CN108275875B - Zinc sulfide modified chalcogenide glass and preparation method thereof - Google Patents
Zinc sulfide modified chalcogenide glass and preparation method thereof Download PDFInfo
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- CN108275875B CN108275875B CN201810102603.0A CN201810102603A CN108275875B CN 108275875 B CN108275875 B CN 108275875B CN 201810102603 A CN201810102603 A CN 201810102603A CN 108275875 B CN108275875 B CN 108275875B
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- chalcogenide glass
- zinc sulfide
- sulfide modified
- modified chalcogenide
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
- C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
Abstract
The invention relates to zinc sulfide modified chalcogenide glass and a preparation method thereof, wherein the preparation method comprises the following steps: mixing arsenic and selenium to obtain a mixture, and mixing the mixture and zinc sulfide according to a molar ratio of 99-99.9: 0.1-1, and adding a deoxidant to obtain a raw material; will be provided withThe raw materials are distilled, purified, melted, quenched and discharged, and the zinc sulfide modified chalcogenide glass is obtained. The metallic element Zn in the zinc sulfide modified chalcogenide glass can exist in the form of ions and can exist with As40Se60In the chalcogenide glass, As can be reduced40Se60The reaction speed of the chalcogenide glass in the alkaline solution can improve As40Se60Alkali resistance of chalcogenide glass.
Description
Technical Field
The invention relates to the technical field of long-wave infrared chalcogenide glass modification, in particular to zinc sulfide modified chalcogenide glass and a preparation method thereof.
Background
Chalcogenide glass is used as an infrared optical material, and has the advantages of wide transmission spectrum range in an infrared band, stable photo-thermal property, excellent chemical stability, continuously adjustable performance, low preparation cost, easy processing, complementarity with infrared crystal materials such as monocrystalline germanium and the like on certain performances, and the like, in the design of an infrared optical component, the chalcogenide glass with low thermal difference coefficient and the crystal material with high thermal difference coefficient are combined and applied to an infrared optical system, so that the selection range of the infrared optical material can be greatly enriched, the flexibility of system design is increased, the system structure is simplified, more importantly, the imaging quality of the system under different environments (-55 ℃ -130 ℃) can be obviously improved, the temperature adaptability of optical systems such as infrared thermal imaging and the like is improved, the design requirement of the system without thermalization is met, therefore, chalcogenide glass is regarded as a new generation of core lens material of the temperature adaptive infrared optical system, the infrared sensor can be widely applied to military (night vision gun aiming, infrared shoulder-carrying missile, fighter plane night vision cruise and the like) and civil (automobile night vision, security monitoring and the like) infrared systems, and has huge market prospect. As40Se60(mol%) is currently the most representative, most market-approved As-SeOne system represents a chalcogenide glass system. As40Se60The weatherability of chalcogenide glass is an important index for the application, and the water resistance and the acid resistance are relatively excellent, but the alkali resistance is relatively poor, which is very unfavorable for the application.
The zinc sulfide crystal belongs to one kind of infrared material, and the infrared transmission spectrum is superposed with the application waveband of the chalcogenide glass transmission range, so that the possibility is provided for realizing the doping between the metal element zinc and the chalcogenide glass. In addition, the zinc sulfide has excellent physical properties such as wide energy band gap, high refractive index and high light transmittance, and has huge potential application prospect in the fields of applied optics, electronics and photoelectronic devices.
Disclosure of Invention
The invention mainly aims to provide novel zinc sulfide modified chalcogenide glass and a preparation method thereof, and aims to solve the technical problem of improving the environmental adaptability of chalcogenide glass, particularly the environmental weather resistance in an alkaline environment, so that the chalcogenide glass is more practical.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The preparation method of the zinc sulfide modified chalcogenide glass provided by the invention comprises the following steps:
mixing arsenic and selenium to obtain a mixture, and mixing the mixture and zinc sulfide according to a molar ratio of 99-99.9: 0.1-1, and adding a deoxidant to obtain a raw material;
distilling, purifying, melting, quenching and discharging the raw materials to obtain the zinc sulfide modified chalcogenide glass.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, in the preparation method of the zinc sulfide modified chalcogenide glass, the molar ratio of arsenic to selenium in the mixture is 40: 60; the purity of the arsenic and the selenium is more than 99.999 percent.
Preferably, in the method for preparing the zinc sulfide modified chalcogenide glass, the purity of the zinc sulfide is more than 99.99%.
Preferably, in the preparation method of the zinc sulfide modified chalcogenide glass, the content of the oxygen scavenger in the raw materials is 1-30ppm, the oxygen scavenger is aluminum, and the purity of the aluminum is more than 99.99%.
Preferably, in the preparation method of the zinc sulfide modified chalcogenide glass, the distillation purification temperature is 310-350 ℃, the distillation purification time is 1-6h, and the vacuum degree is less than or equal to 1 × 10-2Pa。
Preferably, in the preparation method of the zinc sulfide modified chalcogenide glass, the melting temperature is 800--2Pa。
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The zinc sulfide modified chalcogenide glass provided by the invention is prepared by the method.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the zinc sulfide modified chalcogenide glass has vickers hardness of 1.39 to 1.41 GPa.
Preferably, the zinc sulfide modified chalcogenide glass has a short-wave absorption limit wavelength of 0.79-0.80 μm; the long-wave cut-off wavelength is 18.2-19.1 μm.
By the technical scheme, the zinc sulfide modified chalcogenide glass and the preparation method thereof at least have the following advantages:
1) the invention dopes zinc sulfide to As40Se60In the chalcogenide glass, the metal element Zn can exist in the form of ions and As40Se60In chalcogenide glasses and can enter As by light irradiation40Se60In chalcogenide glass network structures, such photo-induced As doping40Se60The behavior of chalcogenide glass can greatly change As40Se60The performance of the chalcogenide glass, such As increasing the density and the transition temperature, and more importantly, the introduction of the metal elements can reduce As40Se60Of chalcogenide glasses in alkaline solutionsReaction speed, can increase As40Se60Alkali resistance of chalcogenide glass;
2) the present invention is at As40Se60The chalcogenide glass is doped with a quantity of zinc sulfide crystalline material to form a crystal modified As40Se60The ZnS chalcogenide glass has good light transmission performance in three atmospheric infrared windows of 1-3 mu m, 3-5 mu m and 8-12 mu m.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given to the zinc sulfide modified chalcogenide glass and the preparation method thereof according to the present invention, and the specific implementation manner, structure, characteristics and effects thereof, in combination with the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
One embodiment of the invention provides zinc sulfide modified chalcogenide glass and a preparation method thereof, wherein the preparation method comprises the following steps:
mixing arsenic and selenium according to a molar ratio of 40:60 to obtain a mixture, and mixing the mixture and zinc sulfide according to a molar ratio of 99-99.9: 0.1-1, adding 1-30ppm of deoxidant to obtain raw materials;
mixing the raw materials in a quartz ampoule bottle, performing integral vacuum heating purification at 310-350 ℃ for 1-6h, naturally cooling to room temperature, and performing vacuum purification at a vacuum of less than 1 × 10-2Fusing and sealing the quartz ampoule bottle by oxyhydrogen flame under the Pa condition; putting the sealed quartz ampoule bottle into a swinging furnace, melting at the temperature of 800-850 ℃, swinging for 8-40h, discharging in a quenching mode when the furnace temperature is reduced to 400-450 ℃, and then carrying out related annealing treatment to obtain the zinc sulfide modified chalcogenide glassGlass.
Preferably, the arsenic and selenium are greater than 99.999% pure.
Preferably, the zinc sulfide is greater than 99.99% pure.
Preferably, the oxygen scavenger is aluminum with a purity greater than 99.99%.
Another embodiment of the present invention provides a zinc sulfide modified chalcogenide glass prepared by the above method. The Vickers hardness of the zinc sulfide modified chalcogenide glass is 1.39-1.41GPa, and the short-wave absorption limit wavelength is 0.79-0.80 mu m; the long-wave cut-off wavelength is 18.2-19.1 μm.
Example 1
One embodiment of the invention provides zinc sulfide modified chalcogenide glass and a preparation method thereof, wherein the preparation method comprises the following steps:
mixing arsenic and selenium according to a molar ratio of 40:60 to obtain a mixture, and mixing the mixture and zinc sulfide according to a molar ratio of 99.5: 0.5, mixing, and adding 10ppm of deoxidant to obtain 300g of raw material;
mixing the raw materials in a quartz ampoule bottle, carrying out integral vacuum heating and purification for 3h at 310 ℃, then heating to 340 ℃ for 30min, and preserving heat for 2 h; naturally cooling to room temperature, and vacuum-cooling to less than 9.8 × 10-3Fusing and sealing the quartz ampoule bottle by oxyhydrogen flame under the Pa condition; and (3) putting the sealed quartz ampoule bottle into a swinging furnace, melting at 820 ℃, swinging for 35h, discharging in a quenching mode when the furnace temperature is reduced to 450 ℃, and then carrying out related annealing treatment to obtain the zinc sulfide modified chalcogenide glass.
Another embodiment of the present invention provides a zinc sulfide modified chalcogenide glass prepared by the method of embodiment 1. The Vickers hardness of the zinc sulfide modified chalcogenide glass is 1.41GPa, and the short-wave absorption limit wavelength is 0.79 mu m; the long-wave cut-off wavelength was 18.5. mu.m. The zinc sulfide modified chalcogenide glass of example 1 was subjected to an alkali resistance test, and had good alkali resistance.
Example 2
One embodiment of the invention provides zinc sulfide modified chalcogenide glass and a preparation method thereof, wherein the preparation method comprises the following steps:
mixing arsenic and selenium according to a molar ratio of 40:60 to obtain a mixture, and mixing the mixture and zinc sulfide according to a molar ratio of 99: 1, mixing, and adding 10ppm of deoxidant to obtain 300g of raw material;
mixing the raw materials in a quartz ampoule bottle, and carrying out integral vacuum heating purification for 4h at 340 ℃; naturally cooling to room temperature, and keeping the vacuum degree at less than 7.6 × 10-3Fusing and sealing the quartz ampoule bottle by oxyhydrogen flame under the Pa condition; and (3) putting the sealed quartz ampoule bottle into a swinging furnace, melting at 810 ℃, swinging for 30h, discharging in a quenching mode when the furnace temperature is reduced to 410 ℃, and then carrying out related annealing treatment to obtain the zinc sulfide modified chalcogenide glass.
Another embodiment of the present invention provides a zinc sulfide modified chalcogenide glass prepared by the method of embodiment 1. The Vickers hardness of the zinc sulfide modified chalcogenide glass is 1.41GPa, and the short-wave absorption limit wavelength is 0.8 mu m; the long-wave cut-off wavelength was 19.0. mu.m. The zinc sulfide modified chalcogenide glass of example 2 was subjected to an alkali resistance test, and had good alkali resistance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (7)
1. A preparation method of zinc sulfide modified chalcogenide glass is characterized by comprising the following steps:
mixing arsenic and selenium according to a molar ratio of 40:60 to obtain a mixture, and mixing the mixture and zinc sulfide according to a molar ratio of 99-99.9: 0.1-1, and adding a deoxidant to obtain a raw material;
mixing the raw materials in a quartz ampoule bottle, performing integral vacuum heating purification at 310-350 ℃ for 1-6h, naturally cooling to room temperature, and performing vacuum purification at a vacuum of less than 1 × 10-2Fusing and sealing the quartz ampoule bottle by oxyhydrogen flame under the Pa condition; putting the sealed quartz ampoule bottle into a swinging furnace, melting at 800-850 ℃ for 8-40h, discharging in a quenching mode when the furnace temperature is reduced to 400-450 ℃, then carrying out relevant annealing treatment,obtaining the zinc sulfide modified chalcogenide glass.
2. The method of claim 1, wherein the mixture comprises arsenic and selenium in a molar ratio of 40: 60; the purity of the arsenic and the selenium is more than 99.999 percent.
3. The method of claim 1, wherein the zinc sulfide modified chalcogenide glass has a purity of greater than 99.99%.
4. The method of claim 1, wherein the raw materials comprise 1-30ppm oxygen scavenger, the oxygen scavenger is aluminum, and the purity of the aluminum is greater than 99.99%.
5. A zinc sulfide-modified chalcogenide glass produced by the method according to any one of claims 1 to 4.
6. The zinc sulfide modified chalcogenide glass according to claim 5, wherein said zinc sulfide modified chalcogenide glass has a Vickers hardness of 1.39-1.41 GPa.
7. The zinc sulfide modified chalcogenide glass according to claim 5, wherein the short wavelength absorption edge wavelength of said zinc sulfide modified chalcogenide glass is 0.79 to 0.80 μm; the long-wave cut-off wavelength is 18.2-19.1 μm.
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| CN114956554A (en) * | 2022-04-21 | 2022-08-30 | 宁波大学 | Preparation method for improving mechanical strength of chalcogenide glass and chalcogenide glass |
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| CN103332851B (en) * | 2013-06-05 | 2015-06-17 | 江苏师范大学 | Preparation method of high-purity and low-loss chalcogenide glass |
| CN105502937A (en) * | 2016-02-23 | 2016-04-20 | 北京玻璃研究院 | Preparation method of high-purity chalcogenide infrared glass |
| CN106116110B (en) * | 2016-07-25 | 2019-07-16 | 中国建筑材料科学研究总院 | The preparation method of chalcogenide glass |
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