CN112608025B - Preparation method of high-purity Ge-Sb-Se system infrared chalcogenide glass - Google Patents
Preparation method of high-purity Ge-Sb-Se system infrared chalcogenide glass Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000005387 chalcogenide glass Substances 0.000 title claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 118
- 239000011521 glass Substances 0.000 claims abstract description 103
- 239000010453 quartz Substances 0.000 claims abstract description 79
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000004821 distillation Methods 0.000 claims abstract description 43
- 238000001816 cooling Methods 0.000 claims abstract description 40
- 239000012535 impurity Substances 0.000 claims abstract description 34
- 238000002844 melting Methods 0.000 claims abstract description 33
- 230000008018 melting Effects 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 32
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
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- 238000009835 boiling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
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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
- C03C4/00—Compositions for glass with special properties
- C03C4/10—Compositions for glass with special properties for infrared transmitting glass
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Abstract
The invention discloses a preparation method of high-purity Ge-Sb-Se system infrared glassThe method adopts a preparation technology of integrating integral distillation purification and melting of chalcogenide glass raw materials, adopts a double-hearth partitioned temperature control asymmetric swing melting equipment double-well type furnace structure, adopts resistance wire heating and accurately controls four temperature zones. The glass component Ge 28‑x Sb 12+ x Se 60 (x is more than or equal to 0 and less than or equal to 3), and the preparation method specifically comprises the following steps: the device comprises a high-efficiency impurity removal process, a specific melting process curve, a specially-made quartz pipe fitting, a special air cooling device and the like. The invention has the advantages of high purity, good optical uniformity and excellent large-size performance of the commercial infrared chalcogenide glass.
Description
Technical Field
The invention relates to the technical field of selenium-based chalcogenide glass preparation, in particular to a preparation method of commercial infrared chalcogenide glass with high purity, good optical uniformity and excellent large-size performance.
Background
Ge-Sb-Se chalcogenide glass is an excellent infrared glass material. The glass has the advantages of environmental friendliness, no toxicity, high glass transition temperature, wide infrared transmission range, good mechanical processability and the like, but the impurity absorption is relatively high, and the difficulty in ensuring the optical uniformity of commercial large-size infrared chalcogenide glass is a main bottleneck limiting the application of the glass.
The Ge-Sb-Se system infrared glass is very sensitive to impurities such as carbon, hydrogen, oxygen and the like in the environment in the preparation process, the introduction of the impurities greatly reduces the infrared transmission performance of the glass, particularly the introduction of oxygen, and the simple Ge is easily combined with the oxygen in the melt to form GeO at high temperature 2 Isooptically absorbing impurities, ge-O absorption peaks at 8.01 μm and 12.81 μm, and 8-14 μm are one of the important atmospheric infrared windows, on one hand, the wavelength corresponding to the radiation spectrum peak of the room temperature object is about 10 μm, and on the other hand, CO with larger output power at present 2 The emission wavelength of the laser is 10.6 μm, so the relevant application of the wavelength band relates to military and civil fields such as night vision, mapping, industrial diagnosis and medical diagnosis. In order to improve the definition and the resolution of a target, an impurity removal process is a key technology and difficulty in the process of preparing the Ge-Sb-Se system infrared glass.
The traditional chalcogenide glass production and preparation process mainly comprises the following steps: raw material purification, high-uniformity glass melting, demoulding and annealing. The key of the preparation process of the commercial large-size Ge-Sb-Se chalcogenide glass is how to ensure the optical uniformity of the material, and the preparation process has a vital influence on the internal defects of optical stripes of the glass and the surface cracks (lunar face) after the glass liquid is solidified, such as the shape and the height of a quartz tube, and the processes (tapping temperature and cooling rate) of swinging speed, angle tapping and the like during smelting.
CN103232161A discloses a preparation method of Ge-Sb-Se system infrared glass, which comprises the following steps: mixing Ge, sb and Se glass raw materials and a deoxidant to form a batch, and carrying out pretreatment; first melting: heating the batch to 850-900 ℃ to obtain first molten glass; then cooling the first molten glass and quenching to form glass clinker; and (3) second melting: transferring the glass clinker into an atmosphere protection preparation device, raising the temperature of a melting chamber to 650-750 ℃, and starting stirring to fully homogenize the glass clinker to form second molten glass; and after cooling, allowing the second molten glass to stand for a period of time for material leakage molding. The Ge-Sb-Se infrared optical system prepared by the method has the advantages of stable composition and performance and uniform internal quality, and further improves the imaging quality of the Ge-Sb-Se infrared optical system.
CN105722801A discloses an infrared transmitting glass containing, in mole%, ge: 0-20% (excluding 0%, 20%); sb:0 to 40% (excluding 0%); bi:0 to 20% (excluding 0%); and S + Se + Te:50 to 80 percent. The infrared transmitting glass has excellent infrared transmittance at a wavelength of about 8 to 12 μm. As an index for evaluating the infrared transmittance at a wavelength of about 8 to 12 μm, a 50% transmission wavelength in the infrared region is mentioned.
Although the prior art has been studied on infrared glasses of Ge-Sb-Se system, the manufacturing method thereof has a disadvantage in controlling the impurity content of the glass system and the uniformity of optical properties (especially, long wavelength region), and at the same time, the prior art method is not suitable for the manufacture of large-sized glasses.
Disclosure of Invention
The invention provides an efficient impurity removal technology and a preparation method of Ge-Sb-Se system infrared glass with large size and good optical uniformity under the original traditional preparation process conditions.
In order to achieve the purpose, the technical scheme of the application adopts the following technical principles to realize the control of the properties of the glass product of the invention:
as three raw material metals of the Ge-Sb-Se system infrared glass easily absorb moisture or are oxidized, the generated Ge-O bond and Se-H bond absorption peaks seriously influence the physical properties of the glass, particularly the infrared transmission performance, and in order to eliminate the influence of impurities to the maximum extent, the invention firstly dries Ge, sb and Se raw material particles, and then purifies the raw materials by adopting a distillation method to remove moisture and other impurities.
The invention adopts the U-shaped quartz tube with a special structure, and the quartz tube has stronger high-temperature resistance. The wall of the quartz tube should be carefully inspected for bubbles, cracks or other defects to prevent the quartz tube from exploding during the high-temperature melting process, and the newly purchased quartz tube should be pretreated in consideration of the fact that the quartz tube usually contains a trace amount of hydroxyl groups and various impurities may be attached to the inner wall of the quartz tube.
And the content of oxidizing groups and other impurities in the finished glass product is controlled by adding an impurity removing agent and combining methods such as distillation and the like. For example, a metal chlorinating agent is added to remove H, and Al is added to remove O. For example, the invention can react with H impurities in the glass liquid to generate HCl which is discharged out of the tube through a distillation process, and the content of the H impurities in the glass can be effectively reduced. The distillation mainly removes O impurities, al reacts with oxygen to fix the oxygen, and finally, through the integral distillation, al oxides and C impurities are left in a raw material area due to small saturated vapor pressure, and high-purity glass is obtained in a finished product area. The technical method of the invention has the advantages that the combination probability of the raw material metal and the free oxygen in the glass is reduced with high efficiency, and the adverse effects on the glass performance such as component nonuniformity and optical performance fluctuation are reduced; the light transmittance of the wavelength in the infrared region is enhanced.
In order to eliminate residual stress in the glass, improve the quality of a glass sample and avoid cracking, breaking and the like of the glass in the later processing process, the quenched quartz tube needs to be placed into an annealing furnace for annealing so as to eliminate the temperature gradient of each component of the glass and release internal stress.
The specific scheme of the invention is as follows:
a preparation method of high-purity Ge-Sb-Se system infrared chalcogenide glass comprises the following steps:
the method comprises the following steps: pretreatment of raw materials: the raw materials are pretreated by adopting high-purity (99.999%) Ge particles, sb particles and Se particles.
Preferably, the raw material pretreatment includes, but is not limited to, drying Ge, sb, and Se, purifying the raw material by distillation to remove moisture and other impurities, and storing the purified raw material in an inert gas atmosphere for later use.
Step two: pretreatment of a quartz tube: a U-shaped quartz tube is adopted, the caliber of the quartz tube is 10-150 mm, the melting point is 1750 ℃, the quartz tube is pretreated, firstly, hydrofluoric acid with the concentration of 25% -30% is used for soaking for 20-30 min, then, deionized water and absolute ethyl alcohol are sequentially used for cleaning, and the quartz tube is placed in a vacuum drying box and dried for 10 hours at the temperature of 150-200 ℃.
Step three: weighing, proportioning and packaging: according to the chemical composition Ge of the prepared Ge-Sb-Se system glass 28- x Sb 12+x Se 60 (x is more than or equal to 0 and less than or equal to 3) calculating the mass of each raw material. The weighing process of the high-purity Ge, sb and Se simple substances is carried out in a dry and clean glove box (firstly, high-purity nitrogen is introduced after vacuum pumping), the raw materials are prevented from being oxidized, a mechanical pump is started to pump out residual air and water vapor on the inner wall of a quartz tube, and a molecular pump is started to seal the quartz tube by using oxyhydrogen flame fusion.
Preferably, the whole process of the third step avoids the inner wall of the quartz tube from being polluted by the sample, the oxyhydrogen flame preheats the outer wall of the quartz tube back and forth, meanwhile, the mechanical pump gradually pumps out residual air and water vapor on the inner wall of the quartz tube, and the mechanical pump pumps the quartz tube to 10 degrees -1 When Pa, the molecular pump is started until the vacuum degree is 10 -5 And sealing the quartz tube by using oxyhydrogen flame at Pa.
Step four: melting: the swinging furnace is characterized in that the temperature of a raw material area is slowly increased to 900-950 ℃ and divided into three gradients, the first gradient is firstly increased from room temperature to 550-650 ℃ at the temperature increase rate of 2-4 ℃/min and then swung in the swinging furnace, the second gradient is increased to 650-750 ℃ at the temperature increase rate of 2-3 ℃/min, the third gradient is increased to 700-950 ℃ at the temperature increase rate of 1-2 ℃/min, the temperature is kept for a sufficient time, so that the raw material is completely melted, and the melting time is 15-20 hours.
Preferably, in the fourth step, the mixture is fully and uniformly mixed, the temperature rising rate is strictly controlled, the quartz tube is prevented from bursting near the melting point and the boiling point of the component with larger vapor pressure, the proper heat preservation can be carried out for 0.5 to 1 hour, meanwhile, the atmosphere temperature is kept consistent with the raw material area, and the finished product area is correspondingly higher than the other two areas by 100 to 200 ℃.
Preferably, in the fourth step, the inclination angle of the rocking furnace is about 45-100 degrees, and the rocking frequency is 8-10 times/min.
Step five: and (3) distillation: adding an impurity removing agent, firstly adopting an open distillation process, and firstly adding TeCl with the mass of 200 ppm-1000 ppm relative to the glass in a weighed quartz tube raw material area 4 The raw material area is 200-300 ℃, the finished product area is 100-200 ℃ higher than the raw material area, the temperature is kept for 1-2 hours, and the oxide layer and the adsorbed water on the surface of the raw material and the structural water in the wall of the quartz tube are pumped out of the tube by a vacuum molecular pump.
Preferably, in said step five, teCl is introduced 4 Can react with H impurities in the glass liquid to generate HCl which is discharged out of the tube through a distillation process, and can effectively reduce the content of the H impurities in the glass.
Preferably, in the fifth step, an Al simple substance with a weight of 2000ppm to 3000ppm of the total weight of the glass is added at the same time, the stage is also divided into three gradients, the first gradient distillation transition stage, the temperature of the finished product area is sharply reduced to 500 ℃ to 550 ℃, the temperature of the furnace top and the temperature of the raw material area are kept to be 900 ℃ to 950 ℃ unchanged, a certain temperature difference, namely a second gradient distillation starting stage, is formed, the temperature of the raw material area and the temperature of the furnace top are simultaneously increased to 1000 ℃ to 1100 ℃, the temperature of the finished product area is kept to be 500 ℃ to 550 ℃, the third gradient complete distillation stage and the third gradient temperature for 18 to 25 hours, and the glass liquid in the raw material area is completely distilled to the finished product area.
Preferably, the distillation in the above stage mainly removes O impurities, and Al reacts with oxygen to form stable Al 2 O 3 Finally, by bulk distillation, al 2 O 3 And C impurities are left in the raw material area due to small saturated vapor pressure, and high-purity glass is obtained in the finished product area.
Step six: in the transition stage, the temperature of the furnace top is reduced to 800-900 ℃, the temperature of the raw materials is reduced to 900-950 ℃, the temperature of the finished product area is increased to 700-750 ℃, and the temperature reduction time in the process is 1-2 hours and is also the early preparation stage of the secondary smelting.
Step seven: secondary smelting: the process is also divided into two gradients, namely a first gradient, wherein the furnace top temperature is maintained at 800-900 ℃, the raw material temperature is maintained at 900-950 ℃, the temperature of a finished product area is increased to 800-900 ℃, and the process time is 1-2 hours. And in the second gradient, the atmosphere of the finished product area and the hearth is kept consistent at 800-900 ℃, the temperature of the raw material area is 100-200 ℃ higher than that of the atmosphere of the finished product area and the hearth, and the glass liquid is obtained by starting a swinging furnace to swing and melt and preserving heat for 2-3 hours at the same time.
Step eight: and (3) cooling: properly adjusting the temperature of the furnace atmosphere and the temperature of the finished product area until the temperature of the furnace atmosphere and the temperature of the finished product area are both reduced to 600-700 ℃, properly reducing the temperature of the raw material area to 700-800 ℃, facilitating discharging, and reducing the temperature for 1-2 hours.
Step nine: righting, standing and discharging: the temperature of the finished product area is 600-700 ℃ consistent with the temperature of the furnace atmosphere, and the finished product area is righted and kept stand for 20-30 min to wait for discharging.
Preferably, the invention adopts air cooling for discharging, adopts special air cooling equipment, changes the traditional point air cooling into surface shape, increases the air cooling area, further enhances the air cooling effect, and is more uniform.
Preferably, the distance l = 5-8 cm from the air cooling end to the center of the glass, the air cooling time t = 3-5 min, and the glass needs to be kept still for 10-20 s in advance.
Step ten: annealing and forming: the invention puts the quartz tube into the temperature 20-40 ℃ lower than the glass transition temperature (Tg), keeps the temperature for 2-3 hours, then anneals for 12-18 hours and slowly reduces the temperature to the room temperature, thus obtaining the high-purity infrared glass.
Compared with the prior art, the invention has the following technical effects:
according to the preparation method of the Ge-Sb-Se system infrared chalcogenide glass, the impurity removing agent is added, and the methods such as distillation and the like are combined, so that the contents of oxide groups and other impurities in a glass finished product are controlled, and the transmission performance of a glass sample in an infrared wavelength region is enhanced; meanwhile, the uniformity of the chemical components of the glass is greatly improved by utilizing secondary melting, and in addition, the defects and residual stress in the glass structure are reduced by combining annealing operation, so that the optical uniformity of the Ge-Sb-Se system infrared glass is improved.
Drawings
FIG. 1 is a flow chart of the production process of infrared glass of Ge-Sb-Se system;
FIG. 2 is a view of a U-shaped pipe fitting made of quartz according to the present invention;
FIG. 3 is a view of a characteristic air cooling apparatus;
FIG. 4 is composition Ge 28 Sb 12 Se 60 Infrared transmission spectrum of glass;
FIG. 5 shows the composition Ge 25 Sb 15 Se 60 Infrared transmission spectrum of glass;
FIG. 6 shows the composition Ge 28 Sb 12 Se 60 Purified and non-purified infrared transmission spectrograms of the glass.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific examples, without however constituting any limitation to the invention, any limited number of modifications being made within the scope of the claims of the invention, which are still within the scope of the claims of the invention.
The preparation method of the infrared chalcogenide glass with the high-purity Ge-Sb-Se system, disclosed by the invention, has the process flow diagram shown in figure 1, and comprises the following steps:
the method comprises the following steps: pretreatment of raw materials: as the raw materials adopt Ge particles, sb particles and Se particles with high purity (99.999 percent), because the metals are easy to absorb moisture or be oxidized, the physical properties of the glass, especially the infrared transmission performance, are seriously influenced by the absorption peaks of Ge-O bonds and Se-H bonds generated by the metals, in order to eliminate the influence of the impurities to the maximum extent, the Ge, sb and Se are dried firstly, then the raw materials are purified by a distillation method to remove moisture and other impurities, and the purified raw materials are stored in an inert gas environment for standby.
Step two: pretreatment of a quartz tube: the invention adopts a U-shaped quartz tube with a special structure, wherein the structure of the quartz tube is shown in figure 2, the caliber of the quartz tube is 10-150 mm, the quartz tube has stronger high temperature resistance, the melting point of the quartz tube is 1750 ℃, whether the tube wall of the quartz tube has air bubbles, cracks or other defects is firstly carefully checked, so as to avoid the explosion of the quartz tube in the high-temperature melting process, the newly purchased quartz tube is required to be pretreated by soaking the newly purchased quartz tube for 20-30 min by using hydrofluoric acid with the concentration of 25-30 percent, then the newly purchased quartz tube is cleaned by using deionized water and absolute ethyl alcohol in sequence, and the quartz tube is placed in a vacuum drying box and dried for 10 hours at the temperature of 150-200 ℃.
Step three: weighing, proportioning and packaging: according to the chemical composition Ge of the prepared Ge-Sb-Se system glass 28- x Sb 12+x Se 60 (x is more than or equal to 0 and less than or equal to 3) calculating the mass of each raw material. The weighing process of high-purity Ge, sb and Se simple substances is carried out in a dry and clean glove box (firstly, high-purity nitrogen is pumped in after vacuum pumping) to prevent raw materials from being oxidized. The inner wall of the quartz tube is prevented from being polluted by a sample in the whole process, oxyhydrogen flame preheats the outer wall of the quartz tube back and forth, air and water vapor remained on the inner wall of the quartz tube are gradually pumped out by a mechanical pump, and the mechanical pump is pumped to vacuum degree of 10 -1 When Pa, the molecular pump is started until the vacuum degree is 10 -5 And sealing the quartz tube by using oxyhydrogen flame at Pa.
Step four: melting: the rocking furnace (the inclination angle is about 45-100 degrees, the rocking frequency is 8-10 times/min) is characterized in that the raw material zone is slowly heated to 900-950 ℃, the temperature is divided into three gradients, the first gradient is heated from room temperature to 550-650 ℃ (the heating rate is 2-4 ℃/min) and then the rocking furnace is rocked, the second gradient is 650-750 ℃ (the heating rate is 2-3 ℃/min), the third gradient is 700-950 ℃ (the heating rate is 1-2 ℃/min) and is smelted nearby each raw material, the temperature is kept for enough time to ensure the raw materials are completely melted, the smelting time is 15-20 hours, the temperature is fully and uniformly mixed, the temperature is strictly controlled, the quartz tube is prevented from bursting nearby the melting point and the boiling point of the component with larger steam pressure, the temperature can be properly kept for 0.5-1 hour, meanwhile, the atmosphere temperature is kept consistent with the raw material zone, and the finished product zone is 100-200 ℃ higher than the other two zones.
Step five: and (3) distillation: adding specific impurity removing agent in the weighing process in the third step, firstly adopting open distillation process, and firstly adding 200-1000 ppm of TeCl into the weighed quartz tube raw material area 4 (the content depends on the quality of the glass), the raw material area is 200-300 ℃, the finished product area is 100-200 ℃ higher than the raw material area, the temperature is kept for 1-2 hours, and the oxide layer and the adsorbed water on the surface of the raw material and the structural water in the wall of the quartz tube are pumped out of the tube by a vacuum molecular pump. TeCl introduced by the process 4 The glass can react with H impurities in glass liquid to generate HCl which is discharged out of the tube through a distillation process, so that the content of the H impurities in the glass can be effectively reduced; and simultaneously adding an Al simple substance (4N) with the weight of 2000ppm to 3000ppm of the total weight of the glass, wherein the stage is also divided into three gradients, the first gradient distillation transition stage is that the temperature of a finished product area is sharply reduced to 500 ℃ to 550 ℃, the temperature of a furnace top and the temperature of a raw material area are kept unchanged (900 ℃ to 950 ℃), a certain temperature difference is formed, namely the second gradient distillation starting stage is formed, the temperature of the raw material area and the temperature of the furnace top are simultaneously increased to 1000 ℃ to 1100 ℃, the temperature of the finished product area is kept at 500 ℃ to 550 ℃, the third gradient complete distillation stage is that the third gradient temperature is kept at the second gradient temperature for 18 to 25 hours, and the glass liquid in the raw material area is completely distilled to the finished product area. The distillation in this stage mainly removes O impurities, al reacts with oxygen to produce stable Al 2 O 3 Finally, by bulk distillation, al 2 O 3 And C impurities are left in the raw material area due to small saturated vapor pressure, and high-purity glass is obtained in the finished product area.
Step six: in the transition stage, the temperature of the furnace top is reduced to 800-900 ℃, the temperature of the raw materials is reduced to 900-950 ℃, the temperature of the finished product area is increased to 700-750 ℃, the temperature reduction time in the process is 1-2 hours, and the method is also an early preparation stage of secondary smelting.
Step seven: secondary smelting: the process is also divided into two gradients, the first gradient, the furnace top temperature is maintained at (800 ℃ -900 ℃), the raw material temperature is maintained at (900 ℃ -950 ℃), the finished product area is heated to (800 ℃ -900 ℃), and the process time is 1-2 hours. And in the second gradient, the atmosphere of the finished product area and the furnace chamber is kept consistent (800-900 ℃), and the temperature of the raw material area is higher than that of the atmosphere of the finished product area and the furnace chamber (100-200 ℃), and the raw material area is started to swing and melt and is kept warm for 2-3 hours, so that the glass liquid which is fully and uniformly mixed is obtained.
Step eight: and (3) cooling: the temperature of the furnace atmosphere and the temperature of the finished product area are properly adjusted until the temperature of the furnace atmosphere and the temperature of the finished product area are both reduced to 600-700 ℃, the temperature of the raw material area is properly reduced to 700-800 ℃, the raw material area is convenient to discharge, and the temperature is reduced for 1-2 hours.
Step nine: righting, standing and discharging: the temperature of the finished product area is 600-700 ℃ consistent with the temperature of the furnace atmosphere, and the finished product area is righted and kept stand for 20-30 min to wait for discharging. The invention adopts air cooling for discharging, and the special air cooling equipment structure is changed into a surface shape from the traditional point air cooling as shown in figure 3, so that the air cooling area is increased, the air cooling effect is further enhanced, and the uniformity is better. The distance l between the air cooling end and the center of the glass is 5-8 cm, and the air cooling time t = 3-5 min needs to be kept still for 10-20 s in advance.
Step ten: annealing and forming: in order to eliminate residual stress in glass, improve the quality of a glass sample and avoid cracking, crushing and other phenomena of the glass in the later processing process, a quenched quartz tube needs to be placed into an annealing furnace for annealing so as to eliminate the temperature gradient of each component of the glass and release internal stress, the quartz tube is placed below the glass transition temperature (Tg) by 20-40 ℃, the temperature is kept for 2-3 hours, and then the quartz tube is annealed for 12-18 hours and slowly cooled to room temperature, so that the high-purity infrared glass is obtained.
The following examples 1-3 were all operated according to the indicated process flow.
Example 1: the glass component is Ge 28 Sb 12 Se 60 Infrared chalcogenide glass
After the raw materials and the quartz tube are pretreated according to the production process flow, 500g of batch materials are prepared in the example, the quality of each raw material is calculated, then the raw materials are respectively filled into a raw material area at one side of a quartz U-shaped tube by using a quartz funnel, and 400ppm of TeCl is added 4 And an Al simple substance (4N) with the total weight of 3000ppm of the batch; heating the raw material area to 250 ℃, heating the finished product area on the other side of the quartz tube to 350 ℃, preserving the heat for 1 hour, and pumping the oxide layer and the adsorbed water on the surface of the raw material and the structural water in the wall of the quartz tube out of the tube through a vacuum molecular pump. The mechanical pump is vacuumized to 10 -1 When Pa is needed, the molecular pump is started,until the vacuum degree is 10 -5 And sealing the quartz tube by using oxyhydrogen flame at Pa.
The first stage is as follows: the glass melting stage, specifically the melting stage of the single substance of the raw material at one side of the U-shaped tube, is divided into three gradients. A first gradient, wherein the heating rate is 3.22 ℃/min (20 ℃→ 600 ℃, the swing starts after the heating is carried out for 3h, and the temperature is kept for 30 min); the second gradient is a third gradient with the temperature rise rate of 2.5 ℃/min (600 ℃ → 750 ℃, 1h, 30min of heat preservation), and the temperature rise rate of 1.67 ℃/min (750 ℃ → 950 ℃,2h of heat preservation, 15h of heat preservation, wherein the raw materials are completely melted and fully and uniformly mixed within the temperature range). At the moment, the temperature of the furnace top atmosphere in the swinging hearth is kept consistent with the melting temperature of the simple substance of the raw material, which is beneficial to the melting of the simple substance. The other side of the U-shaped tube is a glass product area, and the temperature of each gradient is kept 100 ℃ higher than the temperature of the raw materials and the temperature of the furnace top in the stage.
And a second stage: distilling stage, distilling the molten glass completely melted and uniformly mixed in the U-shaped tube to a glass product area with a certain temperature difference, and adding Al in advance 2 O 3 And C is remained in the raw material melting area due to small saturated vapor pressure, and high-purity glass is obtained on the other side of the U-shaped tube. This phase also divides into three gradients. In the first gradient, distillation transition stage, the cooling rate of the finished product area is 8.33 ℃/min (1050 ℃ → 550 ℃, cooling for 1h, and stopping swinging), while the smelting area and the furnace top atmosphere are kept unchanged (950 ℃, heat preservation for 1 h), and because the temperature of the finished product area is sharply reduced, the temperature of the raw material area and the furnace top atmosphere is higher than that of the finished product area, the raw material steam slowly enters the finished product area, and distillation is started; a second gradient, namely a distillation starting stage, wherein the temperatures of the raw material zone and the furnace top are simultaneously increased to 1100 ℃ (950 ℃ → 1100 ℃, and the temperature is increased for 1 hour), the temperature of the finished product zone is kept at 550 ℃, and the distillation is started; and a third gradient, namely a complete distillation stage, wherein the temperatures of the raw material area and the furnace top are maintained at 1100 ℃, the temperature of the finished product area is maintained at 550 ℃, and the process can ensure that the raw materials are completely distilled to the finished product area after heat preservation for 19.5 hours.
And a third stage: in the transition stage, the temperature of the furnace top is reduced to 850 ℃ (1100 ℃ → 850 ℃,60 min), the temperature of the raw material zone is reduced to 950 ℃ (1100 ℃ → 950 ℃,60 min), and the temperature of the finished product zone is increased to 700 ℃ (550 ℃ → 700 ℃,60 min), and the process is also the early preparation stage of the secondary smelting.
A fourth stage: a secondary smelting stage, which is divided into two gradients, wherein the first gradient finished product area is in a temperature rise stage (700 ℃ → 850 ℃ and 1.5 h), the temperature of the atmosphere of a hearth above the finished product area is maintained at 850 ℃ and 1.5h, and when the actual temperatures of the two are consistent, the swinging furnace is started again to swing; in the second gradient complete melting and homogenizing stage, the atmosphere temperature of the finished product area and the hearth is maintained at 850 ℃ for 2h, and the temperature of the raw material area is maintained at 950 ℃ in the process, so that complete secondary melting is ensured.
The fifth stage: and in the temperature reduction stage, the furnace atmosphere temperature and the finished product area temperature are properly adjusted until both are reduced to 650 ℃, the raw material area temperature is properly reduced to 750 ℃, discharging is facilitated, and the temperature is reduced for 1 hour.
The sixth stage: and (4) righting and standing, preparing for a discharging stage, righting and standing the swing furnace for 30min, keeping the temperature of a finished product area and the temperature of the furnace atmosphere at 650 ℃, and waiting for discharging. The glass is molded by adopting a characteristic air cooling process, the distance l between an air cooling end and the center of the glass is =5.5cm, the air cooling time is 3.5min, and the glass needs to be kept stand for 15s in advance.
A seventh stage: and in the annealing stage, the annealing temperature is 280 ℃, the temperature is kept for 2 hours, and the temperature is slowly reduced to the room temperature for 18 hours, so that the high-purity infrared glass is obtained.
Example 2: the glass component is Ge 25 Sb 15 Se 60 Infrared chalcogenide glass
After the raw materials and the quartz tube are pretreated according to the production process flow, 600g of batch materials are prepared in the example, the quality of each raw material is calculated, then the raw materials are respectively filled into a raw material area at one side of a quartz U-shaped tube by using a quartz funnel, and then 500ppm of TeCl is added 4 And 2000ppm of Al simple substance (4N) based on the total weight of the batch; heating the raw material area to 200 ℃, heating the finished product area on the other side of the quartz tube to 300 ℃, preserving the heat for 1 hour, and pumping the oxide layer and the adsorbed water on the surface of the raw material and the structural water in the wall of the quartz tube out of the tube through a vacuum molecular pump. The mechanical pump is vacuumized to 10 -1 When Pa, the molecular pump is started until the vacuum degree is 10 -5 And sealing the quartz tube by using oxyhydrogen flame at Pa.
The first stage is as follows: the glass melting stage, specifically the melting stage of the single substance of the raw material at one side of the U-shaped tube, is divided into three gradients. A first gradient, wherein the heating rate is 2.94 ℃/min (20 ℃→ 550 ℃, the swing is started after the heating is carried out for 3h, and the temperature is kept for 30 min); the second gradient is a third gradient with the temperature rise rate of 2.5 ℃/min (550 ℃ → 700 ℃,1 hour of temperature rise and 30 minutes of heat preservation), and the temperature rise rate of 1.67 ℃/min (700 ℃ → 900 ℃,2 hours of temperature rise and 15 hours of heat preservation, wherein the raw materials are completely melted and fully and uniformly mixed within the temperature range). At the moment, the temperature of the furnace top atmosphere in the swinging hearth is kept consistent with the melting temperature of the simple substance of the raw material, which is beneficial to the melting of the simple substance. The other side of the U-shaped tube is a glass product area, and the temperature of each gradient is kept 150 ℃ higher than the temperature of the raw materials and the temperature of the furnace top in the stage.
And a second stage: distilling stage, distilling the molten glass completely melted and uniformly mixed in the U-shaped tube to a glass product area with a certain temperature difference, and adding Al in advance 2 O 3 And C is remained in the raw material melting area due to small saturated vapor pressure, and high-purity glass is obtained on the other side of the U-shaped tube. This phase also divides into three gradients. In the first gradient, distillation transition stage, the cooling rate of the finished product area is 8.33 ℃/min (1050 ℃ → 550 ℃, cooling for 1h, and stopping swinging), while the atmosphere of the raw material area and the furnace top is kept unchanged (900 ℃, heat preservation for 1 h), and because the temperature of the finished product area is sharply reduced, the temperature of the atmosphere of the raw material area and the furnace top is higher than that of the finished product area, the raw material steam slowly enters the finished product area, and distillation is started; a second gradient, namely a distillation starting stage, wherein the temperatures of the raw material area and the furnace top are simultaneously increased to 1000 ℃ (900 ℃ → 1000 ℃, and the temperature is increased for 1 hour), the temperature of the finished product area is kept at 550 ℃, and the distillation is started; and a third gradient, namely a complete distillation stage, wherein the temperatures of the raw material area and the furnace top are maintained at 1000 ℃, the temperature of the finished product area is maintained at 550 ℃, and the process can ensure that the raw materials are completely distilled to the finished product area after heat preservation for 20 hours.
And a third stage: in the transition stage, the temperature of the furnace top is reduced to 800 ℃ (1000 ℃ → 800 ℃ and 60 min), the temperature of the raw material zone is reduced to 900 ℃ (1000 ℃ → 900 ℃ and 60 min), and the temperature of the finished product zone is increased to 650 ℃ (550 ℃ → 650 ℃ and 60 min), and the process is also the early preparation stage of the secondary smelting.
A fourth stage: a secondary smelting stage, which is divided into two gradients, wherein a first gradient finished product area heating stage (650 ℃→ 800 ℃ and 1.5 h), the temperature of the furnace atmosphere above a finished product area is maintained at 800 ℃ for 1.5h, and when the actual temperatures of the two are consistent, the swinging furnace is started again to swing; in the second gradient complete melting homogenization stage, the atmosphere temperature of the finished product area and the furnace chamber is maintained at 800 ℃ for 2 hours, the temperature of the raw material area is maintained at 900 ℃ in the process, and the complete secondary melting is ensured.
The fifth stage: and in the cooling stage, the temperature of the furnace atmosphere and the temperature of the finished product area are properly adjusted until the temperature of the furnace atmosphere and the temperature of the finished product area are both reduced to 600 ℃, the temperature of the raw material area is properly reduced to 700 ℃, discharging is facilitated, and the temperature is reduced for 1 hour.
The sixth stage: and (3) righting and standing, in preparation of a discharging stage, righting and standing the swing furnace for 20min, wherein the temperature of a finished product area is 600 ℃ consistent with the temperature of the furnace atmosphere, and waiting for discharging. The glass is molded by adopting a characteristic air cooling process, wherein the distance l between an air cooling end and the center of the glass is =7.5cm, the air cooling time is 2min, and the glass needs to be kept stand for 20s in advance.
A seventh stage: and in the annealing stage, the annealing temperature is 270 ℃, the temperature is kept for 2 hours, and the temperature is slowly reduced to the room temperature for 12 hours, so that the high-purity infrared glass is obtained.
Example 3: comparative example, glass composition Ge 28 Sb 12 Se 60 Non-distillable infrared chalcogenide glass
After the raw materials and the quartz tube are pretreated according to the production process flow, 100g of batch materials are prepared in the example, the quality of each raw material is calculated, then the raw materials are respectively filled into the quartz single tube by using a quartz funnel, when the vacuum degree is 10-1Pa by using a mechanical pump, a molecular pump is started, and the quartz tube is sealed by using oxyhydrogen flame until the vacuum degree is 10-5 Pa.
The first stage is as follows: a temperature rising stage: the heating rate is 3.33 ℃/min (0 ℃→ 600 ℃, the heating rate is 3h, the temperature begins to swing at 2h, and the temperature is kept for 30 min).
And a second stage: a temperature rising stage: the heating rate is 2.5 ℃/min (600 ℃ → 750 ℃, heating for 1h, and keeping the temperature for 30 min).
And a third stage: a temperature rising stage: the heating rate is 1.33 ℃/min (750 ℃→ 950 ℃, heating time is 2.5 h).
A fourth stage: and in the heat preservation smelting stage, the heat preservation time is 12 hours, and the raw materials are completely melted and fully and uniformly mixed.
The fifth stage: and in the cooling stage, the temperature is reduced by 5 ℃/min (950 ℃ → 650 ℃, the temperature is reduced for 1h, and the swing strengthening and the standing are stopped).
The sixth stage: after the rocking is stopped, the rocking furnace is righted and kept stand for 30min, and the steel plate is immediately taken out of the furnace for cooling at 650 ℃.
And a seventh stage: and in the annealing stage, the annealing temperature is 280 ℃, the temperature is kept for 2 hours, and the temperature is slowly reduced to the room temperature for 12 hours, so that the high-purity infrared glass is obtained.
The glass samples of examples 1-2 and comparative examples were compared for performance testing. FIGS. 4 and 5 are Ge 28 Sb 15 Se 60 And Ge 25 Sb 15 Se 60 An infrared transmission spectrum of the glass sample; fig. 6 is a sample of a comparative example that did not include distillation and purification processes. The thickness of the glass sample was measured to be 5mm. In the sample of example 1, the more than 50% transmission wavelength is 14 μm, the glass sample of the present invention can maintain the more than 50% light transmittance for the infrared region of the wavelength to the vicinity of 14 μm, and the fluctuation range of the light transmittance property is small; example 2 sample, over 50% transmitted infrared region with wavelength to 13 μm. However, the comparative example, which is a glass sample not subjected to distillation purification, shows a rapid attenuation of transmittance in the infrared region wavelength range (. About.14 μm) and a large fluctuation in optical properties due to the presence of the oxidized groups OH, ge-O in the final glass product.
The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the scope of the present invention is defined by the claims. Various modifications and equivalents may be made by those skilled in the art within the spirit and scope of the present invention, and such modifications and equivalents should also be considered as falling within the scope of the present invention.
Claims (6)
1. A preparation method of high-purity Ge-Sb-Se system infrared chalcogenide glass comprises the following steps:
the method comprises the following steps: pretreatment of raw materials: the raw materials adopt high-purity (99.999%) Ge particles, sb particles and Se particles for pretreatment;
step two: pretreatment of a quartz tube: a U-shaped quartz tube is adopted, the caliber of the quartz tube is 10-150 mm, the melting point is 1750 ℃, the quartz tube is pretreated, firstly, hydrofluoric acid with the concentration of 25% -30% is used for soaking for 20-30 min, then, deionized water and absolute ethyl alcohol are sequentially used for cleaning, and the quartz tube is placed in a vacuum drying box and dried for 10 hours at the temperature of 150-200 ℃;
step three: weighing, proportioning and packaging: according to the chemical composition Ge of the prepared Ge-Sb-Se system glass 28-x Sb 12+ x Se 60 X is more than or equal to 0 and less than or equal to 3, the mass of each raw material is calculated, the weighing process of high-purity Ge, sb and Se simple substances is carried out in a dry and clean glove box, the raw materials are prevented from being oxidized by vacuumizing and then introducing high-purity nitrogen, a mechanical pump is started to pump out residual air and water vapor on the inner wall of the quartz tube, a molecular pump is started, and the quartz tube is sealed by oxyhydrogen flame fusion; in the third step, oxyhydrogen flame is used for preheating the outer wall of the quartz tube back and forth, simultaneously, a mechanical pump gradually pumps out air and water vapor remained on the inner wall of the quartz tube, and the mechanical pump pumps the quartz tube to 10 degrees -1 When Pa, the molecular pump is started until the vacuum degree is 10 -5 Sealing the quartz tube by using oxyhydrogen flame in a fusing way when the pressure is Pa;
step four: melting: the raw material area is slowly heated to 900-950 ℃ by the swinging furnace, the temperature is divided into three gradients, the first gradient is heated to 550-650 ℃ from room temperature at the heating rate of 2-4 ℃/min, then swinging of the swinging furnace is carried out, the temperature is heated to 650-750 ℃ at the heating rate of 2-3 ℃/min by the second gradient, the temperature is heated to 700-950 ℃ at the heating rate of 1-2 ℃/min by the third gradient, the temperature is kept for a sufficient time, so that the raw material is completely melted, and the melting time is 15-20 hours;
step five: and (3) distillation: adding an impurity removing agent, firstly adopting an open distillation process, and firstly adding TeCl with the mass of 200 ppm-1000 ppm relative to the glass in a weighed quartz tube raw material area 4 The temperature of the raw material area is 200-300 ℃, the temperature of the finished product area is 100-200 ℃ higher than that of the raw material area, the temperature is kept for 1-2 hours, and an oxide layer and adsorbed water on the surface of the raw material and structural water in the wall of the quartz tube are pumped out of the tube by a vacuum molecular pump; in the fifth step, an Al simple substance with the weight of 2000ppm to 3000ppm of the total weight of the glass is added, the stage is also divided into three gradients, the first gradient distillation transition stage, the temperature of the finished product area is sharply reduced to 500 ℃ to 550 ℃, the temperature of the furnace top and the temperature of the raw material area are kept unchanged at 900 ℃ to 950 ℃, a certain temperature difference is formed, namely the second gradient distillation starting stage, the temperatures of the raw material area and the furnace top are simultaneously increased to 1000 ℃ to 1100 ℃, and the finished product is formedThe temperature of the zone is maintained at 500-550 ℃, the third gradient complete distillation stage, the third zone is maintained at the second gradient temperature for 18-25 hours, and the glass liquid in the raw material zone is completely distilled to a finished product zone;
step six: the transition stage, wherein the temperature of the furnace top is reduced to 800-900 ℃, the temperature of the raw materials is reduced to 900-950 ℃, the temperature of the finished product area is increased to 700-750 ℃, the temperature reduction time of the process is 1-2 hours, and the process is also an early preparation stage of secondary smelting;
step seven: secondary smelting: the method comprises the following steps of dividing the furnace into two gradients, namely a first gradient, maintaining the furnace top temperature at 800-900 ℃, maintaining the raw material temperature at 900-950 ℃, heating a finished product area to 800-900 ℃, keeping the process time at 1-2 hours, and a second gradient, maintaining the atmosphere of the finished product area and the furnace hearth to be consistent at 800-900 ℃, and maintaining the temperature of the raw material area to be 100-200 ℃ higher than that of the finished product area and the furnace hearth, starting a swinging furnace, swinging, melting and simultaneously preserving heat for 2-3 hours to obtain fully and uniformly mixed molten glass;
step eight: and (3) cooling: properly adjusting the temperature of the furnace atmosphere and the temperature of the finished product area until the temperature of the furnace atmosphere and the temperature of the finished product area are both reduced to 600-700 ℃, properly reducing the temperature of the raw material area to 700-800 ℃, facilitating discharging, and reducing the temperature for 1-2 hours;
step nine: righting, standing and discharging: the temperature of the finished product area is 600-700 ℃ consistent with the temperature of the furnace atmosphere, and the finished product area is righted and kept stand for 20-30 min to wait for discharging;
step ten: annealing and forming: putting the quartz tube below the glass transition temperature (Tg) by 20-40 ℃, preserving the temperature for 2-3 hours, annealing for 12-18 hours, and slowly cooling to room temperature to obtain the high-purity infrared glass.
2. The method for preparing high-purity Ge-Sb-Se system infrared chalcogenide glass according to claim 1, wherein the raw material pretreatment in the step one includes but is not limited to drying Ge, sb and Se, purifying the raw material by distillation to remove moisture and other impurities, and storing the purified raw material in an inert gas environment for later use.
3. The method for preparing high-purity Ge-Sb-Se system infrared chalcogenide glass according to claim 1, wherein in the fourth step, the temperature rise rate is strictly controlled by fully and uniformly mixing, the temperature is properly kept for 0.5 to 1 hour near the melting point and the boiling point of the component with larger vapor pressure, meanwhile, the atmosphere temperature is kept consistent with that of the raw material area, and the finished product area is correspondingly higher than that of the other two areas by 100 to 200 ℃.
4. The method for preparing high-purity Ge-Sb-Se system infrared chalcogenide glass according to claim 1, wherein in the fourth step, the inclination angle of the rocking furnace is 45-100 degrees, and the rocking frequency is 8-10 times/min.
5. The method for preparing the high-purity Ge-Sb-Se system infrared chalcogenide glass according to the claim 1, wherein in the ninth step, the sheet air cooling is performed by adopting air cooling furnace discharge.
6. The method for preparing high-purity Ge-Sb-Se system infrared chalcogenide glass according to claim 5, wherein the distance l = 5-8 cm from the air cooling end to the center of the glass, the air cooling time t = 3-5 min, and the glass needs to be kept still for 10-20 s in advance.
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