CN115304292B - Gradient refractive index infrared chalcogenide glass, preparation method and application thereof, infrared thermal imaging lens and application thereof - Google Patents
Gradient refractive index infrared chalcogenide glass, preparation method and application thereof, infrared thermal imaging lens and application thereof Download PDFInfo
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- 239000005387 chalcogenide glass Substances 0.000 title claims abstract description 61
- 238000001931 thermography Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000011521 glass Substances 0.000 claims abstract description 148
- 239000000758 substrate Substances 0.000 claims abstract description 81
- 239000002344 surface layer Substances 0.000 claims abstract description 67
- 229910005900 GeTe Inorganic materials 0.000 claims abstract description 24
- 239000010410 layer Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 11
- 230000003247 decreasing effect Effects 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims description 34
- 238000009792 diffusion process Methods 0.000 claims description 33
- 238000000137 annealing Methods 0.000 claims description 28
- 238000004321 preservation Methods 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 18
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- 238000010791 quenching Methods 0.000 claims description 17
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- 238000007731 hot pressing Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
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- 238000004519 manufacturing process Methods 0.000 claims description 4
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- 230000008859 change Effects 0.000 abstract description 11
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- 238000009826 distribution Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000010453 quartz Substances 0.000 description 14
- 238000002425 crystallisation Methods 0.000 description 11
- 230000009477 glass transition Effects 0.000 description 11
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- 238000001069 Raman spectroscopy Methods 0.000 description 8
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- 238000003384 imaging method Methods 0.000 description 6
- 150000004770 chalcogenides Chemical class 0.000 description 5
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- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B23/00—Re-forming shaped glass
- C03B23/02—Re-forming glass sheets
- C03B23/023—Re-forming glass sheets by bending
- C03B23/03—Re-forming glass sheets by bending by press-bending between shaping moulds
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- 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
- C03C3/323—Chalcogenide glasses, e.g. containing S, Se, Te containing halogen, e.g. chalcohalide glasses
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B13/00—Optical objectives specially designed for the purposes specified below
- G02B13/14—Optical objectives specially designed for the purposes specified below for use with infrared or ultraviolet radiation
Abstract
The invention provides gradient refractive index infrared chalcogenide glass, a preparation method and application thereof, an infrared thermal imaging lens and application thereof, and relates to the technical field of chalcogenide glass. The invention provides gradient refractive index infrared chalcogenide glass, which comprises a first surface layer substrate glass, a sandwich substrate glass and a second surface layer substrate glass which are sequentially laminated; the number of layers of the sandwich substrate glass is more than or equal to 0; the chemical composition of the first surface layer substrate glass, the sandwich substrate glass and the second surface layer substrate glass is xAgI (1-x) GeTe 4.3 X is independently 0 to 30%; and x is gradually decreased along the direction from the first surface layer substrate glass to the second surface layer substrate glass. The gradient refractive index infrared chalcogenide glass provided by the invention has 0-30% of AgI in GeTe 4.3 The continuous distribution of the glass has the advantages of improving the refractive index of the gradient refractive index infrared chalcogenide glass, realizing large gradient change of the refractive index, and having good application prospect in infrared thermal imaging.
Description
Technical Field
The invention relates to the technical field of chalcogenide glass, in particular to gradient refractive index infrared chalcogenide glass, a preparation method and application thereof, an infrared thermal imaging lens and application thereof.
Background
Infrared thermal imaging technology is a wavelength conversion technology that converts infrared radiation that is not visible to the naked eye into visible light. With the continuous development of infrared detection technology in recent years, the infrared thermal imaging technology is widely applied in the fields of military and civil use, and the infrared thermal imaging technology is increasingly widely applied in the fields of security monitoring, biomedical treatment, fire rescue, industrial detection and the like. The infrared optical lens is one of core devices of the infrared thermal imaging technology, and is a key channel for acquiring infrared radiation signals of a target, so that the capability of the infrared optical lens for capturing infrared radiation and accurately imaging determines the performance of the infrared thermal imaging equipment.
The conventional infrared lens is often formed by combining a plurality of lenses with a single refractive index, and light is still transmitted in a straight line after passing through the combined lenses, so that the thickness and the surface curvature of the lenses need to be changed to eliminate aberration and realize imaging. With the complexity of the application scene, especially in the application scene of multi-light fusion, more lenses are needed to eliminate the aberration of the traditional infrared lens, but the optical design of the lens is more complex, heavy and huge, and the imaging quality is affected due to more serious light intensity attenuation. In addition, the pixel size in the current advanced infrared focal plane array detector can be as small as a micron, and the design standard of the infrared optical system reaches the optical diffraction limit, so that the requirement of a lens with single refractive index cannot be met, and the development of a novel optical lens imaging material is urgent.
Gradient index (GRIN) lenses refer to optical lenses in which the refractive index inside the material continuously varies in a certain direction, and can be classified into three types: axial gradient refractive index, radial gradient refractive index, and spherical gradient refractive index. GRIN has the advantage that it changes the way light travels straight in a single index medium, bending the light path due to the gradient of the internal index, creating a self-focusing or self-defocusing effect. The lens correction aberration is easier by combining refractive index gradient change and lens curvature optimization, for example, the axial GRIN lens can reduce the number of lenses from a plurality of lenses to 2 lenses, and meanwhile, the thickness of the lenses is also greatly reduced, so that the complexity of an optical system is greatly reduced, the weight of the lens is reduced, the volume of the lens is reduced, and the production cost is greatly reduced. Therefore, development of infrared GRIN lens materials is an alternative to development of infrared thermal imaging technology and to solving the problem of miniaturization, light weight and high quality imaging of the probe device.
Germanium single crystals, zinc selenide, and chalcogenide glass are currently the most commonly used materials for infrared lenses, the former two being crystalline materials, and because of their crystalline nature it is difficult to adjust the refractive index properties to a large extent by component design or other means, and thus are not generally used for the preparation of GRIN lenses. While chalcogenide glass has the characteristic of an irregular network structure, the components of which can be greatly adjusted according to the refractive index requirement, which is certainly a key advantage of manufacturing GRIN lenses.
For example, U.S. naval laboratories D.Gibson et al developed a chalcogenide GRIN glass having a refractive index difference (Δn) of about 0.2 and a glass graded layer thickness of about 3.5mm (D.Gibson, S.Bayya, V.Nguyen, et al, "IR GRIN optics: design and fabrication" Proc.SPIE 10181,Advanced Optics for Defense Applications:UV through LWIR II,101810B (1 june 2017); doi: 10.1117/12.2262706) with a refractive index of less than 2.9 and did not disclose the composition of chalcogenide GRIN glass. 20GeSe is reported by K.Richardson et al, university of Florida, U.S.A 2 -60As 2 Se 3 20PbSe glass (K. Richardson, A. Buff, C. Smith, et al, "Engineering novel infrared glass ceramics for advanced optical solutions" Proc.SPIE 9822,Advanced Optics for Defense Applications:UV through LWIR,982205 (17 May 2016); doi: 10.1117/12.2224239) having a refractive index of less than 3.3. Chinese patent CN107162429a discloses a chalcogenide GRIN lens, comprising the following components: (1-x) Ge 28 Sb 12 Se 60 xM, where x=0.1 to 0.4, M is a Ga or In metal element, the refractive index difference (Δn) of which can reach 0.2, and the refractive index of which is lower than 2.72. However, the refractive index difference of the conventional chalcogenide GRIN glass is low.
Disclosure of Invention
In view of the above, the invention aims to provide a gradient refractive index infrared chalcogenide glass, a preparation method and application thereof, an infrared thermal imaging lens and application thereof, and the gradient refractive index infrared chalcogenide glass provided by the invention has refractive index difference delta n more than or equal to 0.3 and excellent focusing and achromatizing performances.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides gradient refractive index infrared chalcogenide glass, which comprises a first surface layer substrate glass, a sandwich substrate glass and a second surface layer substrate glass which are sequentially laminated; the number of layers of the sandwich substrate glass is more than or equal to 0;
the chemical composition of the first surface layer substrate glass, the sandwich substrate glass and the second surface layer substrate glass is xAgI (1-x) GeTe 4.3 Wherein x is independently 0 to 30%;
and x in the gradient refractive index infrared chalcogenide glass is gradually decreased along the direction from the first surface layer substrate glass to the second surface layer substrate glass.
Preferably, the thickness of the first surface layer substrate glass and the second surface layer substrate glass is independently 1-20 mm, and the thickness of the laminated substrate glass is 0.5-2 mm.
The invention provides a preparation method of the gradient refractive index infrared chalcogenide glass, which comprises the following steps:
preparing each layer of matrix glass by adopting a melting quenching method after preparing according to the chemical composition of each layer, and respectively obtaining first surface layer matrix glass, sandwich matrix glass and second surface layer matrix glass;
preferably, the melt quenching method includes sequentially performing vacuum melting, quenching and annealing treatments.
Preferably, the vacuum degree of the vacuum melting is less than 10 -3 Pa, the heat preservation temperature is 800-900 ℃, and the heat preservation time is 10-20 h; the temperature rise rate from room temperature to the vacuum melting heat preservation temperature is 60-120 ℃/h.
Preferably, the annealing treatment comprises thermal insulation annealing and cooling annealing in sequence; the temperature of the heat preservation annealing is 121-146 ℃, and the heat preservation time is 3-10 h; the cooling rate of the cooling annealing is 5-10 ℃/h.
And sequentially laminating the first surface layer substrate glass, the sandwich substrate glass and the second surface layer substrate glass, and then performing hot-pressing diffusion to obtain the gradient refractive index infrared chalcogenide glass.
Preferably, the heat preservation temperature of the hot-pressing diffusion is 160-220 ℃, the pressure is 0-50 MPa, the time is 1-30 days, and the vacuum degree is less than 10 -2 Pa; the temperature rise rate from the room temperature to the heat preservation temperature of the hot-press diffusion is 5-20 ℃/min.
The invention provides an infrared thermal imaging lens, which comprises the gradient refractive index infrared chalcogenide glass prepared by the technical scheme or the preparation method of the technical scheme.
The invention provides the gradient refractive index infrared chalcogenide glass according to the technical scheme, the gradient refractive index infrared chalcogenide glass prepared by the preparation method according to the technical scheme or the application of the infrared thermal imaging lens according to the technical scheme in infrared thermal imaging.
The invention provides gradient refractive index infrared chalcogenide glass, which comprises a first surface layer substrate glass, a sandwich substrate glass and a second surface layer substrate glass which are sequentially laminated; the number of layers of the sandwich substrate glass is more than or equal to 0; the chemical composition of the first surface layer substrate glass, the sandwich substrate glass and the second surface layer substrate glass is xAgI (1-x) GeTe 4.3 Wherein x is independently 0 to 30%; and x in the gradient refractive index infrared chalcogenide glass is gradually decreased along the direction from the first surface layer substrate glass to the second surface layer substrate glass. The AgI in the gradient refractive index infrared chalcogenide glass (GRIN chalcogenide glass) provided by the invention is in GeTe 4.3 The components are continuously distributed, so that the refractive index of the GRIN chalcogenide glass is improved; in addition, 0 to 30% of AgI is in GeTe 4.3 The large gradient doping range in the components effectively solves the problem of small adjustment range of the chalcogenide matrix components, so that the refractive index of the GRIN chalcogenide glass has large gradient change. As shown by the test results of examples, the maximum refractive index difference of the GRIN chalcogenide glass provided by the invention is more than or equal to 0.3, and the GRIN chalcogenide glass has high refractive indexThe gradient refractive index infrared chalcogenide glass has excellent focusing and achromatism performance, and has good application prospect in infrared thermal imaging.
The invention provides a preparation method of the gradient refractive index infrared chalcogenide glass, which comprises the following steps: preparing AgI, ge and Te according to chemical compositions of all layers, and preparing all layers of matrix glass by adopting a melting quenching method to obtain a first surface layer of matrix glass, a sandwich matrix glass and a second surface layer of matrix glass respectively; and sequentially laminating the first surface layer substrate glass, the sandwich substrate glass and the second surface layer substrate glass, and then performing hot-pressing diffusion to obtain the gradient refractive index infrared chalcogenide glass. The invention makes AgI in GeTe by lamination-thermal diffusion method 4.3 Diffusion movement occurs in the composition such that AgI is in GeTe 4.3 The GRIN chalcogenide glass with high refractive index and large gradient refractive index difference is prepared by continuously distributing the components. The preparation method provided by the invention is simple to operate, low in preparation cost and suitable for industrial production.
The invention provides an infrared imaging lens, which adopts high-refractive-index gradient refractive-index infrared chalcogenide glass as the infrared imaging lens, has excellent focusing and achromatism performance, has smaller volume and lighter weight compared with the traditional homogeneous imaging lens, and has important significance for miniaturization and light weight of an infrared imaging system.
Drawings
FIG. 1 shows xAgI (1-x) GeTe 4.3 A relation diagram of AgI doping concentration and refractive index of a glass system;
FIG. 2 is an xAgI (1-x) GeTe 4.3 A relation diagram of AgI doping concentration of a glass system and glass transition temperature and glass initial crystallization temperature;
fig. 3 is a graph showing the change in raman intensity of GRIN glass obtained after diffusion of x=5% and 30% glass in example 1, as a function of diffusion distance;
fig. 4 is a graph showing the change in raman intensity of GRIN glass obtained after diffusion of x=5%, 10%, 15%, 20%, 25%, 30% glass in example 2, as a function of diffusion distance.
Detailed Description
The invention provides gradient refractive index infrared chalcogenide glass, which comprises a first surface layer substrate glass, a sandwich substrate glass and a second surface layer substrate glass which are sequentially laminated; the number of layers of the sandwich substrate glass is more than or equal to 0. In the invention, the chemical composition of the first surface layer substrate glass, the sandwich substrate glass and the second surface layer substrate glass is xAgI (1-x) GeTe 4.3 Wherein x is independently 0 to 30%, preferably 5 to 30%, particularly preferably 5%, 10%, 15%, 20%, 25% and 30%. In the invention, x in the gradient refractive index infrared chalcogenide glass is gradually decreased along the direction from the first surface layer substrate glass to the second surface layer substrate glass, and the difference value of x in the first surface layer substrate glass and the second surface layer substrate glass is preferably more than or equal to 20%, more preferably 20-30%, and even more preferably 25-30%.
In the present invention, the thickness of the first surface layer matrix glass and the second surface layer matrix glass is independently preferably 1 to 20mm, more preferably 2 to 10mm; the thickness of the laminated substrate glass is preferably 0.5 to 2mm, more preferably 0.5 to 1.5mm. The shape and the size of the gradient refractive index infrared chalcogenide glass are not particularly limited, and the gradient refractive index infrared chalcogenide glass can be adjusted according to actual needs.
The invention provides a preparation method of the gradient refractive index infrared chalcogenide glass, which comprises the following steps:
preparing each layer of matrix glass by adopting a melting quenching method after preparing according to the chemical composition of each layer, and respectively obtaining first surface layer matrix glass, sandwich matrix glass and second surface layer matrix glass;
and sequentially laminating the first surface layer substrate glass, the sandwich substrate glass and the second surface layer substrate glass, and then performing hot-pressing diffusion to obtain the gradient refractive index infrared chalcogenide glass.
In the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise.
According to the invention, after the chemical compositions of all layers are respectively proportioned, all layers of matrix glass are prepared by adopting a melting quenching method, and a first surface layer matrix glass, a sandwich matrix glass and a second surface layer matrix glass are respectively obtained.
In the present invention, the ingredients preferably comprise AgI, ge and Te, or AgI and GeTe 4.3 Glass.
In the present invention, the melt quenching method preferably includes sequentially performing vacuum melting, quenching and annealing treatments.
In the present invention, the vacuum degree of the vacuum melting is preferably < 10 -3 Pa; the heat preservation temperature of the vacuum melting is preferably 800-900 ℃, more preferably 820-880 ℃, and even more preferably 840-860 ℃; the heat preservation time of the vacuum melting is preferably 10-20 hours, more preferably 12-18 hours, and even more preferably 14-16 hours; the heating rate from room temperature to the holding temperature for vacuum melting is preferably 60 to 120 ℃/h, more preferably 70 to 110 ℃/h, still more preferably 80 to 100 ℃/h. In a specific embodiment of the present invention, the vacuum melting is preferably: placing the ingredients of each layer into a cleaned quartz tube, vacuumizing and heating to remove surface water vapor, and keeping the vacuum degree in the quartz tube below 10 -3 And (3) sealing the quartz tube after Pa, placing the quartz tube in an electric heating swinging smelting furnace, heating a hearth to the heat preservation temperature of vacuum smelting, and then preserving heat and swinging smelting. In the present invention, the heating temperature of the vacuum heating is 90 to 100 ℃, more preferably 95 ℃, and the time is preferably 1 to 3 hours, more preferably 2 hours.
After the vacuum melting is finished, the invention preferably further comprises heat preservation after cooling treatment, wherein the cooling rate of the cooling treatment is preferably 60-120 ℃/h, more preferably 70-110 ℃/h, and further preferably 80-100 ℃/h; the temperature of the heat preservation is preferably 500-650 ℃, more preferably 600 ℃; the time for the heat preservation is preferably 20 to 60 minutes, more preferably 30 to 50 minutes.
In the invention, the quenching is water quenching or high-pressure air gun quenching. In the present invention, the temperature of the water for water quenching is preferably 5 to 80 ℃, more preferably 10 to 30 ℃. The high-pressure air gun quenching is not particularly limited, and the high-pressure air gun quenching conditions well known to those skilled in the art can be adopted.
In the invention, the annealing treatment preferably comprises thermal insulation annealing and cooling annealing in sequence; the temperature of the thermal annealing is preferably lower than xAgI (1-x) GeTe 4.3 The glass transition temperature of (C) is 5-20deg.C, more preferably less than xAgI- (1-x) GeTe 4.3 The glass transition temperature of (C) is 8-15 ℃, more preferably less than xAgI- (1-x) GeTe 4.3 The glass transition temperature of (2) is 8-12 ℃, and specifically, the temperature of the heat preservation annealing is preferably 121-146 ℃; the time for the heat preservation is preferably 3 to 10 hours, more preferably 4 to 8 hours, and even more preferably 5 to 6 hours. In the present invention, when x=5%, the soak temperature of the soak annealing is preferably 131 to 146 ℃, more preferably 141 ℃; when x=10%, the holding temperature of the holding annealing is preferably 128-143 ℃, more preferably 138 ℃; when x=15%, the holding temperature of the holding annealing is preferably 123-138 ℃, more preferably 133 ℃; when x=20%, the heat preservation temperature of the heat preservation annealing is preferably 121-136 ℃, more preferably 131 ℃; when x=25%, the holding temperature of the holding annealing is preferably 118-133 ℃, more preferably 128 ℃; when x=30%, the soak temperature of the soak annealing is preferably 116 to 131 ℃, more preferably 126 ℃. In the invention, the cooling rate of the cooling annealing is preferably 5-10 ℃/h, more preferably 6-10 ℃/h, and even more preferably 8-10 ℃/h; the final temperature of the cooling annealing is preferably 10-50 ℃, more preferably room temperature.
After the first surface layer substrate glass, the sandwich substrate glass and the second surface layer substrate glass are obtained, the first surface layer substrate glass, the sandwich substrate glass and the second surface layer substrate glass are sequentially laminated and then thermally pressed and diffused, so that the gradient refractive index infrared chalcogenide glass is obtained.
In the present invention, the substrate glass layers are preferably cut and polished before being laminated in sequence, and the present invention is not particularly limited, and the surface of each substrate glass layer is smooth and the thickness is controlled to be 1-20 mm on the surface layer and 0.5-2 mm on the interlayer.
In the invention, the heat preservation temperature of the hot-press diffusion is preferably higher than xAgI (1-x) GeTe 4.3 And below xAgI (1-x) GeTe 4.3 The initial crystallization temperature of (a) is particularly preferably 160 to 220 ℃, more preferably 200 ℃; the heating rate from the room temperature to the heat preservation temperature of the hot-press diffusion is preferably 5-20 ℃/min, more preferably 8-18 ℃/min, and even more preferably 10-15 ℃/min; the pressure of the hot-press diffusion is preferably 0 to 50MPa, more preferably 5 to 40MPa, and even more preferably 10 to 30MPa; the time for the hot-press diffusion is preferably 1 to 30 days, more preferably 1 to 10 days, and still more preferably 2 to 5 days; the vacuum degree of the hot-press diffusion is preferably less than 10 -2 Pa. In a specific embodiment of the present invention, the hot-press diffusion is preferably that each layer of glass substrate is loaded into a hot-press mold according to the descending order of x, the hot-press mold is placed into a hot press, a furnace chamber of the hot press is vacuumized, the furnace chamber is heated to the temperature of the hot-press diffusion, pressure is applied, and the hot-press diffusion is performed under the conditions of heat preservation and pressure maintaining.
After the hot-pressing diffusion is completed, the method preferably further comprises the steps of sequentially removing pressure, cooling to room temperature, demolding and surface polishing to obtain the gradient refractive index infrared chalcogenide glass. In the present invention, the cooling rate of the cooling is preferably 5 to 20℃per minute, more preferably 10 to 15℃per minute. The present invention is not particularly limited to the above-described demolding, and may employ a demolding operation well known to those skilled in the art. The present invention is not particularly limited as to the surface polishing, and a surface polishing operation well known to those skilled in the art may be employed.
The crystallization of the thermal induced crystallization method is poor in controllability, particularly the precision of temperature field distribution is far from reaching the requirement of regional control crystallization on glass with smaller thickness, and in addition, the influence of crystallization on the optical permeability of the material is larger. While the invention is realized by the method of the invention in GeTe 4.3 The components are doped with 0-30% of AgI which is continuously distributed, the gradient change of the refractive index is solved from the aspect of component design, and the GRIN chalcogenide glass with higher gradient uniformity of the refractive index and better optical performance can be prepared without the accurate control of temperature field gradient in the preparation process.
The invention provides an infrared thermal imaging lens, which comprises the gradient refractive index infrared chalcogenide glass prepared by the technical scheme or the preparation method of the technical scheme.
The invention provides the gradient refractive index infrared chalcogenide glass according to the technical scheme, the gradient refractive index infrared chalcogenide glass prepared by the preparation method according to the technical scheme or the application of the infrared thermal imaging lens according to the technical scheme in infrared thermal imaging. In the present invention, the infrared thermal imaging preferably includes infrared thermal imaging in biomedical, fire rescue, or industrial detection in security monitoring, diagnosis and treatment of non-disease.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of xAgI (1-x) GeTe 4.3 Glass, wherein x=5% and x=30%, comprises the following specific steps:
(1) According to the stoichiometric ratio, respectively weighing AgI, ge, te raw materials with x=5% and x=30%, respectively placing the raw materials into 2 cleaned quartz tubes with the inner diameter phi=20 mm, placing the quartz tubes into a vacuumizing device for vacuumizing, heating the outside of the quartz tubes with a 95 ℃ heating device for 1h, and keeping the vacuum degree below 10 -3 Fusing and sealing the quartz tube after Pa;
(2) Placing 2 fused quartz tubes into an electric heating swing smelting furnace, heating a hearth to 850 ℃ at a heating rate of 100 ℃/h, preserving heat and swing smelting for 15h, then cooling the hearth to 600 ℃ at a cooling rate of 100 ℃/h, standing for 30min, rapidly quenching in water, then placing the water into an annealing furnace to preserve heat for 5h, setting the preserving temperature of x=5% glass to 141 ℃ and the preserving temperature of x=30% glass to 126 ℃, cooling to room temperature at 10 ℃/h after the preserving is finished, taking out, polishing into glass sheets with diameters of 20mm and thicknesses of 5mm, and respectively obtaining x=5% matrix glass and x=30% matrix glass;
(3) Filling prepared matrix glass with x=5% and x=30% into a hot-pressing die with an inner diameter of 20mm, placing glass sheets with x=30% at the lower end and x=5% at the upper end, filling into a hot press, vacuumizing a furnace chamber of the hot press, and keeping the vacuum degree below 10% -2 After Pa, heating the hearth to 200 ℃ at the speed of 10 ℃/min, applying 10MPa pressure, maintaining hot-pressing diffusion for 2 days in the state, removing the pressure after the diffusion is finished, cooling the hearth to room temperature at the speed of 10 ℃/h, and then taking out the glass;
(4) And (3) grinding and polishing the two side surfaces of the glass sheet, wherein the polished surfaces are parallel to each other, so as to obtain the gradient refractive index infrared chalcogenide glass with the refractive index difference of 0.3.
A plane of the gradient refractive index infrared chalcogenide glass is selected for Raman line scanning test in the vertical direction, the relation of the change of the Raman intensity of the gradient refractive index infrared chalcogenide glass along with the change of the diffusion distance is shown in figure 3, and as can be seen from figure 3, xAgI (1-x) GeTe 4.3 The raman intensity of the AgI doping concentration in the glass also changes continuously, the test result shows that the raman signal intensity from the x=5% end to the x=30% end shows continuous change in intensity, the middle section change is approximately linear, and the diffusion is successful, and the diffusion distance is about 300 μm.
Example 2
Preparation of xAgI (1-x) GeTe 4.3 Glass, wherein x=5%, x=10%, x=15%, x=20%, x=25% and x=30%, comprises the following specific steps:
(1) According to the stoichiometric ratio, weighing AgI, ge, te raw materials of x=5%, x=10%, x=15%, x=20%, x=25% and x=30%, respectively, loading the raw materials into 6 cleaned quartz tubes with the inner diameter of phi=20 mm, loading the quartz tubes into a vacuumizing device for vacuumizing, heating the outside of the quartz tubes at 95 ℃ for 1h, and setting the vacuum degree below 10 -3 Fusing and sealing the quartz tube after Pa;
(2) Placing the sealed 6 quartz tubes into an electric heating swing smelting furnace, heating a hearth to 850 ℃ at a heating rate of 100 ℃/h, preserving heat and swing smelting for 15h, then cooling the hearth to 600 ℃ at a cooling rate of 100 ℃/h, standing for 30min, rapidly quenching in water, then placing the quartz tubes into an annealing furnace and preserving heat for 5h, wherein the preserving heat temperatures of x=5%, x=10%, x=15%, x=20%, x=25% and x=30% glass are respectively set to 141 ℃, 138 ℃, 133 ℃, 131 ℃, 128 ℃ and 126 ℃, cooling to the vicinity of room temperature at 10 ℃/h after the preserving heat is finished, and taking out, cutting and polishing glass sheets with diameters of 20mm and thicknesses of 2mm to obtain matrix glass with x=5%, x=10%, x=15%, x=20%, x=25% and x=30%;
(3) The prepared matrix glass of x=5%, x=10%, x=15%, x=20%, x=25% and x=30% is filled into a hot-pressing die with an inner diameter of 20mm, the filling positions are sequentially from top to bottom, the matrix glass is placed from low to high (namely, x=5% (uppermost), x=10%, x=15%, x=20%, x=25% and x=30% (lowermost)) according to doping concentration, then the die with the sample is filled into a hot-pressing machine, a furnace chamber of the hot-pressing machine is vacuumized, and the vacuum degree is lower than 10 -2 After Pa, heating the hearth to 200 ℃ at the speed of 10 ℃/min, applying 20MPa pressure, maintaining hot-pressing diffusion for 5 days in the state, removing the pressure after the diffusion is finished, cooling the hearth to room temperature at the speed of 10 ℃/h, and then taking out the glass;
(4) And (3) grinding and polishing the two side surfaces of the glass sheet, wherein the polished surfaces are parallel to each other, so as to obtain the gradient refractive index infrared chalcogenide glass with the refractive index difference of 0.3.
The relationship between the AgI doping concentration and the refractive index, the glass transition temperature and the glass initial crystallization temperature in the matrix glass of x=5%, x=10%, x=15%, x=20%, x=25% and x=30% is shown in fig. 1-2 and table 1, wherein fig. 1 is a graph of the AgI doping concentration and the refractive index, and fig. 2 is a graph of the AgI doping concentration and the glass transition temperature and the glass initial crystallization temperature.
TABLE 1AgI doping concentration and refractive index, glass transition temperature, glass onset crystallization temperature relationship
| x value/% | Refractive index | Glass transition temperature/DEGC | Initial crystallization temperature/DEGC |
| 5 | 3.43 | 151 | 233 |
| 10 | 3.49 | 148 | 236 |
| 15 | 3.57 | 143 | 238 |
| 20 | 3.63 | 141 | 241 |
| 25 | 3.66 | 138 | 243 |
| 30 | 3.73 | 136 | 249 |
As can be seen from Table 1 and FIG. 1, xAgI- (1-x) GeTe 4.3 The good refractive index gradient and the high refractive index difference of the glass system are key parameters of GRIN performance.
As can be seen from Table 1 and FIG. 2, xAgI- (1-x) GeTe 4.3 The glass transition temperature in the glass system changes along with the value x, and the data prove that the glass transition temperature of the system changes less, and the glass transition temperature is suitable for the GRIN preparation mode of the invention, which is the basic condition of the process technology. The glass crystallization onset temperature is the upper threshold of the preparation temperature.
A plane of the gradient refractive index infrared chalcogenide glass is selected for carrying out a Raman line scanning test in the vertical direction, and a test result shows that the intensity of a Raman signal from an x=5% end to an x=30% end shows strong and weak change, as shown in fig. 4, the whole gradient refractive index infrared chalcogenide glass is relatively linear as shown in fig. 4, and the success of diffusion is indicated.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The gradient refractive index infrared chalcogenide glass is characterized by comprising a first surface layer substrate glass, a sandwich substrate glass and a second surface layer substrate glass which are sequentially laminated; the number of layers of the sandwich substrate glass is more than or equal to 0;
the chemical composition of the first surface layer substrate glass, the sandwich substrate glass and the second surface layer substrate glass is xAgI (1-x) GeTe 4.3 Wherein, x in the first surface layer substrate glass is 30%, x in the sandwich substrate glass is 0-30%, and x in the second surface layer substrate glass is 0-5%; the thickness of the first surface layer substrate glass and the second surface layer substrate glass is independently 1-20 mm, and the thickness of the sandwich substrate glass is 0.5-2 mm;
x in the gradient refractive index infrared chalcogenide glass is gradually decreased along the direction from the first surface layer substrate glass to the second surface layer substrate glass;
the preparation method of the gradient refractive index infrared chalcogenide glass comprises the following steps:
preparing each layer of matrix glass by adopting a melting quenching method after preparing according to the chemical composition of each layer, and respectively obtaining first surface layer matrix glass, sandwich matrix glass and second surface layer matrix glass;
sequentially laminating the first surface layer substrate glass, the sandwich substrate glass and the second surface layer substrate glass, and then performing hot-pressing diffusion to obtain gradient refractive index infrared chalcogenide glass; the heat preservation temperature of the hot-pressing diffusion is 160-200 ℃, the pressure is 10-30 MPa, the time is 1-5 days, and the vacuum degree is less than 10 -2 Pa。
2. The method for preparing the gradient-index infrared chalcogenide glass according to claim 1, comprising the steps of:
preparing each layer of matrix glass by adopting a melting quenching method after preparing according to the chemical composition of each layer, and respectively obtaining first surface layer matrix glass, sandwich matrix glass and second surface layer matrix glass;
sequentially laminating the first surface layer substrate glass, the sandwich substrate glass and the second surface layer substrate glass, and then performing hot-pressing diffusion to obtain gradient refractive index infrared chalcogenide glass;
the heat preservation temperature of the hot-pressing diffusion is 160-200 ℃, the pressure is 10-30 MPa, the time is 1-5 days, and the vacuum degree is less than 10 - 2 Pa。
3. The method according to claim 2, wherein the melt quenching method comprises sequentially performing vacuum melting, quenching and annealing treatments.
4. The method according to claim 3, wherein the vacuum degree of vacuum melting is less than 10 -3 Pa, the heat preservation temperature is 800-900 ℃, and the heat preservation time is 10-20 h; the temperature is raised from room temperature to the vacuum meltingThe temperature rising rate of the heat preservation temperature is 60-120 ℃/h.
5. The method according to claim 3, wherein the annealing treatment comprises sequentially performing thermal annealing and cooling annealing; the temperature of the heat preservation annealing is 121-146 ℃, and the heat preservation time is 3-10 hours; and the cooling rate of the cooling annealing is 5-10 ℃/h.
6. The preparation method according to claim 2, wherein the heating rate from room temperature to the heat preservation temperature of the hot-press diffusion is 5-20 ℃/min.
7. An infrared thermal imaging lens, comprising the graded-index infrared chalcogenide glass according to claim 1 or the graded-index infrared chalcogenide glass produced by the production method according to any one of claims 2 to 6.
8. Use of a graded index infrared chalcogenide glass according to claim 1, a graded index infrared chalcogenide glass produced by the method of any one of claims 2 to 6, or an infrared thermal imaging lens according to claim 7 in infrared thermal imaging.
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| [联邦德国]H·舒尔兹.《玻璃的本质结构和性质》.中国建筑工业出版社,1984,(第1版),第308页. * |
| Novel acousto-optic material based on Ge-Te-AgI chalcohalide glasses;Shengjie Ding etal.;Ceramics International;第47卷(第9期);第12072-12077页 * |
| 王迎军 主编.《新型材料科学与技术 无机材料卷》.华南理工大学出版社,2016,(第1版),第493-494页. * |
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