 35 S 65 Weighing a sulfur (S) raw material in the form of fragments and having a purity of not less than 99.999%, and weighing an aluminum strip (Al) as a metal deoxidizer, and uniformly mixing the weighed sulfur (S) raw material and the metal deoxidizer aluminum strip (Al) to obtain a mixture; wherein the weighed amount of the metal deoxidizer aluminum strip (Al) is 0.03wt% of the total amount of the mixture;

[0085] Step 3, heating the obtained mixture at a predetermined reaction temperature of 650° C. for a predetermined reaction time of 10 hours, so that the metal deoxidizer aluminum strip (Al) in the mixture reacts with the sulfur (S) element to undergo a dehydroxylation reaction, thereby completing the dehydroxylation treatment of the sulfur (S) element by the metal deoxidizer aluminum strip (Al);

[0086] Step 4, start the vacuum pump 7, load the mixture after the dehydroxylation reaction (i.e., the mixture of the metal deoxidizer aluminum strip (Al) and the sulfur raw material) into the glass raw material tube 1, and load the non-sulfur elemental arsenic (As) raw material constituting the chemical formula of the high-purity sulfur-based glass to be prepared into the distillation transition tube 2, and perform heating and heat preservation treatment on the distillation transition tube 2 and the glass melting tube 3 respectively; wherein the heating and heat preservation treatment here is to wrap a heating belt around the outer side of the distillation transition tube 2 for heating and wrap a heating belt around the outer side of the glass melting tube 3 for heating;

[0087] It should be noted that by wrapping the heating tape around the distillation transition tube 2 for heating, water molecules and volatile oxides attached to the surface of the raw materials in the mixed material in the distillation transition tube can be eliminated; of course, by wrapping the heating tape around the glass melting tube 3 for heating, water molecules and volatile oxides attached to the surface of the arsenic (As) raw material in the glass melting tube can be eliminated;

[0088] Step 5, placing the glass raw material tube 1 into a tubular heating furnace for high-temperature heating and slowly raising the temperature of the glass raw material tube 1 to a first preset temperature range of 550-600°C, so that the sulfur (S) vapor formed by the sulfur (S) element being subjected to high temperature slowly passes through the filtering device 5 and is distilled into the distillation transition tube 2, and impurities such as carbon (C), SiO2 and MgO with high boiling points in the mixture remain in the glass raw material tube 1. The distillation is continued for 6 hours. After all the raw materials in the glass raw material tube 1 are distilled, the first connecting tube 4 between the glass raw material tube 1 and the distillation transition tube 2 is sealed with a hydrogen-oxygen flame; here, by selecting to heat the glass raw material tube in a tubular heating furnace, the tubular heating furnace can better control the heating temperature in real time to achieve the purpose of controlling the distillation rate, and observe the experimental phenomenon; for example, in this embodiment, for the first preset temperature range, the temperature of the glass raw material tube 1 is slowly raised to 550°C;

[0089] Specifically, the temperature in the tubular heating furnace is first raised to 300° C. and kept warm. When the mixed material in the glass raw material tube 1 becomes molten, the vacuum pump 7 is turned on and the vacuum degree is 1×10 -3 Pa is subjected to excessive distillation, and the temperature of the glass raw material tube 1 is slowly raised to 550-600° C. within 3 hours; due to the presence of the filtering device 5, the rate at which the raw material vapor flow in the glass raw material tube 1 condenses into the distillation transition tube 2 is greatly reduced, so the first preset temperature range is set to 550-600° C.;

[0090] Step 6, using a tubular heating furnace to heat the distillation transition tube 2 and slowly raising the temperature of the distillation transition tube 2 to a second preset temperature range of 500-550° C., so as to slowly distill sulfur (S) vapor formed by sulfur (S) being subjected to high temperature and arsenic (As) vapor formed by non-sulfur elemental arsenic (As) into the glass melting tube 3, and continuing the distillation for 3 hours. After all the raw materials in the distillation transition tube 2 are distilled, the second connecting tube 6 is sealed with a hydrogen-oxygen flame; for example, for the second preset temperature range, the temperature of the distillation transition tube 2 is slowly raised to 500° C.;

[0091] It should be noted that, due to the treatment in step 5, the sulfur (S) element in the original glass raw material tube 1 has been distilled into the distillation transition tube 2 in the form of vapor, and in step 6, the temperature of the distillation transition tube 2 is slowly increased to a second preset temperature range of 500-550° C., so that it can ensure that the sulfur (S) vapor and arsenic (As) vapor enter the glass melting tube 3 through the second connecting tube 6 in the form of vapor, and it can also avoid the particulate impurities in the arsenic (As) raw material being brought into the glass melting tube 3 by the vapor in the distillation transition tube 2, which will cause an adverse effect on the purity of the raw materials for subsequent reactions; since no particulate impurities are introduced into the mixture formed by the subsequent reaction of sulfur (S) and arsenic (As) in the glass melting tube, the particle scattering caused by the particulate impurities in the subsequent prepared sulfur-based glass is eliminated;

[0092] Step 7, put the glass melting tube 3 into the swing furnace for heating and slowly raise the temperature of the glass melting tube 3 to the third preset temperature range of 650-700°C, and then swing melt for a preset time of 12-18 hours, take out the glass melting tube 3 for air cooling and wall removal treatment, and anneal the chalcogenide glass obtained by the air cooling and wall removal treatment, so as to obtain the high-purity chalcogenide glass with ultra-low particle scattering to be prepared. In this embodiment, the annealing treatment here is to keep the chalcogenide glass obtained after the air cooling and wall removal treatment at a glass transition point temperature of ±5°C for 2 hours, and then cool the chalcogenide glass to room temperature within 10 hours. For example, in this embodiment, for the third preset temperature range, the temperature of the glass melting tube 3 here is slowly raised to 650°C.

[0093] It should be noted that by placing the glass melting tube 3 into a rocking furnace for heating and rocking melting, the vapor sulfur (S) and vapor arsenic (As) in the glass melting tube can be fully and evenly mixed and reacted to form uniform high-quality glass.

[0094] Embodiment 6

[0095] In the sixth embodiment, the chemical formula of the ultra-low particle scattering high-purity chalcogenide glass to be prepared is As 35 S 65 Specifically, the method for preparing high-purity chalcogenide glass with ultra-low particle scattering comprises the following steps:

[0096] Step 1, prepare a set of high-purity quartz ampoule devices containing a glass raw material tube 1, a distillation transition tube 2 and a glass melting tube 3, and perform dehydroxylation pretreatment on the high-purity quartz ampoule device; wherein, refer to Figure 1As shown, the upper end of the glass raw material tube 1 is open, the upper and lower ends of the distillation transition tube 2 are open, and the upper and lower ends of the glass melting tube 3 are open. The upper end opening of the glass raw material tube 1 is connected to the lower end opening of the distillation transition tube 2 through a first connecting tube 4. A filtering device 5 for filtering particles is arranged in the first connecting tube 4. The filtering device 5 is made of SiO2. The filtering device 5 is micron-grade. For example, the pore size of the filtering hole of the filtering device 5 is 10μm. According to actual needs, multiple filtering devices 5 can be loaded in sequence in the first connecting tube 4 for multiple purifications, so as to obtain purer glass. The upper end opening of the distillation transition tube 2 is connected to the lower end opening of the glass melting tube 3 through a second connecting tube 6. The upper end opening of the glass melting tube 3 is connected to a vacuum pump 7. The glass raw material tube 1, the distillation transition tube 2 and the glass melting tube 3 of the high-purity quartz ampoule device are all pre-treated for dehydroxylation.

[0097] Step 2: According to the chemical formula of the high-purity chalcogenide glass to be prepared, As 35 S 65 Weighing a sulfur (S) raw material in the form of fragments and having a purity of not less than 99.999%, and weighing an aluminum strip (Al) as a metal deoxidizer, and mixing the weighed sulfur (S) raw material and the metal deoxidizer aluminum strip (Al) uniformly to obtain a mixture; wherein the weighed amount of the metal deoxidizer aluminum strip (Al) is 0.1wt% of the total amount of the mixture;

[0098] Step 3, heating the obtained mixture at a predetermined reaction temperature of 650° C. for a predetermined reaction time of 10 hours, so that the metal deoxidizer aluminum strip (Al) in the mixture reacts with the sulfur (S) element to undergo a dehydroxylation reaction, thereby completing the dehydroxylation treatment of the sulfur (S) element by the metal deoxidizer aluminum strip (Al);

[0099] Step 4, start the vacuum pump 7, load the mixture after the dehydroxylation reaction (i.e., the mixture of the metal deoxidizer aluminum strip (Al) and the sulfur raw material) into the glass raw material tube 1, and load the non-sulfur elemental arsenic (As) raw material constituting the chemical formula of the high-purity sulfur-based glass to be prepared into the distillation transition tube 2, and perform heating and heat preservation treatment on the distillation transition tube 2 and the glass melting tube 3 respectively; wherein the heating and heat preservation treatment here is to wrap a heating belt around the outer side of the distillation transition tube 2 for heating and wrap a heating belt around the outer side of the glass melting tube 3 for heating;

[0100] It should be noted that by wrapping the heating tape around the distillation transition tube 2 for heating, water molecules and volatile oxides attached to the surface of the raw materials in the mixed material in the distillation transition tube can be eliminated; of course, by wrapping the heating tape around the glass melting tube 3 for heating, water molecules and volatile oxides attached to the surface of the arsenic (As) raw material in the glass melting tube can be eliminated;

[0101] Step 5, placing the glass raw material tube 1 into a tubular heating furnace for high-temperature heating and slowly raising the temperature of the glass raw material tube 1 to a first preset temperature range of 550-600°C, so that the sulfur (S) vapor formed by the sulfur (S) element being subjected to high temperature slowly passes through the filtering device 5 and is distilled into the distillation transition tube 2, and impurities such as carbon (C), SiO2 and MgO with high boiling points in the mixture remain in the glass raw material tube 1. The distillation is continued for 6 hours. After all the raw materials in the glass raw material tube 1 are distilled, the first connecting tube 4 between the glass raw material tube 1 and the distillation transition tube 2 is sealed with a hydrogen-oxygen flame; here, by selecting to heat the glass raw material tube in a tubular heating furnace, the heating temperature can be better controlled in real time by the tubular heating furnace to achieve the purpose of controlling the distillation rate, and the experimental phenomenon is observed; for example, in this embodiment, for the first preset temperature range, the temperature of the glass raw material tube 1 is slowly raised to 600°C;

[0102] Specifically, the temperature in the tubular heating furnace is first raised to 300° C. and kept warm. When the mixed material in the glass raw material tube 1 becomes molten, the vacuum pump 7 is turned on and the vacuum degree is 1×10 -3 Pa is subjected to excessive distillation, and the temperature of the glass raw material tube 1 is slowly raised to 550-600° C. within 3 hours; due to the presence of the filtering device 5, the rate at which the raw material vapor flow in the glass raw material tube 1 condenses into the distillation transition tube 2 is greatly reduced, so the first preset temperature range is set to 550-600° C.;

[0103] Step 6, using a tubular heating furnace to heat the distillation transition tube 2 and slowly raising the temperature of the distillation transition tube 2 to a second preset temperature range of 500-550° C., so as to slowly distill sulfur (S) vapor formed by sulfur (S) being subjected to high temperature and arsenic (As) vapor formed by non-sulfur elemental arsenic (As) into the glass melting tube 3, and continuing the distillation for 3 hours. After all the raw materials in the distillation transition tube 2 are distilled, the second connecting tube 6 is sealed with a hydrogen-oxygen flame; for example, for the second preset temperature range, the temperature of the distillation transition tube 2 is slowly raised to 550° C.;

[0104] It should be noted that, due to the treatment in step 5, the sulfur (S) element in the original glass raw material tube 1 has been distilled into the distillation transition tube 2 in the form of vapor, and in step 6, the temperature of the distillation transition tube 2 is slowly increased to a second preset temperature range of 500-550° C., so that it can ensure that the sulfur (S) vapor and arsenic (As) vapor enter the glass melting tube 3 through the second connecting tube 6 in the form of vapor, and it can also avoid the particulate impurities in the arsenic (As) raw material being brought into the glass melting tube 3 by the vapor in the distillation transition tube 2, which will cause an adverse effect on the purity of the raw materials for subsequent reactions; since no particulate impurities are introduced into the mixture formed by the subsequent reaction of sulfur (S) and arsenic (As) in the glass melting tube, the particle scattering caused by the particulate impurities in the subsequent prepared sulfur-based glass is eliminated;

[0105] Step 7, put the glass melting tube 3 into the swing furnace for heating and slowly raise the temperature of the glass melting tube 3 to the third preset temperature range of 650-700°C, and then swing melt for a preset time of 12-18 hours, take out the glass melting tube 3 for air cooling and wall removal treatment, and anneal the chalcogenide glass obtained by the air cooling and wall removal treatment, so as to obtain the high-purity chalcogenide glass with ultra-low particle scattering to be prepared. In this embodiment, the annealing treatment here is to keep the chalcogenide glass obtained after the air cooling and wall removal treatment at a glass transition point temperature of ±5°C for 2 hours, and then cool the chalcogenide glass to room temperature within 10 hours. For example, in this embodiment, for the third preset temperature range, the temperature of the glass melting tube 3 here is slowly raised to 700°C.

[0106] It should be noted that by placing the glass melting tube 3 into a rocking furnace for heating and rocking melting, the vapor sulfur (S) and vapor arsenic (As) in the glass melting tube can be fully and evenly mixed and reacted to form uniform high-quality glass.

[0107] Although the preferred embodiments of the present invention are described in detail above, it should be clearly understood that various modifications and variations are possible for those skilled in the art. Any modification, equivalent substitution, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing high-purity chalcogenide glass with ultra-low particle scattering, characterized in that: The steps include: Step 1, preparing a group of high-purity quartz ampoule devices including a glass raw material tube, a distillation transition tube and a glass melting tube, and performing a dehydroxylation pretreatment on the high-purity quartz ampoule device; wherein the upper end of the glass raw material tube is open, the upper and lower ends of the distillation transition tube are both open, the upper and lower ends of the glass melting tube are both open, the upper end opening of the glass raw material tube is connected to the lower end opening of the distillation transition tube through a first connecting tube, a filtering device for filtering particles is arranged in the first connecting tube, the upper end opening of the distillation transition tube is connected to the lower end opening of the glass melting tube through a second connecting tube, and the upper end opening of the glass melting tube is connected to a vacuum pump; Step 2, weighing a sulfur-based elemental raw material in a broken block form according to the chemical formula of the high-purity sulfur-based glass to be prepared, and weighing a metal deoxidizer, and mixing the weighed sulfur-based elemental raw material and the metal deoxidizer evenly to obtain a mixture; Step 3, heating the obtained mixture at a predetermined reaction temperature for a predetermined reaction time, so that the metal deoxidizer in the mixture reacts with the sulfur-based elemental raw material to undergo a dehydroxylation reaction, thereby completing the dehydroxylation treatment of the sulfur-based elemental raw material by the metal deoxidizer; Step 4, starting the vacuum pump, loading the mixture after the dehydroxylation reaction into the glass raw material tube, and loading the non-sulfur-based single material constituting the chemical formula of the high-purity sulfur-based glass to be prepared into the distillation transition tube, and heating and heat preservation treatment is respectively performed on the distillation transition tube and the glass melting tube; wherein the heating and heat preservation treatment is to wrap a heating belt around the outside of the distillation transition tube for heating and wrap a heating belt around the outside of the glass melting tube for heating; Step 5, placing the glass raw material tube into a tubular heating furnace for high-temperature heating and slowly raising the temperature of the glass raw material tube to a first preset temperature range, so that the sulfur-based vapor formed by the sulfur-based element after being subjected to high temperature slowly passes through the filtering device and is distilled into the distillation transition tube. After all the raw materials in the glass raw material tube are distilled, the first connecting tube between the glass raw material tube and the distillation transition tube is sealed with a hydrogen-oxygen flame; Step 6, using a tubular heating furnace to heat the distillation transition tube and slowly raising the temperature of the distillation transition tube to a second preset temperature range, so as to slowly distill the sulfur-based vapor formed by the sulfur-based element after being subjected to high temperature and the non-sulfur-based vapor formed by the non-sulfur-based element into the glass melting tube, and after all the raw materials in the distillation transition tube are distilled, the second connecting tube is sealed with a hydrogen-oxygen flame; Step 7, put the glass melting tube into the swing furnace for heating and slowly raise the temperature of the glass melting tube to the third preset temperature range and then perform swing melting for a preset time, take out the glass melting tube for air cooling and wall removal treatment, and anneal the chalcogenide glass obtained by the air cooling and wall removal treatment, so as to obtain the high-purity chalcogenide glass with ultra-low particle scattering to be prepared.

2. The method for preparing high-purity chalcogenide glass with ultra-low particle scattering according to claim 1, characterized in that: The filter device is made of SiO2 or Al2O3, and the diameter of the filter holes is in the size range of 10 μm to 100 μm.

3. The method for preparing high-purity chalcogenide glass with ultra-low particle scattering according to claim 1 or 2, characterized in that: The weighed amount of the metal deoxidizer is 0.03-0.1wt% of the total amount of the mixture; the predetermined reaction temperature is 650°C, and the predetermined reaction time is 10 hours; the first preset temperature range is 550-600°C, and the distillation time of the sulfur vapor is 6 hours; the second preset temperature range is 500-550°C, and the distillation time of the sulfur vapor and the non-sulfur vapor is 3 hours; the third preset temperature range is 650-700°C, and the preset time of the swing melting is 12-18 hours.

4. The method for preparing high-purity chalcogenide glass with ultra-low particle scattering according to claim 1 or 2, characterized in that: The annealing treatment is to keep the chalcogenide glass obtained after the air-cooling and wall-removing treatment at a temperature of ±5° C. at the glass transition point for 2 hours, and then cool the chalcogenide glass to room temperature within 10 hours.

5. The method for preparing high-purity chalcogenide glass with ultra-low particle scattering according to claim 1 or 2, characterized in that: A plurality of filtering devices are sequentially loaded in front and behind in the first connecting pipe.

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