CN113480171A - Se-free long-wave infrared transparent chalcogenide glass and preparation method thereof - Google Patents
Se-free long-wave infrared transparent chalcogenide glass and preparation method thereof Download PDFInfo
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Abstract
The invention discloses Se-free long-wave infrared transparent chalcogenide glass and a preparation method thereof, wherein the molar composition of the Se-free long-wave infrared transparent chalcogenide glass is represented by a chemical formula as follows: (1-x-y) Sb2S3·xIn2S3And yCsI, wherein x is 0-0.20, and y is 0.1-0.35, the material has good glass forming capability and a wider infrared transmission window, and is suitable for developing novel infrared optical materials. The invention also discloses a preparation method of the Se-free long-wave infrared transparent chalcogenide glass, and the prepared chalcogenide glass contains non-toxic elements, is an environment-friendly infrared optical material and can be used in the fields of switch devices, storage devices, thermal imaging, radiation thermometers, night vision, glass optical fibers and the like.
Description
Technical Field
The invention relates to the technical field of chalcogenide glass, in particular to Se-free long-wave infrared transparent chalcogenide glass and a preparation method thereof, and belongs to the field of infrared optical materials.
Background
The development of infrared detection technology has made demands on novel infrared optical systems to meet the high performance requirements of infrared thermal imagers. Currently, researchers combine different infrared optical materials (including crystals such as ZnS, ZnSe, and germanium single crystals and amorphous infrared materials such as chalcogenide glass) to realize novel optical designs. In commercial amorphous infrared materials, chalcogenide glass is the only material which can be used for 8-12 mu m long-wave infrared thermal imaging systems. The optical characteristics can be flexibly adjusted through component modification. A variety of commercially available chalcogenide glasses, including Ge-Sb-Se, As-Se (S), and Ge-As-Se systems, are commercially available from glass manufacturers worldwide. However, these commercial chalcogenide glasses usually contain As or Se element. As is readily oxidized to produce a variety of toxic compounds, and although Se has a micronutrient value, it is also one of the most toxic natural elements, especially when exposed to excessive levels. Therefore, the search for new As-free/Se-free long-wave infrared transparent chalcogenide glasses has been attracting attention in recent years.
Sulfide glasses are one of the most widely studied chalcogenide glasses because of their good glass forming ability, high rare earth solubility, and excellent thermal and mechanical properties. However, the long-wavelength infrared cutoff edge of common sulfide glasses (Ge-S and Ga-S glasses) is limited to about 11 μm, and the application thereof to an infrared lens causes the loss of infrared signals of more than 11 μm. Therefore, the long-wavelength infrared cut edge of the sulfide glass needs to be extended to 12 μm or more. The long wavelength infrared cut-off edge of the optical material is determined by the maximum phonon energy. According to hooke's law, heavy atoms are beneficial to reducing the maximum phonon energy of an optical material and widening the long-wave infrared cut-off edge. Studies have reported that the introduction of the heavy atom Sb in Ge-S glass can extend the transmission window to 12.5 μm. However, due to the presence of [ GeS ] in the glass structure4](maximum phonon energy of 340cm-1) Further expanding the long-wave infrared cut-off edge is extremely difficult. Subsequently, researchers developedDoes not contain GeS2Novel sulfide glasses for glass formers are needed to meet the requirements for long wave infrared applications. Sb2S3Base glass due to its low phonon energy (-300 cm)-1) Have received a great deal of attention. Due to Sb2S3Introduction of metal halide and Ga, not as a glass former2S3Glass formation may be promoted. Some Sb2S3Based chalcogenide glasses, e.g. Sb2S3-MX (MX ═ metal halide) and Sb2S3-Ga2S3-MX, developed and exhibiting excellent optical properties. However, the above Sb2S3The ability of the chalcogenide glass to form is still poor. Therefore, Sb having excellent glass formability was obtained by searching for the relationship between glass formation and structure2S3The chalcogenide glass is expected to be applied to the novel infrared optical system.
Disclosure of Invention
The invention aims to provide Se-free long-wave infrared transparent chalcogenide glass, which has good glass forming capacity and a wider infrared transmission window and is suitable for developing novel infrared optical materials.
The technical scheme adopted by the embodiment of the invention is as follows: the Se-free long-wave infrared transparent chalcogenide glass is provided, and the molar composition of the Se-free long-wave infrared transparent chalcogenide glass is represented by the chemical formula: (1-x-y) Sb2S3·xIn2S3yCsI, wherein x is 0 to 0.20 and y is 0.1 to 0.35.
The chalcogenide glass prepared by the invention contains non-toxic elements and is an environment-friendly infrared optical material. In addition, the chalcogenide glass has a wider infrared transmission window, the infrared cut-off wavelength can be extended to 14 micrometers, the glass has higher transmittance in a spectral range of 0.6-13.5 micrometers, and the chalcogenide glass covers each atmospheric window of 1-3 micrometers, 3-5 micrometers and 8-12 micrometers, and can be used in the fields of switching devices, memory devices, thermal imaging, radiation thermometers, night vision, glass optical fibers and the like.
Optionally, the chalcogenide glass has an infrared cutoff wavelength of 14 μm.
Optionally, the chalcogenide glass has a transmittance of 60 to 70% in a spectral range of 0.6 to 13.5 μm; preferably, the chalcogenide glass has a transmittance of 65 to 70% in a spectral range of 0.6 to 13.5 μm.
The second purpose of the invention is to provide a preparation method of Se-free long-wave infrared transparent chalcogenide glass, and the prepared material has good glass forming capability.
The technical scheme adopted by the embodiment of the invention is as follows: the preparation method of the Se-free long-wave infrared transparent chalcogenide glass comprises the following steps:
s1, weighing raw materials, wherein the raw materials comprise simple substances Sb, S, In and CsI compounds, putting the raw materials into a quartz reactor, vacuumizing, sealing the quartz reactor by melting, and removing impurities and purifying the raw materials to obtain a purified substance;
s2, placing the quartz reactor filled with the purified product into a swinging heating furnace, slowly heating, keeping the temperature for 8-20 hours under the swinging condition, and then cooling and quenching; impurity removal is carried out on the raw materials, mainly impurity oxygen in the raw materials is removed, the extrinsic loss of the chalcogenide glass is reduced, and the influence of the impurity oxygen on the optical loss of the chalcogenide glass is reduced;
s3, annealing the quenched quartz reactor to obtain Se-free long-wave infrared transparent chalcogenide glass.
Optionally, the step S1 includes the following steps: s11, uniformly mixing the weighed Sb, S and In simple substances and the CsI compound to obtain a mixture, and weighing an oxygen scavenger, wherein the weighing amount of the oxygen scavenger is 0.03-0.1 wt% of the total amount of the mixture; the dosage of the oxygen scavenger is less than 0.03 wt%, oxygen impurities in the chalcogenide glass cannot be sufficiently removed, and if the dosage of the oxygen scavenger is more than 0.1 wt%, the glass is crystallized due to excessive mixing of the oxygen scavenger, so that the glass is devitrified during drawing;
s12, the quartz reactor is an H-shaped double-tube quartz ampoule which comprises a raw material tube, a purifying tube and a connecting tube for connecting the raw material tube and the purifying tube, one end of the raw material tube is provided with an opening, the mixture and the deoxidant are uniformly mixed and placed in the raw material tube, and the opening of the raw material tube is sealed by fusion after the H-shaped double-tube quartz ampoule is vacuumized; the operation of the step is to provide a vacuum environment for the raw materials placed in the H-shaped double-tube quartz ampoule, so as to avoid the raw materials from being oxidized and introduce impurities into the materials, thereby reducing the extrinsic absorption of chalcogenide glass in an infrared region.
S13, placing the H-shaped double-tube quartz ampoule into a double-temperature-zone distillation furnace, performing distillation purification, obtaining purified Sb, S, In and CsI In the purification tube, and then sealing the connection tube by using flame; the step is operated, raw materials are purified in a raw material distillation mode; the extrinsic loss of the glass material is generated in the manufacturing process and mainly caused by the absorption of impure components in the raw materials and the structural defects, and the purification of the raw materials can reduce the extrinsic loss of the chalcogenide glass finished product.
Optionally, In step S11, the purities of the simple substances Sb, S, and In are all above 5N, and the purity of the CsI compound is above 4N; the higher the purity of the feedstock, the less the impurity oxygen content from the feedstock.
Optionally, in step S11, the oxygen scavenger is Mg or Al; the deoxidant is magnesium element simple substance or aluminum element simple substance, the two elements are active elements, the two elements have the capability of combining with oxygen preferentially to form bonds, a series of harmful absorbed X-O bonds existing in chalcogenide glass and caused in near, middle and far infrared regions are eliminated, and the generated oxide has lower vapor pressure, so that trace deoxidant can remove oxide impurities in chalcogenide glass.
Optionally, in step S12, the degree of vacuum of the H-shaped double-tube quartz ampoule is less than 10-3Pa。
Optionally, in step S2, the quartz reactor is slowly heated to 850-950 ℃, cooled to 750-850 ℃ and quenched.
Optionally, in step S3, annealing the quenched quartz reactor at 130-200 ℃ for 2-5h to obtain the Se-free long-wave infrared transparent chalcogenide glass.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
compared with the prior art, the invention has the advantages that: the invention discloses novel long-wave infrared transparent chalcogenide glass applicable to infrared optics and a preparation method thereofThe method is carried out. By studying the relationship between the glass composition and the structure, the glass composition is optimized, and In is adjusted2S3CsI ratio, Sb prepared2S3The chalcogenide glass has good glass forming ability, and no microcrystal particles exist in the glass.
Drawings
FIG. 1 is a DSC curve of a sulfur-based glass in example 2 of the present invention;
FIG. 2 is an X-ray diffraction pattern of chalcogenide glasses according to examples 1-6 and comparative examples of the present invention;
FIG. 3 is a transmission spectrum of chalcogenide glass having a thickness of 2mm in example 2 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The application aims to provide a method which does not contain GeS2The Se-free long-wave infrared transparent chalcogenide glass of the glass forming body has the following molar composition according to a chemical formula: (1-x-y) Sb2S3·xIn2S3And yCsI, wherein x is 0-0.20, and y is 0.1-0.35, the material has an environment-friendly infrared transmission window with stable physicochemical properties and a wider infrared transmission window, and is suitable for developing novel infrared optical materials.
The application also aims to provide a preparation method of the Se-free long-wave infrared transparent chalcogenide glass, which comprises the following steps:
s1, weighing raw materials, wherein the raw materials comprise simple substances Sb, S, In and CsI compounds, putting the raw materials into a quartz reactor, vacuumizing, sealing the quartz reactor by melting, and removing impurities and purifying the raw materials to obtain a purified substance;
s2, placing the quartz reactor filled with the purified product into a swinging heating furnace, slowly heating, keeping the temperature for 8-20 hours under the swinging condition, and then cooling and quenching;
s3, annealing the quenched quartz reactor to obtain Se-free long-wave infrared transparent chalcogenide glass.
Further, annealing the quenched quartz reactor, in fact, the refined product is annealed under vacuum conditions in order to form chalcogenide glass.
Further, step S1 is to obtain a purified raw material, and is to remove oxygen impurities from the raw material and reduce the influence of extrinsic absorption loss in chalcogenide glass on its infrared characteristics. In the field of chalcogenide glass preparation, three purification methods, namely a vacuum distillation method, an oxygen scavenger method and a vacuum distillation combined oxygen scavenger method, mainly exist, and the method for removing impurities and purifying raw materials to obtain purified products belongs to the protection range of the application.
Furthermore, the chalcogenide glass is purified by a vacuum distillation method, namely the chalcogenide glass is distilled by utilizing the characteristic that the steam pressure of the simple substance and the oxide of the simple substance in the raw materials has larger difference at a certain temperature so as to remove oxygen and other non-volatile impurities and achieve the effect of removing oxygen.
Furthermore, the oxygen scavenger method is to add oxygen scavenger, such as at least one element simple substance raw material of aluminum, magnesium and the like, into the quartz reactor under the vacuum condition or under the protection of inert gas, wherein the elements are all active elements, the ability of preferentially combining with oxygen is that X-O bonds existing in chalcogenide glass and causing a series of harmful absorption in near, middle and far infrared regions are eliminated, and the generated oxide has lower vapor pressure. Therefore, trace elemental substances of magnesium, aluminum and the like are added into the chalcogenide glass to remove oxide impurities in the chalcogenide glass.
Specifically, in the scheme of the present invention, a purification method combining vacuum distillation with an oxygen scavenger is adopted, that is, the step S1 includes the following steps:
s11, uniformly mixing the weighed Sb, S and In simple substances and the CsI compound to obtain a mixture, and weighing an oxygen scavenger, wherein the weighing amount of the oxygen scavenger is 0.03-0.1 wt% of the total amount of the mixture;
s12, the quartz reactor is an H-shaped double-tube quartz ampoule which comprises a raw material tube, a purifying tube and a connecting tube for connecting the raw material tube and the purifying tube, one end of the raw material tube is provided with an opening, the mixture and the deoxidant are uniformly mixed and placed in the raw material tube, and the opening of the raw material tube is sealed by fusion after the H-shaped double-tube quartz ampoule is vacuumized;
and S13, putting the H-shaped double-tube quartz ampoule into a double-temperature-zone distillation furnace, performing distillation purification, obtaining purified Sb, S, In and CsI In the purification tube, and then sealing the connecting tube by using flame.
Specifically, step S12 may be replaced by the following: the quartz reactor is double-barrelled quartz ampoule of H type, and this double-barrelled quartz ampoule of H type includes former feed tube, purification pipe and the connecting pipe of switch-on former feed tube and purification pipe, and the one end of former feed tube and the one end of purification pipe all are equipped with the opening, and in putting into the former feed tube mixture and deoxidant misce bene, melt the opening on the former feed tube, behind the double-barrelled quartz ampoule of evacuation H type, melt the opening on the purification pipe.
Specifically, In step S11, the purities of the simple substances Sb, S, and In are all 5N or more, and the purity of the CsI compound is 4N or more.
Specifically, in step S11, the oxygen scavenger is Mg or Al; .
Specifically, in step S12, the degree of vacuum of the H-shaped double-tube quartz ampoule is less than 10-3Pa。
Specifically, in the step S2, the quartz reactor is slowly heated to 850-950 ℃, cooled to 750-850 ℃ and quenched.
Specifically, in the step S3, the quenched quartz reactor is annealed at 130-200 ℃ for 2-5h to obtain Se-free long-wave infrared transparent chalcogenide glass.
Specifically, the steps S11-S13 are to remove impurities and purify the raw materials, and eliminate the [ -OH ] and [ H-O-H ] impurities in the chalcogenide glass. The above steps omit some routine experimental operations during the experiment, such as dehydroxylation pretreatment of the H-type double-tube quartz ampoule before step S1.
Further, the dehydroxylation pretreatment is specifically that the H-shaped double-tube quartz ampoule is sequentially cleaned by hydrofluoric acid, deionized water and absolute ethyl alcohol, and finally the H-shaped double-tube quartz ampoule is placed into a dry oven to be completely dried, so that the H-shaped double-tube quartz ampoule is prevented from bringing impurity oxygen to the reaction.
Furthermore, the oxygen-hydrogen flame or the oxyacetylene flame is adopted for melting and sealing the quartz material and sealing off the quartz material in the whole process, so that the impurity oxygen brought to the reaction in the sealing process is reduced.
The material prepared by the preparation method has good glass forming capability.
For better technical solutions, the technical solutions will be described in detail below with reference to the drawings and specific embodiments of the specification.
Example 1
The embodiment provides a preparation method of Se-free long-wave infrared transparent chalcogenide glass, which comprises the following steps: taking 5N-purity Sb simple substance, In simple substance, S simple substance and 4N-purity CsI compound as raw materials, calculating the weight of each raw material according to the molar composition, wherein the molar composition is expressed by a chemical formula as follows: (1-x-y) Sb2S3·xIn2S3yCsI, where x is 0.05 and y is 0.3, the molar composition of the chalcogenide glass is 65Sb according to the formula2S3·5In2S330 CsI. Weighing 10g of raw materials in a glove box filled with inert gas and uniformly mixing; then the uniformly mixed raw materials are put into a glass raw material tube of an H-shaped double-tube quartz ampoule, the quartz ampoule is dried in advance and is pre-filled with 0.03-0.1 wt% of magnesium strips, in the embodiment, 0.1 wt% of magnesium strips are specifically adopted, the 0.1 wt% of magnesium strips is the weight percentage concentration of the magnesium strips in the glass mixture, the magnesium strips can react with oxides in the raw materials to remove oxygen impurities in the raw materials, the purpose of purifying the raw materials is achieved, and meanwhile, magnesium is not mixed with glass to be smelted. The quartz ampoule was evacuated to 1.0X 10-3Pa, then sealing the quartz ampoule by oxyhydrogen flame; and (3) putting the sealed quartz ampoule into a double-temperature-zone distillation furnace, setting the temperature of the cold end to be 100 ℃ and the temperature of the hot end to be 400 ℃, and performing distillation purification. Obtaining purified Sb, In, S and CsI substances In a purified glass tube of a quartz ampoule, and then sealing off the double tubes by oxyhydrogen flame; putting the sealed purified glass tube filled with the purified substance into a swinging heating furnace for high temperatureMelting, slowly heating to 900 ℃ in a multi-stage heating mode, preserving heat for 10 hours under the condition of swinging, cooling to 800 ℃, quenching, quickly putting into an annealing furnace, preserving heat for 2 hours at 180 ℃, slowly cooling to room temperature, and breaking quartz ampoules to obtain chalcogenide glass samples.
In this example, the Se-free long-wave infrared transparent chalcogenide glass prepared by the above method had a molar composition of 65Sb2S3·5In2S3·30CsI。
The DSC curve of the sulfur-based glass sample of this example is shown in FIG. 1. As can be seen, the glass transition temperature T of the chalcogenide glass sample of example 1gAt 215 ℃ and an initial crystallization temperature TxAt a temperature of 331 ℃ and a.DELTA.T thereof>At 100 ℃. Thus, the chalcogenide glass sample of example 1 had good glass forming ability.
In FIG. 2, the curve (a) is the X-ray diffraction pattern of the chalcogenide glass sample in this example, and no significant diffraction peak is observed, indicating that the chalcogenide glass is amorphous and no crystallite particles are present in the glass.
FIG. 3 is a transmission spectrum of a chalcogenide glass sample of 2mm thickness in this example. As can be seen from FIG. 3, the long-wavelength infrared cut-off edge of the chalcogenide glass sample can reach 14 μm, and the transmittance within the range of 0.6 to 13.5 μm is 70. + -. 3%.
Example 2
The embodiment provides a preparation method for preparing Se-free long-wave infrared transparent chalcogenide glass, which comprises the following steps of: taking 5N-purity Sb simple substance, In simple substance, S simple substance and 4N-purity CsI compound as raw materials, calculating the weight of each raw material according to the molar composition, wherein the molar composition is expressed by a chemical formula as follows: (1-x-y) Sb2S3·xIn2S3yCsI, where x is 0.1 and y is 0.15, the molar composition of the chalcogenide glass is 75Sb2S3·10In2S315 CsI. Weighing 10g of raw materials in a glove box filled with inert gas and uniformly mixing; then, the uniformly mixed raw materials were charged into a glass raw material tube of an H-type double-tube quartz ampoule which was previously dried and previously charged with 0.1 wt% of magnesiumStrip, evacuating a quartz ampoule to 1.0X 10-3Pa, then sealing the quartz ampoule by melting with oxyacetylene flame; putting the sealed quartz ampoule into a double-temperature-zone distillation furnace, setting the temperature of a cold end to be 100 ℃ and the temperature of a hot end to be 400 ℃, performing distillation purification to obtain purified Sb, In, S and CsI In a purified glass tube of the quartz ampoule, and then sealing off the double tubes by oxyhydrogen flame; and (3) putting the sealed purified glass tube filled with the purified substance into a swinging heating furnace for high-temperature melting, slowly heating to 930 ℃ in a multi-stage heating mode, preserving heat for 12 hours under the condition of swinging, cooling to 830 ℃, quenching, quickly putting into an annealing furnace, preserving heat for 3 hours at 160 ℃, slowly cooling to room temperature, and breaking a quartz ampoule to obtain a chalcogenide glass sample.
In this example, the Se-free long-wavelength infrared transparent chalcogenide glass prepared by the above method had a molar composition of 75Sb2S3·10In2S3·15CsI。
The glass transition temperature T of the chalcogenide glass sample in the present example was determinedgAt 210 ℃ and an initial crystallization temperature TxAt 315 ℃ and a.DELTA.T thereof>100℃。
In fig. 2, curve (b) is an X-ray diffraction pattern of the chalcogenide glass sample in this example, and no significant diffraction peak is observed, indicating that the chalcogenide glass is amorphous and no crystallite particles are present in the glass. The chalcogenide glass of example 2 has a long-wave infrared cut edge of about 14 μm and a transmittance of 65. + -. 3% in the range of 0.65 to 13.3. mu.m.
Example 3
The embodiment provides a preparation method for preparing Se-free long-wave infrared transparent chalcogenide glass, which comprises the following steps of: taking 5N-purity Sb simple substance, In simple substance, S simple substance and 4N-purity CsI compound as raw materials, calculating the weight of each raw material according to the molar composition, wherein the molar composition is expressed by a chemical formula as follows: (1-x-y) Sb2S3·xIn2S3yCsI, where x is 0.15 and y is 0.25, the molar composition of the chalcogenide glass is represented by the formula 60Sb2S3·15In2S325 CsI. In a glove box filled with inert gasWeighing 10g of raw materials and uniformly mixing; then, the uniformly mixed raw materials were charged into a glass raw material tube of an H-shaped double-tube quartz ampoule which had been previously dried and previously charged with 0.1 wt% magnesium rod, and the quartz ampoule was evacuated to 1.0X 10-3Pa, then sealing the quartz ampoule by oxyhydrogen flame; putting the sealed quartz ampoule into a double-temperature-zone distillation furnace, setting the temperature of a cold end to be 100 ℃ and the temperature of a hot end to be 400 ℃, performing distillation purification to obtain purified Sb, In, S and CsI In a purified glass tube of the quartz ampoule, and then sealing off the double tubes by oxyhydrogen flame; and (3) putting the sealed purified glass tube filled with the purified substance into a swinging heating furnace for high-temperature melting, slowly heating to 880 ℃ in a multi-stage heating mode, preserving heat for 15 hours under the condition of swinging, cooling to 780 ℃, quenching, quickly putting into an annealing furnace, preserving heat for 3 hours at 140 ℃, slowly cooling to room temperature, and breaking a quartz ampoule to obtain a chalcogenide glass sample.
In this example, the Se-free long-wave infrared transparent chalcogenide glass prepared by the above method had a molar composition of 60Sb2S3·15In2S3·25CsI。
The glass transition temperature T of the chalcogenide glass sample in the present example was determinedgAt 206 ℃ and an initial crystallization temperature TxAt 309 ℃ and. DELTA.T thereof>100℃。
In fig. 2, curve (c) is the X-ray diffraction pattern of the chalcogenide glass sample in this example, no obvious diffraction peak is observed, which indicates that the chalcogenide glass has no crystallization phenomenon and still maintains the complete amorphous structure. The chalcogenide glass of example 3 has a long-wave infrared cut edge of about 14 μm and a transmittance of 68. + -. 3% in the range of 0.6 to 13.4. mu.m.
Example 4
The embodiment provides a preparation method for preparing Se-free long-wave infrared transparent chalcogenide glass, which comprises the following steps of: taking 5N-purity Sb simple substance, In simple substance, S simple substance and 4N-purity CsI compound as raw materials, calculating the weight of each raw material according to the molar composition, wherein the molar composition is expressed by a chemical formula as follows: (1-x-y) Sb2S3·xIn2S3yCsI, whereinWhen x is 0.05 and y is 0.35, the molar composition of the chalcogenide glass is 60Sb2S3·5In2S335 CsI. Weighing 10g of raw materials in a glove box filled with inert gas and uniformly mixing; then, the uniformly mixed raw materials were charged into a glass raw material tube of an H-shaped double-tube quartz ampoule which had been previously dried and previously charged with 0.1 wt% magnesium rod, and the quartz ampoule was evacuated to 1.0X 10-3Pa, then sealing the quartz ampoule by oxyhydrogen flame; putting the sealed quartz ampoule into a double-temperature-zone distillation furnace, setting the temperature of a cold end to be 100 ℃ and the temperature of a hot end to be 400 ℃, performing distillation purification to obtain purified Sb, In, S and CsI In a purified glass tube of the quartz ampoule, and then sealing off the double tubes by oxyhydrogen flame; and (3) putting the sealed purified glass tube filled with the purified substance into a swinging heating furnace for high-temperature melting, slowly heating to 890 ℃ in a multi-stage heating mode, preserving heat for 16h under the condition of swinging, cooling to 790 ℃, quenching, quickly putting into an annealing furnace, preserving heat for 4h at 170 ℃, slowly cooling to room temperature, and breaking a quartz ampoule to obtain a chalcogenide glass sample.
In this example, the Se-free long-wave infrared transparent chalcogenide glass prepared by the above method had a molar composition of 60Sb2S3·5In2S3·35CsI。
The glass transition temperature T of the chalcogenide glass sample in the present example was determinedgAt 209 ℃ and an initial crystallization temperature TxAt 322 ℃ and. DELTA.T thereof>100℃。
In FIG. 2, the curve (d) is the X-ray diffraction pattern of the sulfur-based glass sample in this example, and no significant diffraction peak is observed. The chalcogenide glass of example 4 has a long-wavelength infrared cut edge of about 14 μm and a transmittance of 60. + -. 3% in the range of 0.6 to 13.5. mu.m.
Example 5
This example provides a method for preparing the Se-free long wave infrared transparent chalcogenide glass of example 9 comprising the steps of: taking 5N-purity Sb simple substance, S simple substance and 4N-purity CsI compound as raw materials, calculating the weight of each raw material according to the molar composition, and expressing the molar composition according to a chemical formulaComprises the following steps: (1-x-y) Sb2S3·xIn2S3yCsI, where x is 0 and y is 0.3. Weighing 10g of raw materials in a glove box filled with inert gas and uniformly mixing; then, the uniformly mixed raw materials were charged into a glass raw material tube of an H-shaped double-tube quartz ampoule which had been previously dried and previously charged with 0.1 wt% magnesium rod, and the quartz ampoule was evacuated to 1.0X 10-3Pa, then sealing the quartz ampoule by oxyhydrogen flame; putting the sealed quartz ampoule into a double-temperature-zone distillation furnace, setting the temperature of a cold end to be 100 ℃ and the temperature of a hot end to be 400 ℃, carrying out distillation purification, obtaining purified Sb, S and CsI in a purified glass tube of the quartz ampoule, and then sealing off a double tube by oxyhydrogen flame; and (3) putting the sealed purified glass tube filled with the purified substance into a swinging heating furnace for high-temperature melting, slowly heating to 920 ℃ in a multi-stage heating mode, preserving heat for 12 hours under the condition of swinging, cooling to 820 ℃, quenching, quickly putting into an annealing furnace, preserving heat for 2 hours at 170 ℃, slowly cooling to room temperature, and breaking a quartz ampoule to obtain a chalcogenide glass sample.
In this example, the Se-free long-wave infrared transparent chalcogenide glass prepared by the above method had a molar composition of 70Sb2S3·30CsI。
The glass transition temperature T of the chalcogenide glass sample of example 5 was determinedgAt 217 ℃ and an initial crystallization temperature TxAt 318 ℃ and a.DELTA.T thereof>100℃。
In fig. 2, curve (e) is the X-ray diffraction pattern of the chalcogenide glass sample in this example, no obvious diffraction peak is observed, which indicates that the chalcogenide glass has no crystallization phenomenon and still maintains the complete amorphous structure. The chalcogenide glass of example 5 has a long-wave infrared cut edge of about 14 μm and a transmittance of 65. + -. 3% in the range of 0.6 to 13.5. mu.m.
Example 6
The embodiment provides a preparation method for preparing Se-free long-wave infrared transparent chalcogenide glass, which comprises the following steps of: the preparation method comprises the following steps: using 5N pure Sb simple substance, In simple substance, S simple substance and 4N pure CsI compound as raw materials, and calculating the raw materials according to the molar compositionThe weight of the material and the molar composition are expressed by the chemical formula: (1-x-y) Sb2S3·xIn2S3yCsI, where x is 0.2 and y is 0.1. Weighing 10g of raw materials in a glove box filled with inert gas and uniformly mixing; then, the uniformly mixed raw materials were charged into a glass raw material tube of an H-shaped double-tube quartz ampoule which had been previously dried and previously charged with 0.1 wt% magnesium rod, and the quartz ampoule was evacuated to 1.0X 10-3Pa, then sealing the quartz ampoule by oxyhydrogen flame; putting the sealed quartz ampoule into a double-temperature-zone distillation furnace, setting the temperature of a cold end to be 100 ℃ and the temperature of a hot end to be 400 ℃, performing distillation purification to obtain purified Sb, In, S and CsI In a purified glass tube of the quartz ampoule, and then sealing off the double tubes by oxyhydrogen flame; and (3) putting the sealed purified glass tube filled with the purified product into a swinging heating furnace for high-temperature melting, slowly heating to 910 ℃, preserving heat for 12 hours under the condition of swinging, cooling to 810 ℃, quenching, quickly putting into an annealing furnace, preserving heat for 3 hours at 190 ℃, slowly cooling to room temperature, and breaking a quartz ampoule to obtain the chalcogenide glass sample.
In this example, the Se-free long-wave infrared transparent chalcogenide glass prepared by the above method had a molar composition of 70Sb2S3·20In2S3·10CsI。
The glass transition temperature T of the chalcogenide glass sample of example 6 was determinedgAt 215 ℃ and an initial crystallization temperature TxAt 316 ℃ and a.DELTA.T thereof>100℃。
In fig. 2, curve (f) is the X-ray diffraction pattern of the chalcogenide glass sample in this example, no obvious diffraction peak is observed, which indicates that the chalcogenide glass has no crystallization phenomenon and still maintains the complete amorphous structure. The chalcogenide glass of example 6 has a long-wavelength infrared cut edge of about 14 μm and a transmittance of 65. + -. 3% in the range of 0.65 to 13.3. mu.m.
Comparative example 1
In this comparative example, there is provided a Se-free long-wavelength infrared transparent chalcogenide glass having a molar composition represented by the formula: (1-x-y) Sb2S3·xIn2S3yCsI, when x is 0.25 and y is 0.4The molar composition of the chalcogenide glass is represented by the formula 35Sb2S3·25In2S340CsI, a process for its preparation, comprising the steps of: taking 5N-purity Sb simple substance, In simple substance, S simple substance and 4N-purity CsI compound as raw materials, calculating the weight of each raw material according to the molar composition, weighing 10g of raw materials In a glove box filled with inert gas, and uniformly mixing; then, the uniformly mixed raw materials were charged into a glass raw material tube of an H-shaped double-tube quartz ampoule which had been previously dried and previously charged with 0.1 wt% magnesium rod, and the quartz ampoule was evacuated to 1.0X 10-3Pa, then sealing the quartz ampoule by oxyhydrogen flame; putting the sealed quartz ampoule into a double-temperature-zone distillation furnace, setting the temperature of a cold end to be 100 ℃ and the temperature of a hot end to be 400 ℃, performing distillation purification to obtain purified Sb, In, S and CsI In a purified glass tube of the quartz ampoule, and then sealing off the double tubes by oxyhydrogen flame; and (3) putting the sealed purified glass tube filled with the purified substance into a swinging heating furnace for high-temperature melting, slowly heating to 940 ℃, preserving heat for 13h under the condition of swinging, cooling to 840 ℃, quenching, quickly putting into an annealing furnace, preserving heat for 4h at 200 ℃, slowly cooling to room temperature, and breaking a quartz ampoule to obtain the chalcogenide glass sample.
Through detection, a curve (g) in fig. 2 is an X-ray diffraction pattern of the chalcogenide glass sample in the embodiment, and an obvious CsI crystal diffraction peak is observed, which indicates that the prepared chalcogenide glass is crystalline and microcrystalline particles exist in the glass. The chalcogenide glass of the comparative example had a long-wavelength infrared cut edge of about 13.5 μm, and the transmittance was significantly reduced to only 20% in the range of 0.65 to 13 μm.
The foregoing has described preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary, and various changes made within the scope of the independent claims of the present invention are within the scope of the present invention.
Claims (10)
1. The Se-free long-wave infrared transparent chalcogenide glass is characterized in that: the molar composition is expressed by the chemical formula: (1-x-y) Sb2S3·xIn2S3yCsI, wherein x is 0 to 0.20 and y is 0.1 to 0.35.
2. The Se-free long-wave infrared transparent chalcogenide glass according to claim 1, wherein: the chalcogenide glass has an infrared cutoff wavelength of 14 μm.
3. The Se-free long-wave infrared transparent chalcogenide glass according to claim 1, wherein: the chalcogenide glass has a transmittance of 60 to 70% in a spectral range of 0.6 to 13.5 μm.
4. A method of making the Se-free long wave infrared transparent chalcogenide glass of claim 1 comprising the steps of:
s1, weighing raw materials, wherein the raw materials comprise simple substances Sb, S, In and CsI compounds, putting the raw materials into a quartz reactor, vacuumizing, sealing the quartz reactor by melting, and removing impurities and purifying the raw materials to obtain a purified substance;
s2, placing the quartz reactor filled with the purified product into a swinging heating furnace, slowly heating, keeping the temperature for 8-20 hours under the swinging condition, and then cooling and quenching;
s3, annealing the quenched quartz reactor to obtain Se-free long-wave infrared transparent chalcogenide glass.
5. The method for preparing Se-free long-wave infrared transparent chalcogenide glass according to claim 4, wherein the step S1 comprises the following steps:
s11, uniformly mixing the weighed Sb, S and In simple substances and the CsI compound to obtain a mixture, and weighing an oxygen scavenger, wherein the weighing amount of the oxygen scavenger is 0.03-0.1 wt% of the total amount of the mixture;
s12, the quartz reactor is an H-shaped double-tube quartz ampoule which comprises a raw material tube, a purifying tube and a connecting tube for connecting the raw material tube and the purifying tube, one end of the raw material tube is provided with an opening, the mixture and the deoxidant are uniformly mixed and placed in the raw material tube, and the opening of the raw material tube is sealed by fusion after the H-shaped double-tube quartz ampoule is vacuumized;
and S13, putting the H-shaped double-tube quartz ampoule into a double-temperature-zone distillation furnace, performing distillation purification, obtaining purified Sb, S, In and CsI In the purification tube, and then sealing the connecting tube by using flame.
6. The method of claim 5, wherein the Se-free long-wave infrared transparent chalcogenide glass is prepared by the steps of: in step S11, the purities of the Sb, S and In simple substances are all more than 5N, and the purity of the CsI compound is more than 4N.
7. The method of claim 5, wherein the Se-free long-wave infrared transparent chalcogenide glass is prepared by the steps of: in step S11, the oxygen scavenger is Mg or Al.
8. The method of claim 5, wherein the Se-free long-wave infrared transparent chalcogenide glass is prepared by the steps of: in the step S12, the vacuum degree of the H-shaped double-tube quartz ampoule is less than 10-3Pa。
9. The method of claim 4 for making Se-free long-wave infrared transparent chalcogenide glass, wherein the Se-free long-wave infrared transparent chalcogenide glass comprises the following steps: in the step S2, the quartz reactor is slowly heated to 850-950 ℃, cooled to 750-850 ℃ and quenched.
10. The method of claim 4 for making Se-free long-wave infrared transparent chalcogenide glass, wherein the Se-free long-wave infrared transparent chalcogenide glass comprises the following steps: and step S3, annealing the quenched quartz reactor at 130-200 ℃ for 2-5h to obtain Se-free long-wave infrared transparent chalcogenide glass.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6064894A (en) * | 1983-09-20 | 1985-04-13 | Fuji Photo Film Co Ltd | Laser recording material |
| EP1215039A2 (en) * | 2000-12-06 | 2002-06-19 | Asahi Glass Co., Ltd. | Laminated glass and glass plate used for producing laminated glass |
| JP2004005905A (en) * | 2002-04-10 | 2004-01-08 | Ricoh Co Ltd | Method for forming flat probe and flat probe |
| CN101492235A (en) * | 2009-02-23 | 2009-07-29 | 宁波大学 | Apparatus and method for producing high-purity sulphur glass |
| CN102351425A (en) * | 2011-07-11 | 2012-02-15 | 宁波大学 | Semiconductor nanocrystalline composite chalcogenide glass ceramic material and preparation method thereof |
| CN103332851A (en) * | 2013-06-05 | 2013-10-02 | 江苏师范大学 | Preparation method of high-purity and low-loss chalcogenide glass |
| CN104402221A (en) * | 2014-11-26 | 2015-03-11 | 江苏师范大学 | Chalcohalide glass and preparation method thereof |
| CN105541111A (en) * | 2015-12-16 | 2016-05-04 | 宁波大学 | Far-infrared high-nonlinear Ge-Te-Se chalcogenide glass and preparation method thereof |
| CN112811816A (en) * | 2021-01-07 | 2021-05-18 | 宁波大学 | High-stability full-spectrum transparent infrared chalcogenide glass material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6064894B2 (en) * | 2013-12-27 | 2017-01-25 | マツダ株式会社 | Hydraulic supply device for valve stop mechanism |
-
2021
- 2021-07-09 CN CN202110774815.5A patent/CN113480171B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6064894A (en) * | 1983-09-20 | 1985-04-13 | Fuji Photo Film Co Ltd | Laser recording material |
| EP1215039A2 (en) * | 2000-12-06 | 2002-06-19 | Asahi Glass Co., Ltd. | Laminated glass and glass plate used for producing laminated glass |
| JP2004005905A (en) * | 2002-04-10 | 2004-01-08 | Ricoh Co Ltd | Method for forming flat probe and flat probe |
| CN101492235A (en) * | 2009-02-23 | 2009-07-29 | 宁波大学 | Apparatus and method for producing high-purity sulphur glass |
| CN102351425A (en) * | 2011-07-11 | 2012-02-15 | 宁波大学 | Semiconductor nanocrystalline composite chalcogenide glass ceramic material and preparation method thereof |
| CN103332851A (en) * | 2013-06-05 | 2013-10-02 | 江苏师范大学 | Preparation method of high-purity and low-loss chalcogenide glass |
| CN104402221A (en) * | 2014-11-26 | 2015-03-11 | 江苏师范大学 | Chalcohalide glass and preparation method thereof |
| CN105541111A (en) * | 2015-12-16 | 2016-05-04 | 宁波大学 | Far-infrared high-nonlinear Ge-Te-Se chalcogenide glass and preparation method thereof |
| CN112811816A (en) * | 2021-01-07 | 2021-05-18 | 宁波大学 | High-stability full-spectrum transparent infrared chalcogenide glass material and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| YING, L ET AL.: "Glass formation and properties of novel GeS2-Sb2S3-In2S3 chalcogenide glasses", 《OPTICAL MATERIALS》 * |
| ZHANG, C ET AL.: "Improvement of third-order nonlinear properties in GeS2-Sb2S3-CsCl chalcogenide glass ceramics embedded with CsCl nano-crystals", 《CERAMICS INTERNATIONAL》 * |
| ZHANG, MJ ET AL.: "Glass forming and properties of Ga2S3-Sb2S3-CsCl chalcohalide system", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 应磊等: "Ho3+掺杂Ge-In-Sb-S玻璃陶瓷光谱特性", 《中国稀土学报》 * |
| 汪俊等: "Pr3+掺杂Ge-Ga-Se-CsI硫卤玻璃性能及光纤制备", 《发光学报》 * |
| 潘磊等: "两种Ge-Sb-Se薄膜的光学性质及微观结构", 《物理学报》 * |
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