CN111187005A - Chalcogenide infrared microcrystalline glass and preparation method thereof - Google Patents
Chalcogenide infrared microcrystalline glass and preparation method thereof Download PDFInfo
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- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
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Abstract
The invention discloses chalcogenide infrared microcrystalline glass and a preparation method thereof, wherein the microcrystalline glass comprises the following components in percentage by mol: 8-35% of Ge; 10-40% of As; 30-60% of Se; 0-25 wt% of Te; 0.2-5% of MX, wherein the MX is one or more of CsCl, CsBr, CsI and RbI; the microcrystalline glass with smaller crystal grains and uniform distribution is obtained by adopting a crystallization treatment technology, the crystallization temperature is in the temperature range from the transition temperature Tg to the transition temperature Tg plus 40 ℃, and heat preservation is carried out. The invention optimizes the nucleating agent and the crystallization treatment process, so that the prepared glass ceramics have relatively high mechanical property and permeability, can be used for infrared thermal imaging or infrared sensing, and is particularly suitable for vehicle-mounted night vision devices, thermal imaging devices and the like.
Description
Technical Field
The invention relates to the field of chalcogenide infrared glass ceramics, in particular to chalcogenide infrared glass ceramics and a preparation method thereof.
Background
The chalcogenide glass is mainly in a chain structure formed by covalent bonds between weak two-coordinate chalcogen elementsThe infrared glass is supplemented with a crosslinking network formed by three-coordinate or four-coordinate IV group and V group elements, the Van der Waals force between chains is weak, so that the mechanical property and the thermal stability are relatively poor, cracks and the like are easy to generate in the processing and using processes, the hardness of the sulfur infrared glass which is applied to more businesses at home and abroad is generally low, and the hardness H of the sulfur infrared glass is highkAbout 110-165X 107Pa, the defect limits the application of the chalcogenide infrared glass to a certain extent.
At present, the mechanical property and the thermal stability of chalcogenide infrared glass can be improved by adjusting the chemical composition, but the improvement effect is limited, and the micro crystallization of chalcogenide glass is another way for improving the performance of chalcogenide glass. Therefore, a crystal phase with nanometer-scale and uniform distribution is precipitated inside the glass by adding a proper nucleating agent and carrying out micro-crystallization treatment, so that the chalcogenide glass ceramics which is transparent in the middle and far infrared region is obtained.
One of the prior art (see "Micro-crystallized transformating loaded chalcogenoside glass in GeSe)2-As2Se3-PbSe system,GeSe2-As2Se3-research on infrared-transmitting sulfur-based glass microcrystallization of PbSe system ", Wang Hua, Zhang Xianghua, Yang Guang, et al, ceramics international, 2009, 35:83-86 and" a selenium-cadmium-containing compound glass and a method for producing the same ", patent application No. of zhao donghui et al: 200510028596.7, "GeSe2-As2Se3Research on the formation of CdSe infrared glass, Wanghua et al, 2005,33(8), 986-.
The second prior art (see "CsCl vs Ge)23Se67Sb10Influence of the texture and Properties of the Infrared glass, Chang Fang 'e et al, functional materials, 14(14), P1998-2002 (2013)', and "Microcrystalization on Ge23Se67Sb10Influence of Infrared glass Properties rare metals materials andengineering, 41(10), P1741-1745(2012) "), performing microcrystallization research on Ge-Sb-Se system glass to form GeSe in the glass2And Sb2Se3The nano crystal improves the hardness of the glass, but the transmittance of the glass is reduced to different degrees.
In the third prior art (see ' preparation and performance of novel gadolinium-containing sulfide glass, Nie is good and equal, silicate science report, 2004, 32(3):274 and ' research on long-wave infrared glass ', Wang Yi, etc., functional materials 2010, 41:196), through experiments, it is found that Gd is added into Ge-S binary system chalcogenide glass to eliminate absorption peaks of impurities, and can improve the glass transition temperature and hardness, so that the thermal stability and mechanical properties of chalcogenide glass are obviously improved, but the introduction of Gd can increase the crystallization characteristic of the system, and the forming capability of the glass can be reduced along with the reduction of the content of Ge of a network forming body atom.
Fourth of the prior art ("Glasses and glass Based on GeSe)2-Sb2Se3andHalides for FarInfrared Transmission based on GeSe2-Sb2Se3Research on far infrared transmittance of glass and glass-ceramic of halide glass system "Calvez L, Ma HL, Lucas J, et. journal of No n-Crystalline solids,2008(354):1123) shows that the chalcogenide glass containing Cu has better crack extension resistance and higher hardness, and the introduction of the chalcogenide glass enhances the devitrification tendency of the glass matrix, but the Cu with large size is generated during the heat treatment process2GeSe3The crystal grain is difficult to control the growth of the crystal grain, and the transmission performance of the microcrystalline glass in an infrared region is easily influenced.
Disclosure of Invention
The invention aims to provide chalcogenide infrared glass ceramics which have relatively high mechanical property and permeability, can be used for infrared thermal imaging or infrared sensing, and is particularly suitable for vehicle-mounted night vision devices, thermal imaging devices and the like.
In addition, the invention also provides a preparation method of the chalcogenide infrared glass ceramics.
The invention is realized by the following technical scheme:
the chalcogenide infrared microcrystalline glass comprises the following components in percentage by mol:
8-35% of Ge; 10-40% of As; 30-60% of Se; 0-25 wt% of Te; 0.2-5% of MX, wherein the MX is one or more of CsCl, CsBr, CsI and RbI.
The mechanical property and the permeability of the microcrystalline glass are related to the uniformity of the grain size and the distribution of the microcrystalline glass, and the composition ratio and the heat treatment process of the microcrystalline glass are key factors influencing the grain size and the distribution.
The chalcogenide infrared glass nucleating agent also has strict requirements, namely the nucleating agent must exist in chalcogenide glass in a small-size and dispersed form, and different types of nucleating agents can change the crystallization behavior of chalcogenide microcrystalline glass, so that the micro-morphology and the distribution state of a precipitated crystal phase are changed.
According to the invention, the high-strength chalcogenide infrared glass ceramics with the grain size less than 200nm can be obtained by optimizing the components and the proportion of the glass ceramics, selecting halide (one or more of CsCl, CsBr, CsI and RbI) as a nucleating agent and combining a heat treatment process, wherein the main crystal phase of the glass ceramics contains GeSe2(ii) a And/or As2Se3(ii) a And/or GeTe; and/or As2Te3So as to improve the mechanical property and the permeability of the microcrystalline glass.
And (4) passing performance verification: the hardness of the microcrystalline glass is 180 multiplied by 107Above Pa, the transmittance of the glass at the position of 10.6um is 60-70%.
In addition, the raw materials used by the invention do not contain Pb, Cd and Gd, and the hardness is improved, the higher transmittance is kept, and the environment protection is facilitated.
Further, the composition comprises the following components:
10-33% of Ge; and/or 12-40% of As; and/or 45-60% of Se; and/or MX 1-5%.
Furthermore, the content of MX is 2-4% by mol percentage.
Further, the main crystal phase of the chalcogenide infrared glass ceramics contains GeSe2(ii) a And/orAs2Se3(ii) a And/or GeTe; and/or As2Te3。
Furthermore, the chalcogenide infrared microcrystalline glass has the hardness of H at the temperature of 20 DEG CkIs 180 x 107Pa is above; and/or a light transmittance of 60% or more, preferably 64% or more, at a wavelength of 10.6um with a thickness of 5 mm; and/or an average transmittance of 2.5 to 12um at a thickness of 5mm of 58% or more, preferably 63% or more; and/or does not contain Pb, Cd, Gd.
Further, the crystal grain size of the chalcogenide infrared glass ceramics is 200nm or less, preferably 100nm or less, and more preferably 50nm or less.
A preparation method of chalcogenide infrared microcrystalline glass comprises the steps of preparing base glass according to a formula of chalcogenide infrared microcrystalline glass, and then forming the microcrystalline glass from the base glass through a crystallization process, wherein a main crystal phase in the microcrystalline glass contains GeSe2(ii) a And/or As2Se3(ii) a And/or GeTe; and/or As2Te3。
Further, the method comprises the following steps:
1) preparing materials: glass raw materials are mixed according to a glass formula and are filled into a reaction container;
2) sealing by fusing: vacuumizing and sealing the reaction container filled with the raw materials in the step 1);
3) smelting: putting the sealed reaction container into a rocking furnace for smelting, wherein the highest smelting temperature is 950-1000 ℃;
4) quenching: slowly cooling the molten glass liquid to 550-650 ℃, discharging, and quickly cooling and forming;
5) annealing: carrying out heat preservation annealing on the quenched glass at the annealing temperature of 200-375 ℃, and then cooling along with the furnace after power failure;
6) and (3) crystallization: and crystallizing the annealed glass at a crystallization temperature.
Further, the crystallization temperature is in the temperature range from the transition temperature Tg of the base glass to the transition temperature Tg +40 ℃.
Furthermore, the heat preservation time of the crystallization treatment is 5 to 40 days.
Further, steps 3) to 6) are all performed under vacuum.
The glass is a metastable state with a tendency to transform to a crystalline state, which can be achieved by heat treatment process temperatures and times. The microcrystalline glass is a composite material consisting of a glass state and a crystalline state. Crystals are precipitated in a glass body, and the preparation of the oxide microcrystalline glass generally needs two steps, namely nucleation and crystal growth of the crystals. The formation of nuclei characterizes the generation of new phases, while the growth of crystals is a further extension of new phases. Wherein, the nucleation process can be divided into uniform nucleation and non-uniform nucleation. The homogeneous nucleation means that no external factors participate in the homogeneous glass, the nucleation process is irrelevant to structural defects of the glass, phase boundaries generated by phase separation and the like, and partial glass bodies are converted into crystals due to fluctuation of the composition and the structure of the glass caused by internal thermal motion of the glass. However, chalcogenide glass cannot be prepared by a uniform nucleation mode (without introducing a nucleating agent), and because chalcogenide glass easily causes nonuniform crystallization in glass and crystal size is difficult to control, the transmittance of glass is reduced and even the glass is opaque.
The chalcogenide glass with greatly improved mechanical properties can be prepared by properly heat treating chalcogenide glass with special components, and is different from oxide glass in that chalcogenide glass is mainly used as an infrared wave-transmitting material and has extremely high requirements on the transmittance of glass. Although the used wavelength of the chalcogenide glass is in the middle and far infrared band (1-12um), theoretically, the size requirement of the microcrystal in the microcrystalline glass is wider than that of the crystal in the visible light-transmitting oxide microcrystalline glass, for example, the microcrystal in the visible light-transmitting microcrystalline glass is required to be smaller than 100nm, namely, the microcrystal can be transparent in the visible light band (400-800nm), and the microcrystal in the chalcogenide microcrystalline glass can still transmit part of the middle and far infrared band light (1-12um) when the size of the microcrystal in the chalcogenide glass reaches 200nm, but even if the transmittance is reduced by only 2%, the imaging of an infrared optical system is blurred, which is unfavorable for the application of the chalcogenide infrared glass material. Therefore, the chalcogenide infrared microcrystalline glass has more strict requirements on the size of a microcrystal in the glass, and the size is less than 50nm, so that the infrared light can not be scattered when being transmitted, and the microcrystal in the glass can not influence the infrared transmittance of the chalcogenide glass. For imaging systems requiring chalcogenide glass materials to transmit only the long wavelength band (8-12um), the crystallite size in the glass-ceramic can be relaxed appropriately to 100nm, since an increase in crystallite size will affect the transmission properties of the infrared short band (1-3um) first, and less for the long wavelength band.
As mentioned above, the size of crystal grains is strictly controlled during the micro-crystallization of chalcogenide glass, so as to avoid the influence of scattering caused by over-large crystal grains on the transmittance of infrared band, therefore, the microcrystallization of chalcogenide glass needs to inhibit the growth of microcrystals, which is obviously different from oxide microcrystalline glass, namely, the oxide microcrystalline glass needs two stages of nucleation and growth of crystals, needs to be kept at different heat treatment temperatures for a period of time, the chalcogenide glass has high crystallization speed, so that the control of crystal growth at a high crystallization temperature is difficult to realize, therefore, the chalcogenide glass microcrystallization heat treatment only has a heat preservation stage of crystal formation, and needs a long heat preservation time, namely, a large number of fine crystals are uniformly precipitated on a chalcogenide glass substrate at a nucleation temperature for a long period of time, and the overgrowth of the crystal size of the glass is inhibited, so that the optimal nucleation temperature and the optimal nucleation heat-preservation time are the key points for preparing the chalcogenide glass ceramics.
In addition, the chalcogenide infrared glass nucleating agent also has strict requirements, namely the nucleating agent must exist in chalcogenide glass in a small-size and dispersed form, and different types of nucleating agents can change the crystallization behavior of chalcogenide microcrystalline glass, so that the microstructure and the distribution state of a precipitated crystal phase are changed. In addition, the nucleating agent of the chalcogenide glass cannot introduce oxides, such as the nucleating agent TiO commonly used in oxide glass ceramics2And ZrO2Neither can be used in chalcogenide glass ceramics because oxygen causes the transmission absorption peaks of a plurality of wavelengths in the infrared band, and further causes the transmittance in the range of middle and far infrared bands to be greatly reduced. When Ti is introduced into a chalcogenide glass, impurities are generated in the glass, and therefore, it is not suitable for use. The nucleating agent without reducing the infrared transmittance of the chalcogenide microcrystalline glass is selected, and halides such as CsCl, CsBr, CsI and RbI are adopted in the invention, so that the absorption peak of the transmittance caused by partial impurities can be eliminated, and the nucleating agent can be used as the nucleating agentThe formation of the microcrystal in the chalcogenide glass provides an interface, and the microcrystal formed in the microcrystalline glass mainly is GeSe in the Ge-As-Se-Te system2And/or As2Se3And/or GeTe, and/or As2Te3。
Whether As2Se3Or GeSe2Have long been found to be glass formers, the difference between which is As2Se3The glass formed is generally of a chain-like structure, while GeSe2With similar SiO2The tetrahedral structure of the glass, Ge is located at the center of the tetrahedron, and the coordination ratio of Ge to Se is 4: 2. When the number of components of the glass former increases, competition occurs between different structural units because the structure becomes complicated. Therefore, the chemical composition of the chalcogenide glass Ge, As and Se can be adjusted to improve the thermal and mechanical properties of the chalcogenide glass, improve the average bond strength of the system, or improve the cross-linking degree of a glass network, or improve the average coordination number of the system.
The performance of the chalcogenide infrared glass ceramics depends on the components and the microstructure, as the factors for inhibiting crack propagation in homogeneous chalcogenide glass are few, once cracks are generated, the cracks can rapidly expand to cause glass fracture, so that the chalcogenide glass is easy to crack in the processing process, in the chalcogenide glass ceramics, the crack propagation is difficult, the existence of a large number of small crystal grains causes phase interfaces between a large number of crystal grains and matrix glass, and the structures and the properties of the two phases are different, so when the cracks are generated, the phase interfaces can change, slow down or even stop the crack propagation, the crack can only expand in a small range and cannot be enough to cause the fracture of a sample, and the fracture toughness of the chalcogenide glass is improved. Therefore, the sulfur series infrared glass is subjected to micro crystallization treatment, and the mechanical property and the thermal stability of the sulfur series infrared glass can be greatly improved. By adding different types and different contents of nucleating agents, the chalcogenide infrared microcrystalline glass with better transmittance and hardness performance can be obtained at proper crystallization temperature and time.
Therefore, the sulfur series infrared glass is subjected to micro crystallization treatment, and the mechanical property and the thermal stability of the sulfur series infrared glass can be greatly improved.
Ge. The Te element has higher glass transition temperature, can inhibit the crystallization tendency of the glass, can improve the density of the glass and increase the hardness of the glass. Ge. The purpose of the invention cannot be achieved when the content of Te is too low, and the glass cannot be formed when the content of Te is too high, so that the content of Ge is controlled within the range of 8-35%, preferably 10-33%; the content of Te is controlled within the range of 0 to 25 wt%.
As element can expand the glass forming range of the base glass, adjust the type and content of crystalline phase and improve the dispersion performance of the glass. As content is too low, the structure of the crystal phase in the glass is single in type, and uniform crystallization is difficult to realize; the dispersion of the glass is increased due to the excessively high content of As, and the application value is low, so that the content of As is controlled within the range of 10-40%, preferably 12-40%.
Se element has high activity, is easy to react with other elements, has high reaction speed, is quickly melted at low pressure and lower temperature, and reacts with other raw materials at lower temperature to reduce the melting temperature. As in base glass2Se3Generally of chain-like structure, and GeSe2With similar SiO2The tetrahedral network structure of the glass, Ge is positioned at the center of tetrahedron, and the coordination ratio of Ge to Se is 4: 2. as the number of components of the glass former increases, the glass forming region may be enlarged due to "competition" between different structural units as the structure becomes complicated. And the bond energy of Ge-Te or Ge-Se bonds is larger, so that the hardness of the glass is increased. When the Se content is lower, the glass in-line range is narrowed, and the control requirement on the smelting forming process of the base glass is strict; when the Se content is too high, the crystal content of the glass can be reduced, and higher hardness cannot be achieved, so that the Se content is controlled within the range of 30-60%, and preferably 45-60%.
MX is taken as a nucleating agent, one or more of CsCl, CsBr, CsI and RbI have the advantages of increasing the termination effect on a glass network, loosening the whole structure of the glass and increasing the crystallization tendency, so the content of the nucleating agent is strictly controlled. GeSe is gradually formed after the base glass is subjected to microcrystallization2、As2Se3And GeTe, in which a part of the chain or network structure in the glass is converted into a crystal structure, thereby further improving the glass qualityEnhancing the hardness of the glass. Too low MX content causes a lower number of crystals in the base glass, resulting in too large grain size and thus a reduction in glass transmittance; the excessive MX content can cause the glass structure to be loose, the strength to be reduced and the glass brittleness to be increased; in addition, the MX content is controlled within the range of 0.2-5%, preferably 1-5%, more preferably 2-4%, because the glass crystallization speed is too high and difficult to control due to too high MX content, and clustering phenomenon is easily generated in crystals.
In conclusion, by adding different types and different contents of nucleating agents, the chalcogenide infrared glass ceramics with better transmittance and hardness performance can be obtained at proper crystallization temperature and time.
The invention relates to chalcogenide infrared microcrystalline glass prepared by optimizing the components and the proportion of the microcrystalline glass, selecting halide (one or more of CsCl, CsBr, CsI and RbI) as a nucleating agent (nucleating agent) at proper crystallization temperature and heat preservation time, wherein the microcrystalline glass has the grain size of less than 200nm, is uniformly distributed in the microcrystalline glass, and has the hardness of 180 multiplied by 107The transmittance of the glass at 10.6um is 60-70 percent under Pa, namely the quantity of crystal nuclei and the size of crystal size in the glass are controlled by a heat treatment process, so that the glass has higher transmittance in an infrared band, the hardness and the processability of the glass are improved, and the comprehensive performance of the material is optimal.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention reasonably selects the components and the content of the chalcogenide infrared glass, introduces the crystal nucleus agent, and obtains the high-strength chalcogenide infrared glass ceramics with the grain size less than 200nm after heat treatment; the quantity of crystal nuclei and the size of crystal size in the glass are controlled by a heat treatment process, so that the glass has higher transmittance in an infrared band, the hardness and the processability of the glass are improved, and the comprehensive performance of the material is optimal.
2. The chalcogenide infrared microcrystalline glass adopts a vacuum melting mode, and is particularly suitable for glass materials of infrared thermal imaging instruments and infrared night vision instruments.
3. The raw materials used in the invention do not contain Pb, Cd and Gd, and the hardness is improved, the transmittance is kept high, and the environment protection is facilitated.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
Unless otherwise indicated in a specific context, numerical ranges set forth herein include upper and lower values, and "above" and "below" include endpoints, all integers and fractions within the range, and are not limited to the specific values listed in the defined range. The term "about" as used herein means that the formulations, parameters, and other quantities and characteristics are not, and need not be, exact, and can be approximate and/or larger or smaller, if desired, reflecting tolerances, conversion factors, measurement error and the like. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.
Example 1:
the chalcogenide infrared microcrystalline glass comprises the following components in percentage by mol:
Ge 32.3％；As 11.8％；Se 53.9％；Te 0％；CsCl 2％。
example 2-example 20:
example 2-example 20 is based on example 1, differing from example 1 in that:
the specific differences between the components in different proportions are shown in tables 1 and 2.
The glasses prepared in examples 1 to 20 were subjected to the performance test, which was as follows:
1) knoop hardness Hk
Knoop hardness H of infrared glass ceramicskAccording to GB/T7962.18-2010Test methods.
The hardness Hk of the infrared microcrystalline glass is 180 multiplied by 107Pa or above.
2) Light transmittance
The glass is made into a sample with the thickness of 5mm +/-0.1 mm, and the transmittance T of the glass at the position of 10.6um is tested10.6umAnd an average transmittance of 2.5 to 12um
The average transmittance of 2.5-12um is in the range of 2.5-12um, and the transmittance of each wavelength is measured by scanning at intervals of 20nm and calculated according to the following formula:
the infrared microcrystalline glass has the light transmittance of more than 60 percent, preferably more than 64 percent, and the light transmittance of 10.6um wavelength with the thickness of 5mm, and is not less than 2 percent of the transmittance of the base glass before crystallization; and/or an average transmittance of 2.5 to 12um at a thickness of 5mm of 58% or more, preferably 63% or more.
3) Grain size
And corroding the sample to be detected with the polished surface in an HF acid solution with the concentration of 4 wt% for 10-30s, cleaning, drying, and evaporating a layer of gold film on the surface of the glass sample. And performing scanning test by using a field emission Scanning Electron Microscope (SEM) to obtain a micro-morphology picture of the surface of the sample microcrystalline glass, and calibrating the grain size according to the apparent morphology picture.
The crystal grain size of the infrared glass ceramics of the present invention is 200nm or less, preferably 100nm or less, and more preferably 50nm or less.
4) Crystal phase testing
The infrared glass ceramics of the present invention are materials having a crystal phase and a glass phase, which are different from amorphous solids. The crystalline phase formed in the glass-ceramic can be analyzed by X-ray diffractometry (Bruker D8-Advance model, Germany) at a scanning speed of 4 DEG/min with a step size of 0.02 deg. And (4) comparing the standard PDF card according to the X-ray diffraction pattern to obtain a phase corresponding to the precipitated crystal. The predominant crystalline phase is determined by X-ray diffraction.
The main crystal phase of the infrared microcrystalline glass contains GeSe2(ii) a And/or As2Se3(ii) a And/or GeTe; and/or As2Te3。
The test results are shown in tables 1 and 2:
TABLE 1
TABLE 2
The preparation method of the chalcogenide infrared glass ceramics in the embodiment 7 comprises the following steps:
1) preparing materials: glass raw materials are proportioned according to the glass formula of example 7 and filled into a reaction vessel;
2) sealing by fusing: vacuumizing the reaction vessel filled with the raw materials in the step 1) to 10 DEG-3Sealing after Pa is below;
3) smelting: putting the sealed reaction vessel into a rocking furnace for smelting, keeping the highest smelting temperature at 960 ℃, preserving the heat for 11 hours, and starting rocking after the raw materials are molten to enable the raw materials to fully react to a uniform state;
4) quenching: slowly cooling the molten glass liquid to 600 ℃, discharging, and quickly cooling and forming;
5) annealing: carrying out heat preservation annealing on the quenched glass at the annealing temperature of 280 ℃ for 4h, and then cooling to room temperature at the speed of-2 ℃/min;
6) and (3) crystallization: and crystallizing the annealed glass at the crystallization temperature of 310 ℃ for 30 days, and then knocking the bottle to take out the glass.
This example provides a high-hardness microcrystalline glass of the Ge-As-Se system containing GeSe2And As2Se3The crystal grain size is 40-60 nm, the hardness reaches 202X 107Pa, the transmittance at 10.6um of the film reaches 67.1 percent (5mm thickness),
is 66.3% (5mm thickness). The method for preparing the chalcogenide infrared glass ceramics according to the embodiment 17 comprises the following steps:
1) preparing materials: glass raw materials were compounded according to the glass formulation of example 17 and charged into a reaction vessel;
2) sealing by fusing: vacuumizing the reaction vessel filled with the raw materials in the step 1) to 10 DEG-3Sealing after Pa is below;
3) smelting: putting the sealed reaction vessel into a rocking furnace for smelting, keeping the highest smelting temperature of 980 ℃ for 12h, and starting rocking after the raw materials are molten to fully react the raw materials to a uniform state;
4) quenching: slowly cooling the molten glass to about 580 ℃, discharging, and quickly cooling and forming;
5) annealing: annealing: carrying out heat preservation annealing on the quenched glass at the annealing temperature of 265 ℃ for 4h, and then cooling to room temperature at a speed of-3 ℃/min;
6) and (3) crystallization: and crystallizing the annealed glass at the crystallization temperature of 290 ℃ for 35 days, and knocking the bottle to take out the glass.
In this example, a high-hardness microcrystalline glass of Ge-As-Se-Te system containing GeSe was obtained2The microcrystalline glass with GeTe as main crystal phase has crystal grain size of 60-80 nm, transmittance of 64.2% (5mm thickness) at 10.6um, and hardness of 231 × 107Pa，
63.0% (5mm thickness).
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
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| CN115626771A (en) * | 2022-10-25 | 2023-01-20 | 宁波海洋研究院 | A kind of high hardness Ge-As-Se chalcogenide glass and its preparation method and application |
| CN116002979A (en) * | 2022-12-07 | 2023-04-25 | 宁波大学 | A highly nonlinear transparent glass-ceramic |
| CN117865471A (en) * | 2023-12-11 | 2024-04-12 | 湖北新华光信息材料有限公司 | A kind of chalcogenide glass and its preparation method and optical element |
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| CN115626771A (en) * | 2022-10-25 | 2023-01-20 | 宁波海洋研究院 | A kind of high hardness Ge-As-Se chalcogenide glass and its preparation method and application |
| CN115626771B (en) * | 2022-10-25 | 2023-12-26 | 宁波海洋研究院 | High-hardness Ge-As-Se chalcogenide glass and preparation method and application thereof |
| CN116002979A (en) * | 2022-12-07 | 2023-04-25 | 宁波大学 | A highly nonlinear transparent glass-ceramic |
| CN117865471A (en) * | 2023-12-11 | 2024-04-12 | 湖北新华光信息材料有限公司 | A kind of chalcogenide glass and its preparation method and optical element |
| CN117865471B (en) * | 2023-12-11 | 2025-12-16 | 湖北新华光信息材料有限公司 | Chalcogenide glass, preparation method thereof and optical element |
| CN119118518A (en) * | 2024-08-21 | 2024-12-13 | 宁波阳光和谱光电科技有限公司 | A Ge-As-Se-CsCl glass ceramic and preparation method thereof |
| CN119118518B (en) * | 2024-08-21 | 2025-10-14 | 宁波阳光和谱光电科技有限公司 | A Ge-As-Se-CsCl glass ceramic and preparation method thereof |
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Application publication date: 20200522 |