CN104402221B - A kind of sulfur-halogen glass and preparation method thereof - Google Patents
A kind of sulfur-halogen glass and preparation method thereof Download PDFInfo
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- CN104402221B CN104402221B CN201410699174.1A CN201410699174A CN104402221B CN 104402221 B CN104402221 B CN 104402221B CN 201410699174 A CN201410699174 A CN 201410699174A CN 104402221 B CN104402221 B CN 104402221B
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Abstract
The invention discloses a kind of sulfur-halogen glass and preparation method thereof, its chemical formula is (1 x y) Ga2S3‑xSb2S3YCsA, wherein, A be Cl, Br or I, 0.1≤x≤0.5,0.20≤y≤0.60；Its preparation method includes：(1) glass mixture is prepared by raw material of Metallic Gallium, simple substance antimony, elemental sulfur and compound CsA；(2) glass mixture being placed in quartz ampoule, melting being carried out within 12～24 hours in 850～900 DEG C of insulations, after taking-up, quenching forms glass；(3) glass of formation is annealed in 220～250 DEG C of insulations for 4～6 hours, room temperature is cooled to 0.1～0.4 DEG C of speed finally.Sulfur-halogen glass of the present invention has excellent translucency in 0.6 12 μ ms, and low cost, environmental friendliness are expected to be used for visible ray to 12 mu m waveband optical transport field of LONG WAVE INFRARED.
Description
Technical field
The present invention relates to a kind of optical glass material, more particularly to a kind of sulfur-halogen glass and preparation method thereof.
Background technology
Chalcogenide glass is that a certain amount of other metals or nonmetalloid formation are introduced based on chalcogen sulphur, selenium, tellurium
Amorphous material, including chalcogenide glass, selenide glass and tellurite glass, their typical transparency range are respectively 0.6
～10 μm, 1～14 μm and 2～20 μm.After halide is introduced in chalcogenide glass, the short-wave absorption side of glass would generally occur indigo plant
Move, and IR-cut side is without significant changes, this causes the transparency range of glass to shortwave direction broadening, this kind of based on chalcogen
It is referred to as sulfur-halogen glass with the glass of halogen.
Part sulfur-halogen glass has excellent printing opacity in visible ray, 1～3 μm, 3～5 μm and 8～12 mu m waveband atmospheric windows
Property, receive publicity in multiband transmitting optical material field in recent years.Commercial multiband transmitting optical material is few at present, main
If CVD ZnSe and CVD ZnS crystal.However, the long preparation period of both crystalline materials, high processing costs, therefore limit
Its all many application.Comparatively speaking, sulfur-halogen glass have prepare simple, moldable shaping, the low advantage of processing cost,
It is comparatively ideal optical material.
At present, the multiband transmission sulfur-halogen glass for having excellent translucency in above-mentioned atmospheric window only has selenium base glass system
Ge-Ga-Se-CsX (X=I, Br), which has higher transmitance at 0.6-14 μm.Compared with selenium base glass, sulfenyl glass tool
Have a stronger chemical bond, therefore with higher mechanical strength, the resistance to mechanical vibration of respective optical element and the ability impacted compared with
It is good.Existing sulfenyl glass has higher transmitance at 0.5～10 μm, and when wavelength is more than 10 μm, multi-phonon absorbs makes sulfenyl
The transmitance of glass declines rapidly, generally 11.5 μm afterwards transmitance be zero.(such as multi-spectral imaging and many in numerous applications
Wave band remote sensing), usually require that multiband transmission material in above-mentioned atmospheric window (particularly whole 8～12 μm of windows) with good
Translucency, not yet have at present meet this requirement sulfenyl glass relevant report.
The content of the invention
For existing sulfenyl glass above shortcomings, the invention provides one kind visible ray, 1～3 μm, 3～5 μm
There is sulfur-halogen glass material of excellent translucency and preparation method thereof with 8～12 mu m waveband atmospheric windows.
To solve above-mentioned technical problem, the present invention is adopted the following technical scheme that：
A kind of sulfur-halogen glass, its chemical formula are (1-x-y) Ga2S3-xSb2S3-yCsA, wherein, A be Cl, Br or I, 0.1≤x
≤ 0.5,0.20≤y≤0.60.
Above-mentioned sulfur-halogen glass is synthesized using vacuum melting method, including step：
(1) chemical formula is pressed as raw material with Metallic Gallium, simple substance antimony, elemental sulfur and halogenations caesium and prepares glass mixture,
Described caesium halide is cesium chloride, cesium bromide or cesium iodide；
(2) glass mixture is loaded in quartz ampoule, is vacuumized, with oxyhydrogen flame sealing-in quartz ampoule；
(3) the sealing-in good quartz ampoule equipped with glass mixture is put in rocking furnace, is warming up to 850～900 DEG C, protected
Temperature took out quenching after 12～24 hours, was then made annealing treatment within 4～6 hours in 220～250 DEG C of insulations, finally with 0.1～
0.4 DEG C of speed is cooled to room temperature, obtains final product sulfur-halogen glass of the present invention.
Preferably, the purity of the Metallic Gallium, simple substance antimony and elemental sulfur for adopting is not less than 99.999%, the chemical combination of employing
The purity of thing caesium halide is not less than 99.9%.
Preferably, the hydroxy radical content of quartz ampoule is less than 5ppm.
Preferably, vacuum is less than 10 in quartz ampoule-2Pa。
The chemical formula that the present invention is provided is (1-x-y) Ga2S3-xSb2S3-yThe sulfur-halogen glass of CsA is a kind of brand-new glass system
System, is to find Ga first2S3、Sb2S3Found with halide mixing and can form glass.Conventional sulfur-halogen glass is generally based on Ge
Or the glass system of As, sulfur-halogen glass of the present invention is without rare expensive Ge and poisonous As, with low cost and environmental friendliness；Together
When, the IR-cut side wave length of sulfur-halogen glass of the present invention does not receive [GeS4] tetrahedron or [AsS3] pyrometric cone network skeleton structure list
The restriction of unit, sulfur-halogen glass structure of the present invention is with [GaS4] tetrahedron and [SbS3] pyrometric cone is cross-linked with each other what is formed for skeleton
Three-dimensional net structure, construction unit phonon energy are relatively low, glass is improved in the translucency of 8～12 mu m wavebands.
The color of sulfur-halogen glass of the present invention be orange～peony, a length of 530-660nm of short-wave absorption notch, long wave cut-off function
Side wave length is more than 13 μm, and density is 3.35～3.75g/cm3, glass transition temperature is 220～250 DEG C, and microhardness is 100
～150kg/mm2, it is 1.80～2.33 in the refractive index of 10 mum wavelengths, is a kind of light for being expected to be used for multiband light transmission field
Learn glass.
Compared with prior art, the present invention can produce following beneficial effect：
(1) compared with existing sulfenyl sulfur-halogen glass, sulfur-halogen glass of the present invention is good in 0.6～12 μm of whole wave band light transmission
Good, transmitance is more than 55%, can meet requirement of the multiband light transmission application to glass transmission.
(2) compared with selenium-base chalcohalide glass, the good mechanical property of sulfur-halogen glass of the present invention, and without rare expensive germanium gold
Category, low cost.
(3) sulfur-halogen glass of the present invention does not contain toxic element, environmental friendliness.
Description of the drawings
Fig. 1 is the photo of glass prepared by the embodiment 1 shot using general visible camera；
Fig. 2 be adopt operation wavelength for 7.5～13 μm infrared camera shoot embodiment 1 prepared by glass photo；
Fig. 3 is the transmitted spectrum of glass prepared by embodiment 1, and thickness of sample is 3mm；
Fig. 4 is the transmitted spectrum of glass prepared by embodiment 2, and thickness of sample is 3mm；
Fig. 5 is the transmitted spectrum of glass prepared by embodiment 3, and thickness of sample is 3mm.
Specific embodiment
The substantive distinguishing features and marked improvement that the present invention will now be further described by way of examples, but the present invention is not only
It is limited to the cited case.
Embodiment 1
0.3Ga2S3-0.5Sb2S3- 0.2CsI glass preparations
The CsI of Ga, Sb, S and purity >=99.9% of purity >=99.999% is prepared into glass mixture in proportion, by glass
During glass compound loads hydroxy radical content less than the clean quartz ampoule of 5ppm, vacuum is evacuated to less than 10-2Pa, uses oxyhydrogen flame
Sealing-in quartz ampoule.The sealing quartz ampoule that will be equipped with glass mixture is put in rocking furnace, is warming up to 900 DEG C and to be incubated 12 little
When, take out the quenching in water；Then made annealing treatment within 4 hours in 245 DEG C of insulations；Finally, cooled down with the speed of 0.4 DEG C/min
To room temperature, that is, obtain 0.3Ga2S3-0.5Sb2S3- 0.2CsI glass.
Fig. 1 and Fig. 2 are the sheet for adopting general visible camera and operation wavelength and shooting for 7.5～13 μm of infrared cameras respectively
Embodiment glass photo, can be clearly seen the word and iron wire for being placed in glass rear respectively through the present embodiment glass.
Glass density is tested using Archimedes method；The vitrifying of glass is tested using TAQ2000 differential scanning calorimeters
Transition temperature, heating rate are 10 DEG C/min；Tested using INSTRON Wilson-Wolpert Tukon 2100B hardness testers
The microhardness of double glazed glass piece, load and time are respectively 100g and 5s；Surveyed using the infrared ellipsometers of J.A.Woollam
The refractive index of amount single-sided polishing sheet glass；Using 950 spectrophotometers of PerkinElmer Lambda and Bruker Tensor
27 Fourier transformation infrared spectrometers test the transmitted spectrum of 3mm heavy sheet glass pieces.
The testing result of the present embodiment glass：Density is 3.75g/cm3, glass transition temperature is 247 DEG C, microhardness
For 150kg/mm2, it is 2.33 in the refractive index of 10 mum wavelengths, a length of 660nm of short-wave absorption notch of glass, long wave cut-off function side wave
A length of 13.2 μm, light transmission refers to Fig. 3.
Embodiment 2
0.3Ga2S3-0.3Sb2S3- 0.4CsBr glass preparations
Ga, Sb, S of purity >=99.999% and purity >=99.9%CsBr are prepared into glass mixture in proportion, by glass
During glass compound loads hydroxy radical content less than the clean quartz ampoule of 5ppm, vacuum is evacuated to less than 10-2Pa, uses oxyhydrogen flame
Sealing-in quartz ampoule.The sealing quartz ampoule that will be equipped with glass mixture is put in rocking furnace, is warming up to 875 DEG C and to be incubated 18 little
When, take out the quenching in water；Then made annealing treatment within 5 hours in 220 DEG C of insulations；Finally, cooled down with the speed of 0.2 DEG C/min
To room temperature, that is, obtain 0.3Ga2S3-0.3Sb2S3- 0.4CsBr glass.
Glass density is tested using Archimedes method；The vitrifying of glass is tested using TAQ2000 differential scanning calorimeters
Transition temperature, heating rate are 10 DEG C/min；Tested using INSTRON Wilson-Wolpert Tukon 2100B hardness testers
The microhardness of double glazed glass piece, load and time are respectively 100g and 5s；Surveyed using the infrared ellipsometers of J.A.Woollam
The refractive index of amount single-sided polishing sheet glass；Using 950 spectrophotometers of PerkinElmer Lambda and Bruker Tensor
27 Fourier transformation infrared spectrometers test the transmitted spectrum of 3mm heavy sheet glass pieces.
The testing result of the present embodiment glass：Density is 3.47g/cm3, glass transition temperature is 223 DEG C, microhardness
For 112kg/mm2, it is 2.06 in the refractive index of 10 mum wavelengths, a length of 572nm of short-wave absorption notch of glass, long wave cut-off function side wave
A length of 13.2 μm, light transmission refers to Fig. 4.
Embodiment 3
0.3Ga2S3-0.1Sb2S3- 0.6CsCl glass preparations
Ga, Sb, S of purity >=99.999% and purity >=99.9%CsCl are prepared into glass mixture in proportion, by glass
During glass compound loads hydroxy radical content less than the clean quartz ampoule of 5ppm, vacuum is evacuated to less than 10-2Pa, uses oxyhydrogen flame
Sealing-in quartz ampoule.The sealing quartz ampoule that will be equipped with glass mixture is put in rocking furnace, is warming up to 850 DEG C and to be incubated 24 little
When, take out the quenching in water；Then made annealing treatment within 6 hours in 220 DEG C of insulations；Finally, cooled down with the speed of 0.1 DEG C/min
To room temperature, that is, obtain 0.3Ga2S3-0.1Sb2S3- 0.6CsCl glass.
Glass density is tested using Archimedes method；The vitrifying of glass is tested using TAQ2000 differential scanning calorimeters
Transition temperature, heating rate are 10 DEG C/min；Tested using INSTRON Wilson-Wolpert Tukon 2100B hardness testers
The microhardness of double glazed glass piece, load and time are respectively 100g and 5s；Surveyed using the infrared ellipsometers of J.A.Woollam
The refractive index of amount single-sided polishing sheet glass；Using 950 spectrophotometers of PerkinElmer Lambda and Bruker Tensor
27 Fourier transformation infrared spectrometers test the transmitted spectrum of 3mm heavy sheet glass pieces.
The testing result of the present embodiment glass：Density is 3.35g/cm3, glass transition temperature is 220 DEG C, microhardness
For 100kg/mm2, it is 1.80 in the refractive index of 10 mum wavelengths, a length of 530nm of short-wave absorption notch of glass, long wave cut-off function side wave
A length of 13.2 μm, light transmission refers to Fig. 5.
Claims (6)
1. a kind of sulfur-halogen glass, it is characterised in that：
Chemical formula is (1-x-y) Ga2S3-xSb2S3- yCsA, wherein, A be Cl, Br or I, 0.1≤x≤0.5,0.20≤y≤
0.60；The sulfur-halogen glass structure is with [GaS4] tetrahedron and [SbS3] pyrometric cone is cross-linked with each other for skeleton the three-dimensional network to be formed
Structure.
2. a kind of preparation method of sulfur-halogen glass as claimed in claim 1, it is characterised in that comprise the steps：
(1) chemical formula is pressed as raw material with Metallic Gallium, simple substance antimony, elemental sulfur and halogenations caesium and prepares glass mixture, it is described
Caesium halide be cesium chloride, cesium bromide or cesium iodide；
(2) glass mixture is loaded in quartz ampoule, is vacuumized, with oxyhydrogen flame sealing-in quartz ampoule；
(3) the sealing-in good quartz ampoule equipped with glass mixture is put in rocking furnace, is warming up to 850～900 DEG C, insulation 12
Quenching is taken out after～24 hours, is then made annealing treatment within 4～6 hours in 220～250 DEG C of insulations, finally with 0.1～0.4 DEG C/
The speed of min is cooled to room temperature, obtains final product sulfur-halogen glass of the present invention.
3. the preparation method of sulfur-halogen glass as claimed in claim 2, it is characterised in that：
The purity of described Metallic Gallium, simple substance antimony and elemental sulfur is not less than 99.999%.
4. the preparation method of sulfur-halogen glass as claimed in claim 2, it is characterised in that：
The purity of described halogenations caesium is not less than 99.9%.
5. the preparation method of sulfur-halogen glass as claimed in claim 2, it is characterised in that：
The hydroxy radical content of described quartz ampoule is less than 5ppm.
6. the preparation method of sulfur-halogen glass as claimed in claim 2, it is characterised in that：
In described quartz ampoule, vacuum is less than 10-2Pa。
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| CN110571636B (en) * | 2019-10-28 | 2021-03-30 | 江苏师范大学 | Sulfide gain optical fiber and preparation method thereof |
| CN112811816B (en) * | 2021-01-07 | 2022-08-05 | 宁波大学 | High-stability full-spectrum transparent infrared chalcogenide glass material and preparation method thereof |
| CN113480171B (en) * | 2021-07-09 | 2022-10-28 | 宁波阳光和谱光电科技有限公司 | Se-free long-wave infrared transparent chalcogenide glass and preparation method thereof |
| CN116282914B (en) * | 2023-03-14 | 2023-08-15 | 杭州长波红外科技有限公司 | Long-wave infrared transmission sulfide glass and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1116190A (en) * | 1994-04-11 | 1996-02-07 | 康宁股份有限公司 | Gallium sulfide glasses |
| CN101293738A (en) * | 2008-05-12 | 2008-10-29 | 中国科学院上海硅酸盐研究所 | Infrared transmission glass material and preparation method thereof |
| CN102066274A (en) * | 2008-04-29 | 2011-05-18 | 康宁股份有限公司 | Ga-P-S glass compositions |
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2014
- 2014-11-26 CN CN201410699174.1A patent/CN104402221B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1116190A (en) * | 1994-04-11 | 1996-02-07 | 康宁股份有限公司 | Gallium sulfide glasses |
| CN102066274A (en) * | 2008-04-29 | 2011-05-18 | 康宁股份有限公司 | Ga-P-S glass compositions |
| CN101293738A (en) * | 2008-05-12 | 2008-10-29 | 中国科学院上海硅酸盐研究所 | Infrared transmission glass material and preparation method thereof |
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Effective date of registration: 20191213 Address after: 211100 No.18, boguang Road, Husu industrial concentration zone, Jiangning District, Nanjing City, Jiangsu Province Patentee after: NANJING WAVELENGTH OPTOELECTRONICS TECHNOLOGY CO., LTD. Address before: 221116 Shanghai Road, Copper Mt. New District, Jiangsu, No. 101, No. Patentee before: Jiangsu Normal University |
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