CN116161959A - Method for preparing wide-spectrum high-strength zinc sulfide optical material - Google Patents
Method for preparing wide-spectrum high-strength zinc sulfide optical material Download PDFInfo
- Publication number
- CN116161959A CN116161959A CN202211561097.4A CN202211561097A CN116161959A CN 116161959 A CN116161959 A CN 116161959A CN 202211561097 A CN202211561097 A CN 202211561097A CN 116161959 A CN116161959 A CN 116161959A
- Authority
- CN
- China
- Prior art keywords
- zns
- powder
- box
- zinc sulfide
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052984 zinc sulfide Inorganic materials 0.000 title claims abstract description 83
- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000003287 optical effect Effects 0.000 title claims abstract description 33
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000001228 spectrum Methods 0.000 title claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 52
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 238000007731 hot pressing Methods 0.000 claims abstract description 24
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 49
- 239000007789 gas Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 10
- 230000005540 biological transmission Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 4
- 230000002093 peripheral effect Effects 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000000280 densification Methods 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 3
- 238000000411 transmission spectrum Methods 0.000 abstract 1
- 238000002834 transmittance Methods 0.000 description 10
- 230000007547 defect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 210000003437 trachea Anatomy 0.000 description 2
- 201000004569 Blindness Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000003031 feeding effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/547—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on sulfides or selenides or tellurides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9646—Optical properties
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a method for preparing wide-spectrum high-strength zinc sulfide optical material, which is characterized in that ZnS powder is firstly subjected to heat treatment to remove impurities, and As is added 2 S 3 As sintering aid, hot pressing and hot isostatic pressing are carried out at a lower temperature (less than or equal to 650 ℃) and a moderate pressure (less than or equal to 100 MPa), the prepared material has fine crystal grains and excellent mechanical property, meanwhile, high densification of the material is realized, scattering and absorption of the material are reduced, the transmission spectrum of the material is expanded, and the material has good optical property in a wave band of 0.4-12 mu m, so that the wide-spectrum high-strength ZnS material is obtained. The invention has simple process, low requirement on equipment and low cost, and is suitable for mass production.
Description
Technical Field
The invention relates to the technical field of optical material preparation, in particular to a method for preparing a broad-spectrum high-strength zinc sulfide optical material.
Background
With the development of modern military science and technology, advanced technologies such as infrared stealth and laser blindness greatly reduce actual combat effectiveness of a traditional photoelectric detection system, and in order to adapt to the continuously developed countermeasure form, multi-band composite imaging detection becomes the development direction of the military photoelectric detection system, so that optical materials used by the system are required to have the performances of wide spectrum transmission, all-weather work and the like, so that the requirements of high precision, light weight and all weather of photoelectric detection equipment are met. The zinc sulfide (ZnS) II-VI wide bandgap semiconductor compound has a bandgap Eg=3.5 eV, has good transmittance to light of 0.4-12 mu m, and has higher transmittance in the bands of visible light, near infrared, mid infrared, far infrared and the like, so that the zinc sulfide II-VI wide bandgap semiconductor compound is a preferred material of a multiband composite window.
The main preparation methods of military ZnS optical windows are Hot Pressing (HP) and Chemical Vapor Deposition (CVD). HP-ZnS and CVDZnS have excellent mechanical properties, but have poor transmittance in the visible light band and the near infrared band, and cannot meet the use requirements of the multiband composite window.
Chinese patent CN102531040a proposes a method for preparing multispectral ZnS: the CVDZnS is processed by using the hot isostatic pressing technology (HIP) to obtain multispectral ZnS (M-ZnS), and the multispectral ZnS has good optical performance in the wave band of 0.4-12 mu M, but after the HIP is processed by adopting the high-temperature and high-pressure technology, the crystal grains of the material are increased from average 3-10 mu M (CVDZnS) to average 70-100 mu M (M-ZnS), so that the hardness of the material is reduced from 230kg/mm < 2 > -160 kg/mm < 2 >, the bending strength is reduced from 103 Mpa-70 MPa, and the good mechanical performance of the CVDZnS is lost.
In the preparation process of HP-ZnS, the main factors influencing the material performance are as follows: (1) ZnS powder often contains SO 4 2- 、O 2- 、OH - S and S 2- Extrinsic absorption by impurity defects such as vacancies; (2) Scattering caused by micro-pores existing in ZnS in the hot pressing process; (3) Density non-uniformity that may be caused during hot pressing thus leads to optical non-uniformity; (4) The ZnS after hot pressing is adhered with the die, micro cracks are introduced during demolding to reduce mechanical properties, and the release agent is diffused into ZnS under high temperature and high pressure to cause pollution.
Chinese patent CN103466687a discloses a method for improving optical performance by treating HP-ZnS using Hot Isostatic Pressing (HIP), in which high temperature and high pressure technology is used, adhesion between ZnS and a hot press mold during hot pressing and contamination of ZnS by a release agent are unavoidable.
Disclosure of Invention
The invention aims to solve the technical problems and provide a method for preparing a wide-spectrum high-strength zinc sulfide optical material, which has wide-spectrum transmission characteristics and good optical performance in a wave band of 0.4-12 mu m while maintaining excellent mechanical properties of HP-ZnS.
In order to solve the technical problems, the invention provides a method for preparing a broad-spectrum high-strength zinc sulfide optical material, which comprises the following steps:
a. placing ZnS powder into a vacuum heat treatment furnace, vacuumizing the vacuum heat treatment furnace to be less than or equal to 10Pa, heating to 350-550 ℃, maintaining for 1-2H, and then introducing H 2 S gas and H 2 Mixed gas of gases, H 2 S：H 2 The molar ratio of the components is 3-6:1, the components are kept for 2-3h, cooled to room temperature and taken out for standby;
b. the ZnS powder after treatment and As 2 S 3 Powder mixing, as 2 S 3 : zns=0.5-1.2 wt%, yielding ZnS and As 2 S 3 Is a mixed powder of (a) and (b);
c. loading the mixed powder into a mold, loading the mold into a vacuum hot-pressing furnace, pre-pressing the powder, keeping the pressure at 40-60MPa, vacuumizing the hot-pressing furnace to be less than or equal to 10Pa, heating to 250-350 ℃, keeping the temperature for 1-2h, then increasing the pressure to 70-100MPa, keeping the heating temperature at 500-650 ℃ for 4-6h, cooling to the room temperature, and taking out ZnS blanks;
d. placing the ZnS blank into a hot isostatic pressing furnace for hot isostatic pressing treatment, wherein the working gas is Ar, the pressure is 70-100MPa, the temperature is 500-650 ℃ and is kept for 10-50h, and cooling to room temperature and taking out to obtain the wide-spectrum high-strength ZnS material.
Further, in a, the heating temperature was 420 ℃.
Further, in a, H 2 S：H 2 =4:1 molar ratio.
Further, in b, as 2 S 3 ：ZnS＝0.6wt％。
Further, in d, the hot isostatic pressing furnace is vacuumized to 40Pa, ar gas is filled in the furnace, the temperature is raised after the pressure reaches 40MPa, the temperature is raised to 650 ℃ at the speed of 15 ℃/min, the pressure is raised to 90MPa in the temperature raising process, the furnace is kept for 10 hours, and finally the furnace is cooled to the room temperature at the speed of 150 ℃/h.
Further, in b, znS powder and As 2 S 3 The powder is mixed by a powder mixing device.
Further, powder mixing arrangement includes the mixing box, the mixing box cross-section is the U type, be provided with the discharge opening in the middle of the mixing box bottom, the mixing box top is provided with the case lid, the case lid is provided with the reinforced box on the surface towards the mixing incasement, the reinforced box passes through the trachea and is connected with the air supply, be provided with discharge gate and air inlet on the reinforced box, still be provided with the mixing stirring leaf in the mixing box, the mixing stirring leaf is connected with driving motor.
Further, the charging box comprises a top cover and a detachable box body, the top cover is fixed on the box cover, an air inlet pipe is arranged in the middle of the top cover, the air inlet pipe is an air inlet of the charging box, and the number of the discharge holes is multiple and uniformly arranged on the outer peripheral surface of the detachable box body.
Further, the number of the feeding boxes is multiple, and an electromagnetic valve is arranged between the air source and the air pipe.
The invention has the beneficial effects that:
(1) ZnS powder material is processed in H 2 S and H 2 Heat treatment is carried out in the mixed gas of (a) to reduce SO 4 2- 、O 2- 、OH - The impurity defects are overcome, the absorption caused by the impurity defects is reduced, and the optical performance of the material is improved;
(2) As is added into ZnS powder 2 S 3 As As sintering aid under hot pressing ZnS process conditions 2 S 3 The liquid phase is formed, so that the mass transfer mode of the system is mainly viscous flow mass transfer, the energy required by densification is reduced, the process that pores are discharged out of the body through ZnS crystal boundaries is promoted, the high densification of ZnS is realized at lower temperature and pressure, the density of micro-pores is greatly reduced, the scattering of materials is reduced, and the visible and near infrared band transmittance of the materials is remarkably improved;
(3) Under hot-pressing ZnS process conditions, metallic Zn can exist in the form of ions in As 2 S 3 In the network structure, not only can reduce SO 4 2- 、O 2- 、OH - S vacancy caused by the existence of impurity defects, and As can be further caused 2 S 3 The network structure of the (C) is kept stable under the high-temperature condition;
(4) Compared with other technologies, the preparation process adopts lower temperature (less than or equal to 650 ℃) and moderate pressure (less than or equal to 100 MPa), avoids the influence of the adhesion problem of a die and ZnS on the performance, and particularly has small crystal grains and average grain size of 5-10 mu m due to lower temperature, thereby maintaining good mechanical properties of the HP-ZnS material: the hardness of the material is not less than 230kg/mm < 2 >, and the bending strength is not less than 100Mpa;
(5) The hot isostatic pressing treatment is carried out on the ZnS after the hot pressing, so that the density non-uniformity of a large-size product or a hood-type product caused by the difference of different position pressures in the hot pressing process is avoided, the uniformity of the material is improved, and the optical performance of the material is further improved;
(6) The invention has simple process, low requirement on equipment and low cost, and is suitable for mass production.
Drawings
FIG. 1 is a graph showing the results of transmittance test of ZnS prepared by the conventional hot pressing method and the hot pressing method of the invention in the infrared band of 400-1100 nm;
FIG. 2 is a graph showing the results of transmittance test of ZnS prepared by the conventional hot pressing method and the hot pressing method of the present invention in the infrared band of 2-14 μm;
FIG. 3 is a schematic view of the stirring device of the present invention;
FIG. 4 is a schematic view of the back structure of FIG. 3;
FIG. 5 is an enlarged schematic view of a portion of the powder feeding device of the present invention;
FIG. 6 is a schematic cross-sectional view of the feed cassette of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Embodiment case 1:
one embodiment of the method of the invention for preparing a broad spectrum high strength zinc sulfide optical material;
firstly, znS powder is put into a vacuum heat treatment furnace, vacuumized to 8Pa, started to be heated to 420 ℃ and kept for 1H, and then H is introduced 2 S gas and H 2 Mixed gas of gases, H 2 S：H 2 =4:1 (molar ratio), total gas flow of 1L/min, holding for 2H, cooling to room temperature at 200 ℃/H, taking out for use, and passing through the gas flow path under H 2 S and H 2 Heat treatment is carried out in the mixed gas of (a) to reduce SO 4 2- 、O 2- 、OH - And the impurity defects are overcome, the absorption caused by the impurity defects is reduced, and the optical performance of the material is improved.
The ZnS powder after treatment is then mixed with As 2 S 3 Fully mixing powder materials and As 2 S 3 : zns=0.6 wt%, yielding ZnS and As 2 S 3 Is a mixed powder of (a) and (b); as As 2 S 3 Is also a common infrared optical material, has a wide spectral transmission area and a compact network-like glass structure, and is about 300 ℃ As due to the lower melting point 2 S 3 The optical property of the material is similar to that of ZnS material, and when the ZnS material is hot-pressed, a proper amount of As is added 2 S 3 As sintering aid, so that during hot pressing of ZnS, as 2 S 3 The liquid phase physical state is adopted, so that the rearrangement, pore filling and mass transfer processes of ZnS particles can be greatly promoted, the characteristic of high mechanical property of hot-pressed ZnS is maintained at relatively low temperature and pressure, meanwhile, the high densification of the hot-pressed ZnS is realized, the scattering is reduced, and the spectral transmission property of the hot-pressed ZnS is improved.
Then the mixed powder is put into a flat window-shaped mould, the mould is put into a vacuum hot-pressing furnace, the powder is pre-pressed at 50MPa, the hot-pressing furnace is vacuumized to 5Pa and then is started to be heated, the temperature is maintained for 1h after 300 ℃, then the pressure is increased to 80MPa, the heating temperature is 600 ℃, the temperature is maintained for 4h, and the ZnS blank is taken out after the temperature is reduced to room temperature at the speed of 150 ℃/h.
Finally, placing the ZnS blank into a hot isostatic pressing furnace for hot isostatic pressing treatment, vacuumizing the hot isostatic pressing furnace to 40Pa, filling Ar gas, heating up after the pressure reaches 40MPa, heating up to 650 ℃ at the speed of 15 ℃/min, simultaneously lifting up the pressure value of 90MPa in the heating up process, keeping for 10h, and cooling down to room temperature at the speed of 150 ℃/h.
The ZnS planar optical window material with the diameter of 150 mm is prepared, performance detection is carried out on the optical window after polishing, the average transmittance of 0.4-0.8 mu m is 68%, the transmittance of 1.0640 mu m is 70%, the average transmittance of 3-5 mu m is 71% as shown in the figure 1, the average transmittance of 8-10 mu m is 72%, the optical uniformity (@0.6328) is 35ppm, the hardness is 240kg/mm < 2 >, and the bending strength is 110Mpa as shown in the figure 2.
Therefore, on the premise of keeping the good mechanical property of the HP-ZnS, the optical property is good in the wave band of 0.4-12 mu m, and the performance requirement of the multi-band composite window material can be met.
Embodiment case 2:
putting ZnS powder into a vacuum heat treatment furnace, vacuumizing to 5Pa, starting to heat to 450 ℃, maintaining for 2H, and then introducing H 2 S gas and H 2 Mixed gas of gases, H 2 S：H 2 The total gas flow rate is 2L/min, the temperature is kept for 1h, and the temperature is reduced to room temperature at the speed of 200 ℃/h and is taken out for standby.
The ZnS powder after treatment and As 2 S 3 Fully mixing powder materials and As 2 S 3 : zns=0.8 wt%, yielding ZnS and As 2 S 3 Is a powder mixture of the above components.
Loading the mixed powder into a hood-shaped mold, loading the mold into a vacuum hot-pressing furnace, pre-pressing the powder, vacuumizing the hot-pressing furnace to 8Pa, starting heating, maintaining the temperature at 350 ℃ for 2 hours, then raising the pressure to 90MPa, maintaining the heating temperature at 650 ℃ for 5 hours, and cooling to room temperature at a speed of 150 ℃/h to take out ZnS blanks.
Placing the ZnS blank into a hot isostatic pressing furnace for hot isostatic pressing treatment, vacuumizing the hot isostatic pressing furnace to 40Pa, filling Ar gas, heating up after the pressure reaches 40MPa, heating up to 650 ℃ at the speed of 15 ℃/min, simultaneously lifting up the pressure value of 100MPa in the heating up process, keeping for 20h, and cooling down to room temperature at the speed of 150 ℃/h.
ZnS head cover material with caliber of 140mm, center thickness of 5mm and sagittal height of 40mm is prepared.
In one embodiment, the ZnS powder and As 2 S 3 The powder has larger proportion difference, larger difficulty in uniform powder mixing and longer mixing time, so ZnS powder and As 2 S 3 The powder is mixed by the powder mixing device provided by the invention so As to improve the mixing efficiency, and referring to fig. 3 and 4, the powder mixing device comprises a mixing box 1, the cross section of the mixing box is U-shaped, znS powder is directly placed in the mixing box, a discharge hole 2 is arranged in the middle of the bottom of the mixing box and used for discharging after the mixing is finished, a box cover 3 is arranged at the top of the mixing box, the box cover can be opened and closed in an auxiliary way through a cylinder mechanism, the operation is labor-saving, a feeding box 4 is arranged on the surface of the box cover facing the mixing box, the feeding box is connected with an air source through an air pipe, a discharge hole 5 and an air inlet 6 are arranged on the feeding box, a mixing stirring blade 9 is also arranged in the mixing box and connected with a transmission motor 10, and the mixing stirring blade is driven by the transmission motor to discharge ZnS powder and As 2 S 3 And stirring and mixing the powder.
When in use, znS powder is directly placed in a mixing box, as is added 2 S 3 Powder is placed in the charging box, and the mixing stirring blade is driven to rotate by a transmission motor arranged outside the mixing box, and the mixing stirring blade is used for mixing As 2 S 3 The powder is initially stirred and dispersed, and air is supplied to the charging box through an air source after dispersion, so that As in the charging box is enabled 2 S 3 Powder is discharged from the discharge hole, and As can be discharged due to the cooperation of gas 2 S 3 Powder blowing off, blown off As 2 S 3 The powder can be contacted with the ZnS powder which is stirred and dispersed in a large area, so that the mixing effect is improved.
During the gas supply, the As in the charging box can be continuously and once used 2 S 3 The powder is blown into the mixing box or the powder can be carried out in batches, and the feeding box is fed by a pulse blowing modeAs in 2 S 3 The powder is blown, and all As can not be blown at one time 2 S 3 The powder is blown into the mixing box, the blowing force is controlled through time and blowing amount, the batch feeding effect is finally realized, and the mixing efficiency is high.
Specifically, referring to fig. 5 and 6, the charging box includes a top cover 7 and a detachable box body 8, the top cover is fixed on the box cover and the middle part is provided with an air inlet pipe, the air inlet pipe is an air inlet of the charging box, and the number of the discharge holes is multiple and uniformly arranged on the outer peripheral surface of the detachable box body. Can adopt joint or threaded connection's mode between top cap and the detachable box body, can set up the sealing washer between the two, intake pipe one end passes case lid to outside, and the connecting air pipe of being convenient for, the intake pipe other end stretches into in the detachable box body, and after detachable box body installation, the installation height of intake pipe is less than the height of gas outlet, guarantees to dismantle the interior powder of box body and has not remained.
Because the mode control degree of difficulty of pulse is great, consequently it is better to adopt continuous air feed mode effect, in order also to can reach the batch feed effect of multitime, sets up the quantity of reinforced box into a plurality of, is provided with the solenoid valve between air supply and the trachea, feeds through a plurality of reinforced boxes of solenoid valve control batch feed, and is simple reliable with low costs.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting thereof; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A method for preparing a broad spectrum high strength zinc sulfide optical material, comprising the steps of:
a. placing ZnS powder into a vacuum heat treatment furnace, vacuumizing the vacuum heat treatment furnace to be less than or equal to 10Pa, heating to 350-550 ℃, keeping for 1-2h,then let in H 2 S gas and H 2 Mixed gas of gases, H 2 S：H 2 The molar ratio of the components is 3-6:1, the components are kept for 2-3h, cooled to room temperature and taken out for standby;
b. the ZnS powder after treatment and As 2 S 3 Powder mixing, as 2 S 3 : zns=0.5-1.2 wt%, yielding ZnS and As 2 S 3 Is a mixed powder of (a) and (b);
c. loading the mixed powder into a mold, loading the mold into a vacuum hot-pressing furnace, pre-pressing the powder, keeping the pressure at 40-60MPa, vacuumizing the hot-pressing furnace to be less than or equal to 10Pa, heating to 250-350 ℃, keeping the temperature for 1-2h, then increasing the pressure to 70-100MPa, keeping the heating temperature at 500-650 ℃ for 4-6h, cooling to the room temperature, and taking out ZnS blanks;
d. placing the ZnS blank into a hot isostatic pressing furnace for hot isostatic pressing treatment, wherein the working gas is Ar, the pressure is 70-100MPa, the temperature is 500-650 ℃ and is kept for 10-50h, and cooling to room temperature and taking out to obtain the wide-spectrum high-strength ZnS material.
2. The method of preparing a broad spectrum high intensity zinc sulfide optical material according to claim 1, wherein in a, the heating temperature is 420 ℃.
3. The method for preparing a broad spectrum high intensity zinc sulfide optical material according to claim 1, wherein in a, H 2 S：H 2 =4:1 molar ratio.
4. The method for preparing a broad spectrum high intensity zinc sulfide optical material according to claim 1, wherein in b, as 2 S 3 ：ZnS＝0.6wt％。
5. The method for preparing a broad-spectrum high-strength zinc sulfide optical material according to claim 1, wherein in d, the hot isostatic pressing furnace is vacuumized to 40Pa, ar gas is filled, the temperature is raised after the pressure reaches 40MPa, the temperature is raised to 650 ℃ at a speed of 15 ℃/min, the pressure is raised to 90MPa in the temperature raising process, the temperature is kept for 10 hours, and finally the temperature is lowered to room temperature at a speed of 150 ℃/h.
6. The method for producing a broad spectrum high strength zinc sulfide optical material according to claim 1, wherein in b, znS powder and As 2 S 3 The powder is mixed by a powder mixing device.
7. The method for preparing a broad-spectrum high-strength zinc sulfide optical material according to claim 6, wherein the powder mixing device comprises a mixing box, the cross section of the mixing box is U-shaped, a discharging hole is formed in the middle of the bottom of the mixing box, a box cover is arranged at the top of the mixing box, a feeding box is arranged on the surface of the box cover, which faces the inside of the mixing box, the feeding box is connected with an air source through an air pipe, a discharging hole and an air inlet are formed in the feeding box, a mixing stirring blade is further arranged in the mixing box, and the mixing stirring blade is connected with a transmission motor.
8. The method for preparing a broad-spectrum high-strength zinc sulfide optical material according to claim 7, wherein the charging box comprises a top cover and a detachable box body, the top cover is fixed on the box cover, an air inlet pipe is arranged in the middle of the top cover, the air inlet pipe is an air inlet of the charging box, and a plurality of discharging holes are uniformly formed in the outer peripheral surface of the detachable box body.
9. The method for preparing broad spectrum high strength zinc sulfide optical material according to claim 7, wherein the number of the charging boxes is plural, and electromagnetic valves are arranged between the air source and the air pipe.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211561097.4A CN116161959B (en) | 2022-12-07 | 2022-12-07 | Method for preparing wide-spectrum high-strength zinc sulfide optical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211561097.4A CN116161959B (en) | 2022-12-07 | 2022-12-07 | Method for preparing wide-spectrum high-strength zinc sulfide optical material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116161959A true CN116161959A (en) | 2023-05-26 |
| CN116161959B CN116161959B (en) | 2023-12-08 |
Family
ID=86417161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211561097.4A Active CN116161959B (en) | 2022-12-07 | 2022-12-07 | Method for preparing wide-spectrum high-strength zinc sulfide optical material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116161959B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL111278A0 (en) * | 1994-10-13 | 1995-07-31 | Israel State | Process for the preparation of zinc sulfide or selenide posessing multispectral properties |
| US5723207A (en) * | 1988-01-21 | 1998-03-03 | The National Research Development Corporation | Infra-red transparant materials |
| CN101066844A (en) * | 2007-05-24 | 2007-11-07 | 北京有色金属研究总院 | Antireflective protecting DLC/BP film for infrared optical window and its prepn |
| CN101349769A (en) * | 2008-09-11 | 2009-01-21 | 北京有色金属研究总院 | Method for preparing ALON protection film for optical element |
| CN102531040A (en) * | 2010-12-24 | 2012-07-04 | 北京有色金属研究总院 | Process method for preparing multispectral zinc sulfide (ZnS) |
| CN106927673A (en) * | 2017-01-13 | 2017-07-07 | 宁波大学 | A kind of optical fiber preparation method of high-purity chalcogenide glass |
| CN107747128A (en) * | 2017-12-04 | 2018-03-02 | 清远先导材料有限公司 | Preparation method of ZnS polycrystal |
| CN108002426A (en) * | 2018-01-05 | 2018-05-08 | 昆明凯航光电科技有限公司 | A kind of method for improving hot-press vulcanization zinc transmitance |
| CN214644986U (en) * | 2021-04-06 | 2021-11-09 | 四川龙锦泰科技有限公司 | Powder mixer |
-
2022
- 2022-12-07 CN CN202211561097.4A patent/CN116161959B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5723207A (en) * | 1988-01-21 | 1998-03-03 | The National Research Development Corporation | Infra-red transparant materials |
| IL111278A0 (en) * | 1994-10-13 | 1995-07-31 | Israel State | Process for the preparation of zinc sulfide or selenide posessing multispectral properties |
| CN101066844A (en) * | 2007-05-24 | 2007-11-07 | 北京有色金属研究总院 | Antireflective protecting DLC/BP film for infrared optical window and its prepn |
| CN101349769A (en) * | 2008-09-11 | 2009-01-21 | 北京有色金属研究总院 | Method for preparing ALON protection film for optical element |
| CN102531040A (en) * | 2010-12-24 | 2012-07-04 | 北京有色金属研究总院 | Process method for preparing multispectral zinc sulfide (ZnS) |
| CN106927673A (en) * | 2017-01-13 | 2017-07-07 | 宁波大学 | A kind of optical fiber preparation method of high-purity chalcogenide glass |
| CN107747128A (en) * | 2017-12-04 | 2018-03-02 | 清远先导材料有限公司 | Preparation method of ZnS polycrystal |
| CN108002426A (en) * | 2018-01-05 | 2018-05-08 | 昆明凯航光电科技有限公司 | A kind of method for improving hot-press vulcanization zinc transmitance |
| CN214644986U (en) * | 2021-04-06 | 2021-11-09 | 四川龙锦泰科技有限公司 | Powder mixer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116161959B (en) | 2023-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114149260B (en) | Low-thermal-conductivity high-entropy ceramic thermal barrier coating material | |
| CN114031376A (en) | Preparation method of high-hardness fine-grain ZTA system complex phase ceramic material | |
| CN113943162B (en) | alpha-SiAlON high-entropy transparent ceramic material and preparation method thereof | |
| CN111777415B (en) | Boron carbide bulletproof material and preparation method thereof | |
| CN115180962B (en) | High-density high-mobility oxide target material and preparation method thereof | |
| CN114538931A (en) | High-performance AlON transparent ceramic and low-temperature rapid preparation method thereof | |
| CN113896528A (en) | Method for preparing high-performance zirconia ceramic material through DLP-3D printing | |
| CN116161959B (en) | Method for preparing wide-spectrum high-strength zinc sulfide optical material | |
| CN113149652A (en) | High-light-transmittance transparent ceramic prepared based on cold sintering technology and preparation method thereof | |
| CN113773084A (en) | Tungsten carbide target material for decorative coating and preparation method thereof | |
| CN116751032B (en) | ZTO target material and preparation method thereof | |
| CN108465817B (en) | Preparation method of high-density pure tungsten product with uniform structure | |
| CN117447188A (en) | Method for preparing IGZO target by three-step sectional sintering process | |
| CN112624741A (en) | Method for preparing high-purity magnesia ceramic setter plate green body by tape casting | |
| CN115974552B (en) | Preparation method of conductive lithium tantalate target for magnetron sputtering | |
| CN109824358B (en) | Processing method of high-toughness cover plate for 5G mobile phone | |
| CN116396076A (en) | Preparation method of conductive lithium niobate target material | |
| CN109650851B (en) | Preparation method of lighting material | |
| CN113979765B (en) | Silicon carbide porous ceramic and preparation method thereof | |
| CN115745575A (en) | Oxide composite powder and preparation method and application thereof | |
| CN112142469B (en) | Graphite-based oxidation-resistant section bar, preparation method and application | |
| CN114853347A (en) | High-thermal-conductivity low-temperature co-fired glass ceramic substrate and preparation method thereof | |
| CN115502387B (en) | Biomedical titanium alloy spherical powder equipment and use method thereof | |
| CN111057892A (en) | Particulate reinforcement α -Al2O3/ZrB2In-situ synthesis method of reinforced aluminum-based composite material | |
| CN118290150A (en) | Hot-press sintering method of optical zinc sulfide fairing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |